ANNUAL REPORT 2006 - · PDF fileannual report 2006 institute ... of intermediates in pulse irradiated p-terphenyl solution in the ionic liquid ... in dry mushroom powder

ANNUAL REPORT2006

INSTITUTEOF NUCLEAR CHEMISTRY

AND TECHNOLOGY

EDITORS

Prof. Jacek Michalik, Ph.D., D.Sc.Wiktor Smułek, Ph.D.

Ewa Godlewska-Para, M.Sc.

PRINTING

Sylwester Wojtas

© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2007All rights reserved

CONTENTS

GENERAL INFORMATION 9

MANAGEMENT OF THE INSTITUTE 11

MANAGING STAFF OF THE INSTITUTE 11

HEADS OF THE INCT DEPARTMENTS 11

SCIENTIFIC COUNCIL (2003-2007) 11

SCIENTIFIC STAFF 14

PROFESSORS 14

ASSOCIATE PROFESSORS 14

SENIOR SCIENTISTS (Ph.D.) 14

RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 17

REACTIONS OF SUPEROXIDE RADICAL ANION WITH METHIONINE-ENKEPHALINAND ITS TERT-BUTOXYCARBONYL DERIVATIVE. PULSE AND GAMMA RADIOLYSIS STUDIESO. Mozziconacci, J. Mirkowski, K. Bobrowski, Ch. Houée-Levin 19

REACTIONS OF HYDROGEN ATOM WITH METHIONINE-ENKEPHALIN AND RELATEDPEPTIDES. PULSE RADIOLYSIS STUDYO. Mozziconacci, K. Bobrowski, C. Ferreri, Ch. Chatgilialoglu 21

PULSE RADIOLYSIS GENERATION OF THE RADICAL ANION DERIVEDFROM 2,3-DIHYDRO-OXOISOAPORPHINE IN ORGANIC SOLVENTSK. Bobrowski, G. Kciuk, E. Sobarzo-Sanchez, J.R. De la Fuente 22

PULSE RADIOLYSIS STUDY OF THE INTERMEDIATES FORMED IN IONIC LIQUIDS. NATUREOF INTERMEDIATES IN PULSE IRRADIATED p-TERPHENYL SOLUTION IN THE IONIC LIQUIDMETHYLTRIBUTYLAMMONIUM BIS[(TRIFLUOROMETHYL)SULFONYL]IMIDEJ. Grodkowski, R. Kocia, J. Mirkowski 23

STEREOELECTRONIC CONTROL OVER THE MECHANISM OF SINGLET OXYGEN-INDUCEDDECARBOXYLATION IN ALKYLTHIOCARBOXYLIC ACIDSM. Celuch, M. Enache, D. Pogocki 25

OXIDATION OF THIOETHERS BY ORGANIC COMPLEXES OF COPPERM. Celuch, K. Serdiuk, J. Sadło, M. Enache, D. Pogocki 27

ORGANOSILVER RADICALS IN ZEOLITESJ. Turek, J. Sadło, J. Michalik 28

EPR STUDY ON RADIATION-INDUCED RADICAL DISTRIBUTION IN MASSIVE BONE GRAFTSJ. Sadło, J. Michalik, G. Strzelczak, , A. Kamiński 30

RADIATION CHEMISTS VIEW ON PANSPERMIA HYPOTHESISZ.P. Zagórski 31

MODIFIED BENTONITE FILLERS IN POLYMER COMPOSITESZ. Zimek, G. Przybytniak, A. Nowicki, K. Mirkowski 33

POLY(SILOXANEURETHANE) UREAS BASED ON ALIPHATIC AND AROMATIC DIISOCYANATESMODIFIED BY IONIZING RADIATIONE.M. Kornacka, G. Przybytniak, J. Kozakiewicz, J. Przybylski 36

RADIATION EFFECTS IN POLYPROPYLENE/POLYSTYRENE BLENDSW. Głuszewski, Z.P. Zagórski 39

APPLICATION OF GAS CHROMATOGRAPHY TO STUDY POSTIRRADIATION PROCESSESOF POLYMER OXIDATIONW. Głuszewski, Z.P. Zagórski 41

CHEMICAL-RADIATION DEGRADATION OF NATURAL POLYSACCHARIDES (CHITOSAN)A.G. Chmielewski, W. Migdał, U. Gryczka, W. Starosta 42

A. Dziedzic-Gocławska

DSC STUDIES OF GAMMA IRRADIATION EFFECT ON INTERACTION OF POTATO STARCHWITH THE SELECTED FATTY ACIDS AND THEIR SODIUM SALTSK. Cieśla, H. Rahier 44

SURFACE TENSION STUDIES OF BINDING CETYLTRIMETHYLAMMONIUM BROMIDETO GAMMA IRRADIATED AND NON-IRRADIATED POTATO AMYLOPECTINK. Cieśla, H. Lundqvist, A.-C. Eliasson 47

GAMMA IRRADIATION INFLUENCE ON STRUCTURE OF POTATO STARCH GELS STUDIEDBY SEMK. Cieśla, B. Sartowska, E. Królak, W. Głuszewski 49

RADIOLYTIC DEGRADATION OF FUNGICIDE CARBENDAZIM BY GAMMA RADIATIONFOR ENVIRONMENTAL PROTECTIONA. Bojanowska-Czajka, P. Drzewicz, Z. Zimek, B. Szostek, H. Nichipor, M. Trojanowicz 52

COMPARISON OF PPSL AND TL METHODS FOR THE DETECTION OF IRRADIATED FOODAND FOOD COMPONENTSG.P. Guzik, W. Stachowicz 56

DEVELOPMENT AND ACCREDITATION OF EPR METHOD FOR DETECTION OF IRRADIATEDFOOD CONTAINING SUGARK. Lehner, W. Stachowicz 58

DETECTION OF IRRADIATION IN HERBAL PHARMACEUTICALS WITH THE USEOF THERMOLUMINESCENCE AND ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRYM. Laubsztejn, K. Malec-Czechowska, G. Strzelczak, W. Stachowicz 60

ACTIVITY OF THE LABORATORY FOR DETECTION OF IRRADIATED FOOD IN 2006W. Stachowicz, K. Malec-Czechowska, K. Lehner, G.P. Guzik, M. Laubsztejn 63

RADIOCHEMISTRY, STABLE ISOTOPES,NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 65103Ru/103mRh GENERATORB. Bartoś, E. Kowalska, A. Bilewicz, G. Skarnemark 67

ZOLEDRONIC ACID LABELED WITH 47Sc AND 177Lu FOR BONE PAIN THERAPYM. Neves, I. Antunes, A. Majkowska, A. Bilewicz 67

Rh[16aneS4]211At AND Ir[16aneS4]211At COMPLEXES AS PRECURSORS FOR ASTATINERADIOPHARMACEUTICALSM. Pruszyński, A. Bilewicz, M.R. Zalutsky 69

FORMATION KINETICS AND STABILITY OF SOME TRI- AND TETRAAZA DERIVATIVECOMPLEXES OF SCANDIUMA. Majkowska, A. Bilewicz 70

IN VITRO STABILITY OF TRICARBONYLTECHNETIUM(I) COMPLEXESWITH N-METHYL-2-PYRIDINECARBOAMIDE AND N-METHYL-2-PYRIDINECARBOTHIOAMIDE– HISTIDINE CHALLENGEM. Łyczko, J. Narbutt 71

ION EXCHANGE STUDIES ON THE ORGANOMETALLIC AQUA-ION fac-[99mTc(CO)3(H2O3]+

IN ACIDIC AQUEOUS SOLUTIONSZ. Samczyński, M. Łyczko, R. Dybczyński, J. Narbutt 73

SYNERGISTIC EFFECT OF NEUTRAL BIDENTATE N-HETEROCYCLIC LIGANDSON THE SEPARATION OF Am(III) FROM Eu(III) BY SOLVENT EXTRACTIONWITH TETRADENTATE 6,6’-BIS-(DIETHYL-1,2,4-TRIAZIN-3-YL)-2,2’-BIPYRIDINEJ. Narbutt, J. Krejzler 75

ESTIMATION OF CYTOSTATIC AND ANTIMICROBIAL ACTIVITY OF PLATINUM(II) COMPLEXESWITH THIOUREA DERIVATIVESE. Anuszewska, B. Gruber, H. Kruszewska, L. Fuks, N. Sadlej-Sosnowska 77

TRANSITION METAL SORPTION BY ALGINATE BIOSORBENTD. Filipiuk, L. Fuks, M. Majdan 79

GALLIUM AND INDIUM ISOTOPE EFFECTS IN THE DOWEX 1-X8/HCl SYSTEMI. Herdzik, , W. Skwara, E. Bulska, A. Wysocka 81

PROFICIENCY TESTING SCHEME PLANTS 6 – DETERMINATION OF As, Cd, Cu, Hg, Pb, Se and ZnIN DRY MUSHROOM POWDER (Suillus bovinus)H. Polkowska-Motrenko, E. Chajduk, J. Dudek, M. Sadowska-Bratek, M. Sypuła 82

W. Dembiński

NEW POLISH CERTIFIED REFERENCE MATERIALS FOR INORGANIC TRACER ANALYSIS:CORN FLOUR (INCT-CF-3) AND SOYA BEAN FLOUR (INCT-SBF-4)H. Polkowska-Motrenko, R. Dybczyński, E. Chajduk, B. Danko, K. Kulisa, Z. Samczyński, M. Sypuła, Z. Szopa 85

DETERMINATION OF CADMIUM, LEAD AND COPPER IN FOOD PRODUCTSAND ENVIRONMENTAL SAMPLES BY ATOMIC ABSORPTION SPECTROMETRYAFTER SEPARATION BY SOLID PHASE EXTRACTIONJ. Chwastowska, W. Skwara, E. Sterlińska, J. Dudek, L. Pszonicki 89

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATELIGANDS. PART LIX. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEXWITH PYRIDAZINE-3,6-DICARBOXYLATE AND WATER LIGANDSM. Gryz, W. Starosta, J. Leciejewicz 91

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATELIGANDS. PART LX. THE CRYSTAL AND MOLECULAR STRUCTURES OF MAGNESIUM(II)AND ZINC(II) COMPLEXES WITH IMIDAZOLE-4-CARBOXYLATE AND WATER LIGANDSM. Gryz, W. Starosta, J. Leciejewicz 92

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATELIGANDS. PART LXI. THE CRYSTAL AND MOLECULAR STRUCTURE OF A MANGANESE(II)COMPLEX WITH PYRAZOLE-3,5-DICARBOXYLATE AND WATER LIGANDST. Premkumar, S. Govindarajan, W. Starosta, J. Leciejewicz 93

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATELIGANDS. PART LXII. THE CRYSTAL STRUCTURE AND MOLECULAR DYNAMICSOF 2-AMINOPYRIDINE-3-CARBOXYLIC ACIDA. Pawlukojć, W. Starosta, J. Leciejewicz, I. Natkaniec, D. Nowak 94

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATELIGANDS. PART LXIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF A CALCIUM(II)COMPLEX WITH PYRAZINE-2,3,5,6-TETRACARBOXYLATE AND WATER LIGANDSW. Starosta, J. Leciejewicz 94

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATELIGANDS. PART LXIV. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEXWITH PYRAZOLE-4-CARBOXYLATE AND WATER LIGANDSM. Gryz, W. Starosta, J. Leciejewicz 96

RADIOBIOLOGY 97

IRON CHELATORS INHIBIT DNIC FORMATION TO THE SAME EXTENT, INDEPENDENTLYOF PERMEABILITYK. Brzóska, H. Lewandowska, S. Męczyńska, B. Sochanowicz, J. Sadło, M. Kruszewski 99

GHRELIN, A LIGAND FOR THE GROWTH HORMONE SECRETAGOGUE RECEPTOR, INCREASESDNA BREAKAGE IN X-IRRADIATED PIGLET BLOOD MONONUCLEAR CELLSM. Kruszewski, T. Iwaneńko, J. Woliński, M. Wojewódzka 100

GHRELIN INCREASES HYDROGEN PEROXIDE-INDUCED DNA BREAKAGE IN PIGLET BLOODMONONUCLEAR CELLST. Bartłomiejczyk, T. Iwaneńko, M. Wojewódzka, J. Woliński, R. Zabielski, M. Kruszewski 101

THE EFFECT OF LEPTIN ON DNA BREAKAGE INDUCED BY GENOTOXIC AGENTS IN HUMANPERIPHERAL BLOOD MONONUCLEAR CELLSM. Kruszewski, T. Iwaneńko, M. Wojewódzka, J. Woliński, R. Zabielski 102

CABAS – A FREELY AVAILABLE PC PROGRAM FOR FITTING CALIBRATION CURVESIN CHROMOSOME ABERRATION DOSIMETRYJ. Deperas, M. Szłuińska, M. Deperas-Kaminska, A. Edwards, D. Lloyd, C. Lindholm, H. Romm, L. Roy, R. Moss,J. Morand, A. Wójcik 103

THE TEMPERATURE EFFECT ON THE FREQUENCY OF RADIATION-INDUCED MICRONUCLEIIN HUMAN PERIPHERAL BLOOD LYMPHOCYTES IS ABOLISHED BY DMSOK. Brzozowska, A. Wójcik 104

VARIABLE RADIOSENSITIVITY OF CHROMOSOMES 2, 8 AND 14 IN HUMAN PERIPHERALBLOOD LYMPHOCYTES EXPOSED TO 480 MeV/n 12C-IONSM. Deperas-Kaminska, G.N. Timoshenko, E.A. Krasavin, A. Wójcik 105

EFFICIENT DOUBLE STRAND BREAK REJONING AND SURVIVAL IN X-IRRADIATED HUMANGLIOMA M059 CELLS ARE DEPENDENT ON EGF RECEPTOR KINASE ACTIVITYI. Grądzka, B. Sochanowicz, I. Szumiel 106

DECREASED PERSISTANCE OF γH2AX FOCI IN X-IRRADIATED xrs6 CELLS TREATEDWITH SIRTUIN INHIBITORM. Wojewódzka, M. Kruszewski, I. Szumiel 107

TWO p53 BINDING PROTEINS ARE PRESENT IN LY-R (REPAIR COMPETENT) AND LY-S (REPAIRDEFICIENT) CELLS IN DIFFERENT PROPORTIONSB. Sochanowicz, I. Szumiel 108

PREMATURE CHROMOSOME CONDENSATION IN BIOLOGICAL DOSIMETRY AFTER HIGH DOSEGAMMA IRRADIATIONS. Sommer, I. Buraczewska, A. Wójcik 109

NUCLEAR TECHNOLOGIES AND METHODS 111

PROCESS ENGINEERING 113METHOD FOR COLLECTION OF NITRATE FROM WATER SAMPLES AND DETERMINATIONOF NITROGEN AND OXYGEN ISOTOPE COMPOSITIONM. Derda, S.M. Cuna, R. Wierzchnicki 113

THE KINETICS OF TRANS-DICHLOROETHYLENE DECOMPOSITION IN AIRUNDER ELECTRON-BEAM IRRADIATIONY. Sun, A.G. Chmielewski, S. Bułka, Z. Zimek, H. Nichipor 114

ELECTRON BEAM OF VOCs TREATMENT EMITTED FROM OIL COMBUSTION PROCESSA. Ostapczuk, J. Licki, A.G. Chmielewski 115

ELECTRON BEAM TREATMENT OF FLUE GAS FROM FUEL OIL COMBUSTIONA.G. Chmielewski, A. Pawelec, B. Tymiński, Z. Zimek, J. Licki, A.A. Basfar 117

DOSIMETRY FOR COMBUSTION FLUE GAS TREATMENT WITH ELECTRON BEAMK. Mehta, S. Bułka 118

CATALYTIC CRACKING OF POLYOLEFINE WASTES IN A LARGE LABORATORY INSTALLATIONB. Tymiński, K. Zwoliński, R. Jurczyk 119

ECONOMICAL COMPARISON OF ABSORPTION AND MEMBRANE METHODS APPLIEDFOR THE ENRICHMENT OF METHANE IN BIOGASM. Harasimowicz, G. Zakrzewska-Trznadel, W. Ziółkowska, A.G. Chmielewski 120

STUDY OF BOUNDARY-LAYER PHENOMENA IN MEMBRANE PROCESSESG. Zakrzewska-Trznadel, A. Miśkiewicz, M. Harasimowicz, E. Dłuska, S. Wroński, A. Jaworska, C. Cojocaru 121

A STUDY OF STABLE ISOTOPE COMPOSITION IN MILKR. Wierzchnicki, M. Derda 123

INTERLABORATORY TESTS OF 3H MEASUREMENTS IN WATER SAMPLESW. Sołtyk, J. Walendziak, J. Palige 124

MODELLING FOR GROUNDWATER FLOW IN THE OPENCAST BEŁCHATÓW AREAR. Zimnicki 124

TRACER AND CFD INVESTIGATIONS OF SEDIMENTATION PROCESSES IN RECTANGULARSETTLERJ. Palige, A. Dobrowolski, S. Ptaszek, A.G. Chmielewski 125

NATIVE AND TRANSPLANTED Pleurozium schreberi (Brid.) Mitt. AS BIOINDICATOROF NITROGEN DEPOSITION IN A HEAVY INDUSTRY AREA OF UPPER SILESIAG. Kosior, A. Samecka-Cymerman, A.G. Chmielewski, R. Wierzchnicki, M. Derda, A.J. Kempers 126

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 128IDENTIFICATION OF LEAD WHITE OF THE 15th CENTURY GDAŃSK PANEL PAINTINGSBY MEANS OF INSTRUMENTAL NEUTRON ACTIVATION ANALYSISE. Pańczyk, J. Olszewska-Świetlik, L. Waliś 128

ELEMENTAL COMPOSITION AND PARTICLES MORPHOLOGY OF LEAD WHITE PIGMENTSB. Sartowska, E. Pańczyk, L. Waliś 130

ULTRAVIOLET BLUE FLUORESCENCE OF CENTRAL EUROPEAN BAROQUE GLASS(FURTHER RESULTS)J. Kunicki-Goldfinger, J. Kierzek, P. Dzierżanowski 134

LATE 17th CENTURY GLASS VESSELS FROM EILAND – TECHNOLOGICAL APPROACHJ. Kunicki-Goldfinger, M. Mádl, P. Dzierżanowski 136

WATER SOLUBLE SILICA BIOCIDES CONTAINING QUATERNARY AMMONIUM SALTSA. Łukasiewicz, D.K. Chmielewska, L. Waliś 141

THE ROLE OF CARBON, CHROMIUM AND NITROGEN IN AUSTENITIZATION OF UNALLOYEDAND ALLOYED STEELS BY INTENSE PLASMA PULSESJ. Piekoszewski, L. Dąbrowski, B. Sartowska, L. Waliś, M. Kopcewicz, J. Kalinowska, M. Barlak, J. Stanisławski,Z. Werner, A. Barcz 141

THERMAL STABILITY OF THE PHASES FORMED IN THE NEAR SURFACE LAYERS OF CARBONSTEEL BY NITROGEN PULSED PLASMA TREATMENTB. Sartowska, J. Piekoszewski, L. Waliś, J. Stanisławski, L. Nowicki, R. Ratajczak, M. Kopcewicz 142

ELECTRON-BEAM IRRADIATION OF PVDF MEMBRANES AS A METHOD FOR OBTAININGBRITTLE FRACTURES FOR SEM OBSERVATIONSB. Sartowska, O. Orelovitch, A. Nowicki 144

SELECTED PROPERTIES OF POLYPYRROLE NANOSTRUCTURES DEPOSITEDIN TRACK-ETCHED MEMBRANE TEMPLATESM. Buczkowski, W. Starosta, B. Sartowska, D. Wawszczak 145

SOL-GEL-DERIVED HYDROXYAPATITE AND ITS APPLICATION TO SORPTION OF HEAVYMETALSA. Deptuła, J. Chwastowska, W. Łada, T. Olczak, D. Wawszczak, E. Sterlińska, B. Sartowska, M. Brykała,K.C. Goretta 147

PHYSICAL AND CHEMICAL PROPERTIES OF YTTERBIUM DOPED KY(WO4)2 NANOCRYSTALSA. Deptuła, M.T. Borowiec, V.P. Dyakonov, W. Łada, T. Olczak, D. Wawszczak, P. Aleshkevych, W. Domuchowski,T. Zayarnyuk, M. Barański, H. Szymczak, M. Brykała 151

SAXS STUDY OF XERO- AND AERO-GELS FORMED FROM MONOSACCHARIDE GELATORSH. Grigoriew, D.K. Chmielewska 153

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS 156MEASUREMENT OF 222Rn AND 220Rn WITH SINGLE SCINTILLATION CELLB. Machaj, P. Urbański, J. Bartak 156

DOSIMETRIC GATE DSP-15E. Świstowski, J. Mirowicz, P. Urbański, J. Pieńkos 158

GAMMA THIN LAYER CHROMATOGRAPHY ANALYZER SC-05E. Świstowski, B. Machaj, E. Kowalska, J. Pieńkos, E. Gniazdowska 159

INVESTIGATION OF DUST POLLUTION IN ASSEMBLING HALL OF TV SETSJ. Pieńkos, P. Urbański 160

COMMERCIAL APPLICATION OF ELECTRON BEAM ACCELERATORS AT R&D AND SERVICECENTERA.G. Chmielewski, W. Migdał, Z. Zimek, I. Kałuska, S. Bułka 161

ELECTRON GUN FOR 10 MeV, 10 kW ELECTRON ACCELERATORZ. Dźwigalski, Z. Zimek 163

THE INCT PUBLICATIONS IN 2006 165

ARTICLES 165

BOOKS 173

CHAPTERS IN BOOKS 173

THE INCT REPORTS 174

CONFERENCE PROCEEDINGS 175

CONFERENCE ABSTRACTS 176

SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 2005 185

NUKLEONIKA 186

INTERVIEWS IN 2006 191

THE INCT PATENTS AND PATENT APPLICATIONS IN 2006 192

PATENTS 192

PATENT APPLICATIONS 192

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006 193

Ph.D./D.Sc. THESES IN 2006 198

Ph.D. THESES 198

D.Sc. THESES 198

EDUCATION 199

Ph.D. PROGRAMME IN CHEMISTRY 199

TRAINING OF STUDENTS 199

RESEARCH PROJECTS AND CONTRACTS 201

RESEARCH PROJECTS GRANTED BY THE MINISTRY OF SCIENCEAND HIGHER EDUCATION IN 2006 AND IN CONTINUATION 201

RESEARCH PROJECTS ORDERED BY THE MINISTRY OF SCIENCEAND HIGHER EDUCATION IN 2006 202

IAEA RESEARCH CONTRACTS IN 2006 202

IAEA TECHNICAL CONTRACTS IN 2006 202

EUROPEAN COMMISSION RESEARCH PROJECTS IN 2006 202

OTHER FOREIGN CONTRACTS IN 2006 203

LIST OF VISITORS TO THE INCT IN 2006 204

THE INCT SEMINARS IN 2006 206

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006 207

LECTURES 207

SEMINARS 209

AWARDS IN 2006 211

INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 212

INDEX OF THE AUTHORS 224

9GENERAL INFORMATION

GENERAL INFORMATION

The Institute of Nuclear Chemistry and Technology (INCT) is one of the successors ofthe Institute of Nuclear Research (INR) which was established in 1955. The latterInstitute, once the biggest Institute in Poland, has exerted a great influence on thescientific and intelectual life in this country. The INCT came into being as one of theindependent units established after the dissolution of the INR in 1983.

At present, the Institute research activity is focused on:• radiation chemistry and technology,• radiochemistry and coordination chemistry,• radiobiology,• application of nuclear methods in material and process engineering,• design of instruments based on nuclear techniques,• trace analysis and radioanalytical techniques,• environmental research.

In the above fields we offer research programmes for Ph.D. students.At this moment, with its nine electron accelerators in operation and with the staff

experienced in the field of electron beam (EB) applications, the Institute is one of themost advanced centres of radiation research and EB processing. The accelerators areinstalled in the following Institute units:• pilot plant for radiation sterilization of medical devices and transplants,• pilot plant for radiation modification of polymers,• experimental pilot plant for food irradiation,• pilot plant for removal of SO2 and NOx from flue gases,• pulse radiolysis laboratory, in which the nanosecond set-up was put into operation

in 2001. A new 10 MeV accelerator was constructed in the INCT for this purpose.Based on the technology elaborated in our Institute, an industrial installation for

electron beam flue gas treatment has been implemented at the EPS “Pomorzany” (DolnaOdra PS Group). This is the second full scale industrial EB installation for SO2 andNOx removal all over the world.

***

In 2006, the INCT scientists published 81 papers in scientific journals registered inthe Philadelphia list, among them 49 papers in journals with an impact factor (IF)higher than 1.0. The INCT research workers are also the authors of one book and 7chapters in scientific books published in 2006.

In 2006, the Ministry of Science and Higher Education (MSHE) granted 5 researchprojects. Altogether the INCT is carrying out 23 MSHE research projects including 3ordered projects and 1 implementation project, and 6 research projects supported finan-cially by the European Commission.

Annual rewards of the INCT Director-General for the best publications in 2006were granted to the following research teams:• First degree group award to Leon Pszonicki, Jadwiga Chwastowska, Witold Skwara

and Elżbieta Sterlińska for two publications in “Talanta” presenting methods forthe determination of platinum, palladium and chromium in trace quantities in envi-ronmental samples and speciation analysis of Cr(VI) in the presence of Cr(III).

10 GENERAL INFORMATION

• Second degree group award to Marcin Kruszewski, Hanna Lewandowska, TeresaBartłomiejczyk, Teresa Iwaneńko and Barbara Sochanowicz for publicationsin the journals “Biochemical and Biophysical Research Communications”, “Journalof Biological Chemistry” and “Acta Biochimica Polonica” devoted to studies of re-lations between the metabolism of iron on a cell level and DNA oxidative damage.

• Third degree group award to Sławomir Siekierski and Kinga Frąckiewicz for theessential contribution to the work on basic studies of secondary periodicity of ele-ments of the block p (group 13) published in “European Journal of Inorganic Chem-istry”.

In 2006, the INCT scientific community was especially active in organizing scien-tific conferences. In total, in 2006, five international meetings have been organized:• Regional Training Course “Application of Monte Carlo modeling methods for

dosimetry calculation in radiation processing” in the frame of the IAEA TechnicalCooperation Project RER/8/010 “Quality control methods and procedures for radia-tion technology” (3-7 April 2006, Warszawa);

• The Workshop “Dosimetry for radiation application in technologies for environ-mental pollution control” in the frame of the Marie Curie Host Fellowships for theEU Transfer of Knowledge “Advanced methods for environment research and con-trol (AMERAC)” (5 April 2006, Warszawa);

• The Workshop “Methods of enviromental research” in the frame of the Marie CurieHost Fellowships for the EU Transfer of Knowledge “Advanced methods for envi-ronment research and control (AMERAC)” (10 August 2006, Warszawa);

• Symposium on Chemistry and Radiation Techniques: Challenge and Possibilities –Jubilee of the 80th Anniversary of Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. (17October 2006, Warszawa);

• IV Conference on Problems of Waste Disposal (27 November 2006, Warszawa).The international journal for nuclear research – NUKLEONIKA, published by

the INCT, was mentioned in the SCI Journal Citation List.

11MANAGEMENT OF THE INSTITUTE

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

DirectorAssoc. Prof. Lech Waliś, Ph.D.

Deputy Director for Research and DevelopmentProf. Jacek Michalik, Ph.D., D.Sc.

Deputy Director for Maintenance and MarketingRoman Janusz, M.Sc.

Accountant GeneralMałgorzata Otmianowska-Filus, M.Sc.

• Department of Nuclear Methods of MaterialsEngineeringWojciech Starosta, Ph.D.

• Department of Radioisotope Instrumentsand MethodsProf. Piotr Urbański, Ph.D., D.Sc.

• Department of RadiochemistryProf. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.

• Department of Nuclear Methods of ProcessEngineeringProf. Andrzej G. Chmielewski, Ph.D., D.Sc.

• Department of Radiation Chemistryand TechnologyZbigniew Zimek, Ph.D.

• Department of Analytical ChemistryProf. Rajmund Dybczyński, Ph.D., D.Sc.

• Department of Radiobiology and HealthProtectionProf. Irena Szumiel, Ph.D., D.Sc.

• Experimental Plant for Food IrradiationAssoc. Prof. Wojciech Migdał, Ph.D., D.Sc.

• Laboratory for Detection of Irradiated FoodWacław Stachowicz, Ph.D.

• Laboratory for Measurements of TechnologicalDosesZofia Stuglik, Ph.D.

HEADS OF THE INCT DEPARTMENTS

1. Prof. Grzegorz Bartosz, Ph.D., D.Sc.University of Łódź• biochemistry

2. Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• radiochemistry, inorganic chemistry

3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc.(Chairman)

Institute of Nuclear Chemistry and Technology• radiation chemistry, photochemistry, biophysics

4. Sylwester Bułka, M.Sc.Institute of Nuclear Chemistry and Technology• electronics

5. Prof. Witold Charewicz, Ph.D., D.Sc.Wrocław University of Technology• inorganic chemistry, hydrometallurgy

SCIENTIFIC COUNCIL (2003-2007)

12 MANAGEMENT OF THE INSTITUTE

6. Prof. Stanisław Chibowski, Ph.D., D.Sc.Maria Curie-Skłodowska University• radiochemistry, physical chemistry

7. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• chemical and process engineering, nuclear che-mical engineering, isotope chemistry

8. Prof. Jadwiga Chwastowska, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• analytical chemistry

9. Prof. Rajmund Dybczyński, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• analytical chemistry

10. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc.(Vice-chairman)Warsaw University of Technology• chemical technology

11. Prof. Leon Gradoń, Ph.D., D.Sc.Warsaw University of Technology• chemical and process engineering

12. Assoc. Prof. Edward Iller, Ph.D., D.Sc.Radioisotope Centre POLATOM• chemical and process engineering, physicalchemistry

13. Assoc. Prof. Marek Janiak, Ph.D., D.Sc.Military Institute of Hygiene and Epidemiology• radiobiology

14. Iwona Kałuska, M.Sc.Institute of Nuclear Chemistry and Technology• radiation chemistry

15. Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• radiobiology

16. Prof. Marek Lankosz, Ph.D., D.Sc.AGH University of Science and Technology• physics, radioanalytical methods

17. Prof. Janusz Lipkowski, Ph.D., D.Sc.Institute of Physical Chemistry, Polish Academyof Sciences• physicochemical methods of analysis

18. Zygmunt Łuczyński, Ph.D.Institute of Electronic Materials Technology• chemistry

19. Prof. Andrzej Łukasiewicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• material science

20. Prof. Bronisław Marciniak, Ph.D., D.Sc.Adam Mickiewicz University• physical chemistry

21. Prof. Józef Mayer, Ph.D., D.Sc.Technical University of Łódź• physical and radiation chemistry

22. Prof. Jacek Michalik, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• radiation chemistry, surface chemistry, radicalchemistry

23. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• radiochemistry, coordination chemistry

24. Jan Paweł Pieńkos, Eng.Institute of Nuclear Chemistry and Technology• electronics

25. Prof. Leon Pszonicki, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• analytical chemistry

26. Prof. Sławomir Siekierski, Ph.D.Institute of Nuclear Chemistry and Technology• physical chemistry, inorganic chemistry

27. Prof. Sławomir Sterliński, Ph.D., D.Sc.Central Laboratory for Radiological Protection• physics, nuclear technical physics

28. Prof. Irena Szumiel, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• cellular radiobiology

29. Prof. Jerzy Szydłowski, Ph.D., D.Sc.Warsaw University• physical chemistry, radiochemistry

30. Prof. Jan Tacikowski, Ph.D.Institute of Precision Mechanics• physical metallurgy and heat treatment of me-tals

31. Prof. Marek Trojanowicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology• analytical chemistry

32. Prof. Piotr Urbański, Ph.D., D.Sc.(Vice-chairman)Institute of Nuclear Chemistry and Technology• radiometric methods, industrial measurementequipment, metrology

33. Assoc. Prof. Lech Waliś, Ph.D.Institute of Nuclear Chemistry and Technology• material science, material engineering

34. Prof. Andrzej Wójcik, Ph.D., D.Sc.(Vice-chairman)Institute of Nuclear Chemistry and Technology• cytogentics

35. Prof. Zbigniew Zagórski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

MANAGEMENT OF THE INSTITUTE 13

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2003-2007)

1. Prof. Antoni Dancewicz, Ph.D., D.Sc.• biochemistry, radiobiology

• physical chemistry, radiation chemistry, elec-trochemistry

36. Zbigniew Zimek, Ph.D.Institute of Nuclear Chemistry and Technology

• electronics, accelerator techniques, radiationprocessing

SCIENTIFIC STAFF

PROFESSORS

SCIENTIFIC STAFF14

1. Bobrowski Krzysztofradiation chemistry, photochemistry, biophysics

2. Chmielewski Andrzej G.chemical and process engineering, nuclear chem-ical engineering, isotope chemistry

3. Chwastowska Jadwigaanalytical chemistry

4. Dybczyński Rajmundanalytical chemistry

5. Leciejewicz Januszcrystallography, solid state physics, material science

6. Łukasiewicz Andrzejmaterial science

7. Michalik Jacekradiation chemistry, surface chemistry, radical che-mistry

8. Ostyk-Narbutt Jerzyradiochemistry, coordination chemistry

9. Piekoszewski Jerzysolid state physics

10. Pszonicki Leonanalytical chemistry

11. Siekierski Sławomirphysical chemistry, inorganic chemistry

12. Szumiel Irenacellular radiobiology

13. Trojanowicz Marekanalytical chemistry

14. Urbański Piotrradiometric methods, industrial measurementequipment, metrology

15. Wójcik Andrzejcytogenetics

16. Zagórski Zbigniewphysical chemistry, radiation chemistry, electro-chemistry

ASSOCIATE PROFESSORS

1. Bartłomiejczyk Teresabiology

2. Borkowski Marianchemistry

3. Buczkowski Marekphysics

4. Cieśla Krystynaphysical chemistry

1. Bilewicz Aleksanderradiochemistry, inorganic chemistry

2. Grigoriew Helenasolid state physics, diffraction research of non--crystalline matter

3. Grodkowski Janradiation chemistry

4. Kruszewski Marcinradiobiology

5. Migdał Wojciechchemistry, science of commodies

6. Pogocki Dariuszradiation chemistry, pulse radiolysis

7. Przybytniak Grażynaradiation chemistry

8. Waliś Lechmaterial science, material engineering

9. Zakrzewska-Trznadel Grażynaprocess and chemical engineering

10. Żółtowski Tadeusznuclear physics

SENIOR SCIENTISTS (Ph.D.)

SCIENTIFIC STAFF 15

5. Danilczuk Marekchemistry

6. Danko Bożenaanalytical chemistry

7. Dembiński Wojciechchemistry

8. Deptuła Andrzejchemistry

9. Derda Małgorzatachemistry

10. Dobrowolski Andrzejchemistry

11. Dudek Jakubchemistry

12. Dźwigalski Zygmunthigh voltage electronics, electron injectors, gaslasers

13. Frąckiewicz Kingachemistry

14. Fuks Leonchemistry

15. Gniazdowska Ewachemistry

16. Grądzka Iwonabiology

17. Harasimowicz Mariantechnical nuclear physics, theory of elementaryparticles

18. Kierzek Joachimphysics

19. Kornacka Ewachemistry

20. Krejzler Jadwigachemistry

21. Kunicki-Goldfinger Jerzyconservator/restorer of art

22. Lewandowska-Siwkiewicz Hannachemistry

23. Machaj Bronisławradiometry

24. Mikołajczuk Agnieszkachemistry

25. Mirkowski Jaceknuclear and medical electronics

26. Nowicki Andrzejorganic chemistry and technology, high-tempera-ture technology

27. Owczarczyk Andrzejchemistry

28. Palige Jacekmetallurgy

29. Panta Przemysławnuclear chemistry

30. Pawelec Andrzejchemical engineering

31. Pawlukojć Andrzejphysics

32. Polkowska-Motrenko Halinaanalytical chemistry

33. Rafalski Andrzejradiation chemistry

34. Sadło Jarosławchemistry

35. Samczyński Zbigniewanalytical chemistry

36. Skwara Witoldanalytical chemistry

37. Sochanowicz Barbarabiology

38. Sommer Sylwesterradiobiology, cytogenetics

39. Stachowicz Wacławradiation chemistry, EPR spectroscopy

40. Starosta Wojciechchemistry

41. Strzelczak Grażynaradiation chemistry

42. Stuglik Zofiaradiation chemistry

43. Sun Yongxiachemistry

44. Szpilowski Stanisławchemistry

45. Szreder Tomaszchemistry

46. Tymiński Bogdanchemistry

47. Warchoł Stanisławsolid state physics

48. Wąsowicz Tomaszradiation chemistry, surface chemistry, radical che-mistry

16 SCIENTIFIC STAFF

49. Wierzchnicki Ryszardchemical engineering

50. Wiśniowski Pawełradiation chemistry, photochemistry, biophysics

51. Wojewódzka Mariaradiobiology

52. Zielińska Barbarachemistry

53. Zimek Zbigniewelectronics, accelerator techniques, radiation pro-cessing

RADIATION CHEMISTRY

AND PHYSICS,

RADIATION TECHNOLOGIES


REACTIONS OF SUPEROXIDE RADICAL ANIONWITH METHIONINE-ENKEPHALIN

AND ITS TERT-BUTOXYCARBONYL DERIVATIVE.PULSE AND GAMMA RADIOLYSIS STUDIES

Olivier Mozziconacci, Jacek Mirkowski, Krzysztof Bobrowski, Chantal Houée-Levin1/

1/ Université Paris-Sud, Orsay, France

The pentapeptide methionine-enkephalin (Met-enk)(Chart 1) is a natural opiate that inhibits signals ofpain. Many studies have demonstrated the connec-tion between the interactions of the opiate and re-active oxygen species (ROS) with cell injuries [1].The aromatic amino acid residues are especiallygood targets for oxidation by ROS during oxida-tive stress. In particular tyrosine can be convertedinto a dimer or into dihydroxyphenylalanine (DOPA)in enkephalins [2,3]. This interesting free-radicalchemistry occurs widely in biological systems butit is still a largely unexplored area of research. Theaddition of superoxide radical anion (O2·–) to a tyro-syl radical (TyrO·) leads to a hydroperoxide, whichgets cyclized by the Michael addition of the amineonto the ring [4]. The stability of the hydroperox-ide depends on the neighboring function [5]. How-ever, the occurrence of this mechanism on peptidesor proteins has never been directly demonstrated.In this report we report evidence for this mecha-nism on a natural peptide, Met-enk. Moreover, weshow that, when the amine function is blocked bythe tert-butoxycarbonyl group – t-Boc-Met-enk(Chart 1), tyrosine is restored by O2·–.

The transient absorption spectrum of Met-enkrecorded 55 μs after the pulse in N2O-saturatedsolution containing azide ions, revealed two ab-sorption bands with maxima in the visible regionat 390 and 405 nm (Fig.1, curve a). This absorp-tion is assigned to TyrO· radicals which were form-ed upon oxidation of the tyrosine residue (TyrOH)in Met-enk by N3· radicals:

TyrOH + N3· → TyrO· + H+ + N3–

Similar transient absorption spectrum with thetwo absorption bands at 390 and 405 nm and againassigned to TyrO· radicals was observed in the sameconditions in solution containing t-Boc-Met-enk(Fig.1, curve b).

Like in N2O-saturated solutions, the transientabsorption spectra recorded 55 μs after the pulseobserved in O2-saturated solutions containingMet-enk and t-Boc-Met-enk were assigned to TyrO·radicals.

However, in O2-saturated solutions containingMet-enk and t-Boc-Met-enk a new absorptionband at 360-380 nm appeared at the millisecondtime scale (Fig.2). This band was attributed to theproduct of the reaction of O2·– with TyrO·. How-ever, the kinetic traces leading to this spectrumwere different (Fig.2, insets). In solution contain-ing t-Boc-Met-enk, the decay at 405 nm reached apseudo-plateau around 1 ms after the pulse.

Two peaks were observed in HPLC chromato-grams after gamma-irradiation in N2O-saturatedsolutions containing Met-enk. The first peak cor-responds to the native Met-enk. The second peakincreased with the dose (Fig.3A). It was the mostintense peak when fluorescence detection (exc. 284nm, em. 425 nm) was applied. Additionally, a thirdpeak appeared which also increased with the doseand was fluorescent with the same characteristics(Fig.3B). Both peaks were attributed to dimers ofMet-enk linked by bityrosine, the most intense as the3,3’-bityrosine. UV-VIS spectrum of the irradiatedMet-enk solution was characteristic of bityrosine.Chart 1.

Fig.1. Absorption spectra obtained after oxidation ofMet-enk ( ) and t-Boc-Met-enk ( ) by N3· radicalsin N2O-saturated aqueous solutions containing 0.1mM of peptides and 50 mM of N3

– taken 55 μs afterthe pulse.

RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES20

In O2-saturated solution containing Met-enk,the peak that corresponds to 3,3’-bityrosine wasvisible only by its very weak fluorescence. This in-dicates a small yield of 3,3’-bityrosine formationin Met-enk dimer. On the other hand, anothernew peak with elution time shorter than the nativeMet-enk was observed. Compared to N2O-saturatedsolution, the shape of the UV-VIS spectrum wasdifferent. The bands at 290 and 315 nm were muchweaker, with two intense absorption bands locatedat 275 and 285 nm. This indicates a lower amountof Met-enk dimers with bityrosine and formationof a new stable product.

In N2O-saturated solution containing t-Boc--Met-enk, the stable product pattern was similarto that observed in N2O-saturated solution contain-ing Met-enk (vide supra).

On the other hand, HPLC chromatograms afterirradiation of O2-saturated solution containingt-Boc-Met-enk showed only one peak (Fig.4B)which had the same retention time as the nativepeptide (Fig.4A) and its density remained very closeto that in non-irradiated solution. This indicatesthat irradiation of Boc-Met-enk in aerobic condi-tions does not lead to oxidation products since theamount of non-modified peptide was unchanged.

All observations described above showed thatblocking the amine function by the tert-butoxy-carbonyl group does not affect the reaction path-way of TyrO· radicals in anaerobic conditions.

In spite of the fact that the first step of oxida-tion of Met-enk and t-Boc-Met-enk by N3· in aero-bic conditions is the same, there are different mecha-nisms for the secondary reactions occurring inMet-enk and t-Boc-Met-enk in the presence ofoxygen compared to its absence.

These differences can be rationalized in the fol-lowing way. In both peptides the addition of O2·– tothe aromatic ring of TyrO· occurs resulting in theirrespective peroxide anion enones which furtherprotonate forming the hydroperoxide enones. InMet-enk the hydroperoxide enone undergoes theMichael-addition-type reaction leading to the cyc-lized compound which further hydrolyses formingstable compound. Its formation might be indicatedby a new peak observed in the HPLC chromatogramof irradiated O2-saturated solutions of Met-enk,but not in t-Boc-Met-enk ones. Since the aminefunctionality is not available in t-Boc-Met-enk, therespective hydroperoxide enone cannot undergoMichael-addition-type reaction. Moreover, it wasobserved [5] that efficient conversion to the respec-tive hydroperoxides occurs only in peptides contain-

Fig.4. HPLC chromatograms recorded in (A) non-irradi-ated, (B) irradiated with 84 Gy O2-saturated aque-ous solutions containing 0.25 mM of t-Boc-Met-enkand 50 mM of N3

–. Detection by UV-Vis absorptionat 274 nm.

Fig.3. HPLC chromatograms recorded in irradiated with84 Gy N2O-saturated aqueous solution containing 0.25mM of Met-enk and 50 mM of N3

–. Detection by: (A)UV-VIS absorption at 274 nm and (B) fluorescence(exc. 284 nm, em. 425 nm).

Fig.2. Absorption spectrum obtained after oxidation oft-Boc-Met-enk ( ) by N3· radicals in O2-saturatedaqueous solutions containing 0.1 mM of the peptideand 5 mM of N3

– taken 1 ms after the pulse. Insets:The time profiles recorded at λ=405 nm in O2-satu-rated aqueous solutions containing 5 mM of N3

– and0.1 mM of Met-enk (left) or t-Boc-Met-enk (right).


ing a free amino group in tyrosine itself. Therefore,in t-Boc-Met-enk one has to consider reaction path-way involving hydroperoxide anion, which mightundergo oxygen elimination with simultaneousformation of phenoxide-type anions followed bytheir instantaneous protonation (regeneration oft-Boc-Met-enk). Blocking the terminal amine hadthus a key role in the protection of tyrosine. Thisfinding might be exploited in the search for newpain inhibitors.

Work was supported by the EC Marie CurieResearch Training Network SULFRAD under con-tract No. HPRN-CT-2002-000184.

References

[1]. Fontana M., Mosca L., Rosei M.A.: Biochem.Pharmacol., 61, 1253-1257 (2001).

[2]. Rosei M.A., Mosca L., De Marco C.: Biochim.Biophys. Acta, 1243, 71-77 (1995).

[3]. Rosei M., Blarzino C., Coccia R., Foppoli C., MoscaL., Cini C.: Int. J. Biochem. Cell Biol., 30, 457-463(1998).

[4]. Jin F., Leitich J., Sonntag von C.: J. Chem. Soc., PerkinTrans., 1583-1588 (1993).

[5]. Winterbourn C.C., Parsons-Mair H.N., Gebicki S.,Gebicki J.M., Davies M.J.: Biochem. J., 381, 241-248(2004).

in order to obtain spectra of isolated radicals de-rived from Tyr, Phe, and Met. Experiments wereperformed with a tripeptide Tyr-Gly-Gly, and twodipeptides, Phe-Leu and Gly-Met under identicalconditions as for enkephalins. These peptides wereselected in order to mimic an appropriate fragmentof either Leu-enkephalin or Met-enkephalin andalso the position with respect to the N- and/orC-terminal functions of the most vulnerable aminoacids (Tyr, Phe and Met) towards the H· attack.The transient spectra obtained from these peptideswere then used as possible components in the resol-ution of the transient spectra following reactionof H· with Leu- and Met-enkephalins. After resol-ution of the spectrum for Met-enkephalin (Fig.1),the G×ε values for Tyr-Gly-Gly and Phe-Leu are1.8×10–4 and 1.5×10–4 dm3J–1cm–1, respectively.Analogously, after resolution of the Leu-enkepha-

The role of hydrogen atoms (H·) in biology hasnot yet been completely assessed. It has been sug-gested that their involvement is not only based onthe effect of ionizing radiation in water systemssince H· can be generated efficiently by the reac-tion of electrons with dihydrogen phosphate an-ion (H2PO4

–) present in the biological environment[1]. Therefore, a peptide and/or protein damagedue to the H· attack has to be considered in greatdetail in order to establish its contribution to thecontext of radical stress to biomolecules [2]. Theselectivity shown by the involvement of methionine(Met) residues could be conveniently evaluated inshort amino acid sequences, which also allowgathering further data on the H· reactivity. As amodel peptide, we considered Met-enkephalin, aneuropeptide composed by five amino acid resi-dues (Tyr-Gly-Gly-Phe-Met; Tyr – tyrosine, Gly –glycine, Phe – phenylalanine), its leucine analogue(Leu instead of Met), and few selected peptidescontaining Met. The presence of aromatic residues(Tyr and Phe) and a sulfur-containing amino acid(Met), together with the possibility of comparinganalogous sequences without Met, represents anideal case to study any selectivity of reducing speciestowards the sulfur-containing amino acid and/orthe participation of other reactive sites in the ovearllmolecular reactivity. Here, we report pulse radi-olysis study of Met- and Leu-enkephalins applyingreaction conditions where the H· are the relevantreactive species, which affect the Met residues.

The optical absorption spectra obtained fromthe pulse irradiation of argon-purged aqueous sol-utions of Met- or Leu-enkphalin (0.1 mM) andtert-butanol – t-BuOH (0.5 M) at pH 1.5 are shownin Figs.1 and 2, respectively. Under these condi-tions, the hydroxyl radicals (·OH) are scavengedby t-BuOH and eaq

– are efficiently converted to H·.In order to evaluate the relative reactivity of thetwo enkephalins towards H· and the site of the at-tack, pulse radiolysis experiments were performed

REACTIONS OF HYDROGEN ATOMWITH METHIONINE-ENKEPHALIN AND RELATED PEPTIDES.

PULSE RADIOLYSIS STUDYOlivier Mozziconacci, Krzysztof Bobrowski, Carla Ferreri1/, Chryssostomos Chatgilialoglu1/

1/ Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council (CNR),Bologna, Italy

Fig.1. Resolution of the spectral components in the tran-sient absorption spectrum following the H· atom re-action with Met-enkephalin (0.1 mM) in argon-satu-rated aqueous solutions containing t-BuOH (0.5 M)at pH 1.5 taken 10 μs after the pulse.


reduced the amount of H· by 55% from furtherreaction with the Tyr and Phe residues. Moreover,the pulse radiolysis experiments indicated thatabout 50% of H· attack the thioether moiety ofMet moiety presumably via a sulfuranyl radical(>S·-OH) [3,4] with formation of CH3SH and/orCH3S· radicals. By using a peptide-liposome model,the cis-trans isomerization of phospholipids hasbeen detected highlighting the role of trans lipidas marker of this radical damage [5].

Work was supported by the EC Marie CurieResearch Training Network SULFRAD under con-tract No. HPRN-CT-2002-000184.

References[1]. Ferreri C., Manco I., Faraone-Minella M.R., Torre-

giani A., Tamba M., Manara S., Chatgilialoglu C.:ChemBioChem., 7, 1738-1744 (2006).

[2]. Lipinski B.: Br. J. Nutr., 87, 93-94 (2002).[3]. Ferreri C., Manco I., Faraone-Minella M.R., Torre-

giani A., Tamba M., Manara S., Chatgilialoglu C.:ChemBioChem., 5, 1710-1712 (2004).

[4]. Wiśniowski P., Bobrowski K., Carmichael I., Hug G.L.:J. Am. Chem. Soc., 126, 14468-14474 (2004).

[5]. Mozziconacci O., Bobrowski K., Ferreri C., Chatgilia-loglu C.: Chem. Eur. J., (2007), in press (available onthe website).

lin spectrum (Fig.2), the G×ε values for Tyr-Gly-Glyand Phe-Leu are 4.0×10–4 and 2.5×10–4 dm3J–1cm–1,respectively. Therefore, substitution of Leu by Met

control over the nature of the radical ionic speciesformed in secondary reactions in irradiated sol-utions, and thus generate both radical anions andcations or preferentially one of them. We have ini-tiated this study in order to obtain a knowledgeabout the spectral properties of radical ions de-rived from oxoisoaporphines. The present work isof interest in shedding some light on spectral prop-erties of the radical anion derived from 2,3-di-hydro-oxoisoaporphine. Both acetonitrile andacetone are known for pulse radiolytic generationof cation as well anion radicals precursors. In thesetwo solvents, both radical ions and only the radi-cal cation are formed under N2 and O2 saturation,respectively [3,4].

The optical absorption spectra obtained fromthe pulse irradiation of argon-purged acetonitrilesolutions of 2,3-dihydro-oxoisoaporphine (0.1mM) are shown in Fig.1.

The transient spectrum recorded 0.2 μs afterelectron pulse show two maxima at 450 and 605nm, respectively (Fig.1, curve a). They become sup-pressed upon O2 saturation (Fig.1, curve c), suggest-ing that they might be associated with the 2,3-di-hydro-oxoisoaporphine radical anion (A·–). Thelocation of the maximum at longer wavelength isin excellent agreement with that calculated for iso-lated 2,3-dihydro-oxoisoaporphine radical anion

Oxoisoaporphines are a family of oxoisoquino-line-derived alkaloids that have been isolated fromMenispermaceae as the sole known natural source[1]. Formation of radical anions (A·–) and neutralhydrogenated radicals (A-NH·) from the tripletmanifold (3A) was postulated during photoreduc-tion of 2,3-dihydro-oxoisoaporphine dye (A) byamines [2]. Quantum mechanical semi-empiricalPM3 and ZINDO/S calculations reproduce ad-equately experimentally observed absorption spec-tra of the excited triplet (3A) and of neutral hydro-genated radicals (A-NH·) with maxima located at450 and 390 nm, respectively [2]. However, thecalculated absorption maximum (λmax~600 nm) ofthe isolated 2,3-dihydro-oxoisoaporphine radicalanion (A·–) did not match the experimentally ob-served transient absorption spectrum with maxi-mum located at λmax~490 nm. Therefore, the latterspectrum was assigned to the radical ion-pair be-tween the radical anion of 2,3-dihydro-oxoisoapor-phine and the radical cation of the respective amine.This assignment was further confirmed by Molecu-lar Mechanics and ZINDO/S calculations [2].

Many previous studies have revealed that radi-cal ions can be easily generated by pulse radiolysisin a number of non-polar, polar-nonprotic, andpolar-polar protic solvents. Therefore, one may, bychoice of solvent and saturating gas, excercise some

Fig.2. Resolution of the spectral components in the tran-sient absorption spectrum following the H· atom re-action with Leu-enkephalin (0.1 mM) in argon-satu-rated aqueous solutions containing t-BuOH (0.5 M)at pH 1.5 taken 10 μs after the pulse.

PULSE RADIOLYSIS GENERATION OF THE RADICAL ANIONDERIVED FROM 2,3-DIHYDRO-OXOISOAPORPHINE

IN ORGANIC SOLVENTSKrzysztof Bobrowski, Gabriel Kciuk, Eduardo Sobarzo-Sanchez1/, Julio R. De la Fuente2/

1/ University of Santiago de Compostela (USC), Spain2/ Universidad de Chile, Santiago de Chile, Chile


(A·–). Therefore, the 605-nm band was unequivo-cally assigned to the radical anion (A·–). While,the radical anion (A·–) decays over a microsecondtime scale (t1/2~5 μs) (Fig.1, right inset), a new tran-sient spectrum appears which is characterized bytwo absorption maxima located at 420 and 500 nm,respectively (Fig.1, curve b). Since these two ab-sorption bands are also suppressed in oxygenatedsolutions they might be assigned to the secondaryproduct(s) derived from the radical anion (A·–).This new absorption could be attributed to the neu-tral N-hydrogen radical of 2,3-dihydro-oxoiso-aporphine (A-NH·) formed through protonation ofthe radical anion (A·–). The decay of neutral N-hy-drogen radical (A-NH·) occurs on the hundred ofmicroseconds time range (Fig.1, left inset).

Acetone is known to give both solute cations andanions, as well excited states. The optical absorp-tion spectra obtained from the pulse irradiation ofargon-purged acetone solutions of 2,3-dihydro-oxo-isoaporphine (0.1 mM) are shown in Fig.2. The tran-sient spectrum recorded 1 μs after electron pulseshow two maxima at 430 and 610 nm, respectively(Fig.2, curve a). As in acetonitrile, both absorp-

tion bands become suppressed upon O2 saturation(Fig.2, curve c). Again, they can be assigned to theradical anion (A·–). However, at shorter wave-length we cannot rule out the contribution of theexcited triplet state of 2,3-dihydro-oxoisoapor-phine (3A) [2]. The decay of radical anion (A·–) inacetone is slightly slower (τ1/2~10 μs) in compari-son to acetonitrile (Fig.2, inset). It is evident thatthe spectral changes observed on a longer timescale (Fig.2, curve b) after decay of the radical an-ion (A·–) are similar to those observed in acetoni-trile. Therefore, the absorption could be attributedagain to the neutral N-hydrogen radical of 2,3-di-hydro-oxoisoaporphine (A-NH·).

References

[1]. Sugimoto Y., Babiker H.A.A., Inanaga S., Kato M.,Isogay A.: Phytochemistry, 52, 1431-1435 (1999).

[2]. De la Fuente J.R., Neira V., Saitz C., Jullian C.,Sobarzo-Sanchez E.: J. Phys. Chem. A, 109, 5897-5904(2005).

[3]. Bobrowski K., Das P.K.: J. Phys. Chem., 90, 927-931(1986).

[4]. Bobrowski K., Das P.K.: J. Phys. Chem., 89, 5733-5738(1985).

Fig.1. Transient absorption spectra recorded (a) 0.2 μs and(b) 50 μs in argon-saturated and (c) 0.2 μs in O2-satu-rated acetonitrile solutions containing 2,3-dihydro-oxo-isoaporphine (0.1 mM) after electron pulse. Insets:Absorption changes at λ=420 nm (left) and λ=605nm (right) vs. time following pulse irradiation of2,3-dihydro-oxoisoaporphine (0.1 mM) in argon-satu-rated acetonitrile solutions.

Fig.2. Transient absorption spectra recorded (a) 1 μs and(b) 40 μs in argon-saturated and (c) 0.2 μs in O2-satu-rated acetone solutions containing 2,3-dihydro-oxo-isoaporphine (0.1 mM) after electron pulse. Inset:Absorption changes at λ=610 nm vs. time followingpulse irradiation of 2,3-dihydro-oxoisoaporphine(0.1 mM) in argon-saturated acetone solutions.

PULSE RADIOLYSIS STUDY OF THE INTERMEDIATESFORMED IN IONIC LIQUIDS. NATURE OF INTERMEDIATES

IN PULSE IRRADIATED p-TERPHENYL SOLUTIONIN THE IONIC LIQUID METHYLTRIBUTYLAMMONIUM

BIS[(TRIFLUOROMETHYL)SULFONYL]IMIDEJan Grodkowski, Rafał Kocia, Jacek Mirkowski

Room temperature ionic liquids (IL) [1-5] are con-sidered non-volatile and non-flammable and serveas good solvents for various reactions and have beenproposed as solvents for green processing and veryeffective media for numerous reactions [3-5]. Prom-ising experiments concerning application of IL in the

nuclear industry brought the question of radiationchemistry in these media. Up to now, only a limitednumber of experiments were directly focused onradiation stability of IL, the rate constants of severalelementary reactions in IL have been studied bythe pulse radiolysis technique instead [6-12].


In this study, the formation of intermediatesderived from p-terphenyl (TP) in the ionic liquid me-thyltributylammonium bis[(trifluoromethyl)sulfo-nyl]imide (R4NNTf2) solutions has been studiedby pulse radiolysis. TP was chosen because result-ing anionic, cationic and excited intermediates haveabsorption spectra in UV/VIS range (Table) [13].The pulse radiolysis of TP solution in R4NNTf2 givessubsequently some insight into the nature of pri-mary products of R4NNTf2 radiolysis. The relationsbetween TP* (excited singlet and triplet states) andTP·– have been already described. TP photocata-lytic activity was the other reason to chose this com-pound for experiments in IL and select the bestconditions for TP·– formation. In photochemicalprocess TP·– (often used in CO2 reduction [14,15and references therein]) is formed mainly from sin-glet excited states 1TP* by reaction with electrondonor triethylamine (TEA) and in radiolysis di-rectly in reaction with solvated electrons [14,15].TP* in IL solution can also be formed by energytransfer from excited radiolysis products of IL andin direct TP excitation by Èerenkov light.

The pulse radiolysis of TP solution in R4NNTf2has been carried out under Ar, CO2, O2 and N2Oin the presence or absence of TEA. Fast kineticmeasurements have been carried out using 10 ns,10 MeV electron pulses from a LAE 10 linear elec-tron accelerator [16] delivering a dose up to 20 Gyper pulse. The details of the computer controlledmeasuring system were described before [11,17].

Resulted under Ar intermediate spectra areformed in two steps, one very fast already completedduring the pulse, and the second lasting hundredsof nanoseconds depending on TP concentrations.The second step is eliminated in the presence ofelectron acceptors. The initial spectra are relatedto the species listed above and also to solvated elec-trons, except 1TP* which is too short lived to beobserved in nanosecond time scale.

In Figure, there is presented an absorption spec-trum corresponding to the second step only. It isset up from the difference between the spectrum at400 ns after the electron pulse (end of the secondstep) and the initial spectrum (corrected for spec-trum of solvated electron) obtained in pulse radi-olysis of Ar-saturated 14 mM TP solutions inR4NNTf2 with 3% TEA added. Very similar spec-trum is calculated from the results without addedTEA. The spectra can be ascribed to the TP·– be-cause of the similarity to the reported before re-sults in frozen systems [13]. Comparison of thecalculated TP·– spectrum with the shape of directexperimental spectra leads to the conclusion that

even under the best conditions for radiolytic TP·–

formation (Ar and TEA presence) TP·– is alwaysaccompanied by other intermediates, mostly 3TP*.TEA enhances the yield of TP·– due to scavengingof cation radicals and 1TP*, however it reacts moreslowly with 3TP* [15]. The presence of solvatedelectron scavengers cuts the initial spectrum in theregion 400-500 nm to about half value. This indi-cates that under Ar most of the TP·– is formed inthe reaction of TP with solvated electrons and theirprecursors, dry electrons. Some of TP·– (less than50%) are produced in the presence of TEA from1TP*.

Kinetics of the total absorption decay (in therange 400-500 nm) is quite complicated and thebest fitting to the experimental results can beachieved using exponential decay equation with atleast three different constants. Addition of O2 tothe TP solution, besides elimination of solvatedelectrons and consequently decreasing the inten-sity of the spectra, drastically increases the rate ofabsorption decay.

The reduction potentials of TP·– and CO2·– inIL are close to each other and the reactions be-tween TP and CO2 and their radical anions in anydirections cannot be seen in pulse radiolysis ex-periments.

Concluding, the primary radiolysis products ofR4NNTf2 solvent constitute of dry and solvated elec-trons, cation radicals and excited species. Reduc-tion potential of cationic species it is not highenough to oxidize Br– or SCN– but allows forma-tion of cation radicals of TP. TP·– is producedmainly in the reaction with dry and solvated elec-trons and its lifetime is in order of tens of micro-seconds in the pulse radiolysis experiments.

References

[1]. Welton T.: Chem. Rev., 99, 8, 2071-2083 (1999).[2]. Wasserscheid P., Keim W.: Angew. Chem. Int. Ed.,

39, 21, 3772-3789 (2000).[3]. Ionic liquids: Industrial application to green chemistry.

Eds. R.D. Rogers, K.R. Seddon. ACS Symp. Ser., 818(2002).

[4]. Chiappe C., Pierracini D.: J. Phys. Org. Chem. 18,275-297 (2005).

Table. Position of λmax of absorption spectra of intermedi-ates derived from TP [13].

Fig. Spectrum at 400 ns after subtraction of the initial spec-trum (corrected for spectrum of solvated electron),Ar-saturated 14 mM TP solutions in R4NNTf2 with3% TEA added, dose – 15 Gy.


philic dissociation [4,5,7]. The observed influenceof β-carboxylic groups on the efficiency of decar-boxylation suggest that β-carboxylate may catalyzedecarboxylation of α-carboxylate in the intramol-ecular process:

The differences in the decarboxylation yield be-tween the acids (Table) can be rationalized in termsof the stereoelectronically controlled Wagner-Meer-wein rearrangement [8,9] previously observed forcarbocations:

The upper branch of this mechanism shows the frag-mentation pathway that could be easily adopted fordecarboxylation of sulphur-centered radical cationsin alkylthiocarboxylic acids.

In this mechanism, the electron from the σ bond(between Cα and carboxylate) is donated to the radi-cal-cation center. The weakening of the bond resultsin a subsequent release of carbon dioxide. There-fore, the quite objective measure of the radical-cat-ion propensity to undergo such fragmentation couldbe distortion of the donor σ bond toward the elec-tron acceptor site at oxidized thioether sulphur.

Our recent investigations have been devoted tounderstanding the irreversible pathways of singletoxygen-induced (1O2-induced) oxidation of car-boxyl-substituted thioethers. The reaction of 1O2with thioether sulphur initially leads to the forma-tion of peroxysulphoxide [1,2]:

1O2 + >S → >S(+)O-O(–) (1)being in the equilibrium with superoxide radicalanion (O2·–) and respective sulphur-centered radi-cal cation:

>S(+)O-O(–) = >S·+ + O2·– (2)The major, enzymatically reversible [3], pathwayof persulphoxide decay is the bimolecular reactionwith the second molecule of thioether that leadsto the formation of respective sulphoxide [1,2]:

>S(+)O-O(–) + >S → 2 >S=O (3)Our previous experimental observation [4,5] for

the following model thioethers: 2,2’-thiodiethanoicacid (TDEA), 3,3’-thiodipropionic acid (TDPA),2-(methylthio)ethanoic acid (MTEA), 3-(carboxy-methylthio)propionic acid (CMTPA), 2-(carboxy-methylthio)succinic acid (CMTSA), have shownthe presence of the competitive, irreversible pro-cess of decarboxylation that can be schematicallyrepresented by below reaction:

R- S·+-CH2-CO2– → R-S-CH2· + CO2 (4)

That process could be quite effective for the sul-phur-centered radical cations of α-carboxyl-sub-stituted thioethers. Moreover, the nucleophilic ca-talysis of reaction (2) seems to be crucial for thecompetitiveness of the irreversible reaction path-way. In such catalytic process, the weak nucleo-phile O2·– (pKA(HO2·/O2·–)≈4.8 [6]) is replaced by astronger nucleophile like OH– or Cl– anions. TheDFT calculations have predicted the formation oftetravalent transient – product of OH– (or halogenicanions) addition to persulphoxide, pointing at theoccurrence of two-step (AN+DN)-type mechanismof subsequent nucleophilic addition and nucleo-

STEREOELECTRONIC CONTROL OVER THE MECHANISMOF SINGLET OXYGEN-INDUCED DECARBOXYLATION

IN ALKYLTHIOCARBOXYLIC ACIDSMonika Celuch, Mirela Enache1/, Dariusz Pogocki

1/ Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest, Romania

[5]. Jain N., Kumar A., Chauchan S., Chauhan S.M.S.:Tetrahedron, 61, 1015-1060 (2005).

[6]. Grodkowski J., Neta P.: J. Phys. Chem. A, 106, 22,5468-5473 (2002).



[9]. Wishart J.F., Neta P.: J. Phys. Chem. B, 107, 30,7261-7267 (2003).

[10]. Grodkowski J., Neta P., Wishart J.F.: J. Phys. Chem.A, 107, 46, 9794-9799 (2003).

[11]. Grodkowski J., Płusa M., Mirkowski J.: Nukleonika,50, Suppl.2, s35-s38 (2005).

[12]. Wishart J.F., Funston A.M., Szreder T.: Radiationchemistry of ionic liquids. In: Molten saltz. TheElectrochemical Society, Pennigton, NJ, USA, 2006.

[13]. Shida T.: Electronic absorption spectra of radicalions. Elsevier, Amsterdam 1988, p. 446.

[14]. Grodkowski J.: Radiacyjna i fotochemiczna redukcjadwutlenku węgla w roztworach katalizowana przezkompleksy metali przejściowych z wybranymi układa-mi makrocyklicznymi. Instytut Chemii i TechnikiJądrowej, Warszawa 2004, 56 p. Raporty IChTJ. SeriaA nr 1/2004 (in Polish).

[15]. Fujiwara H., Kitamura T., Wada Y., Yanagida S.,Kamat P.V.: J. Phys. Chem. A, 103, 4874-4878 (1999).

[16]. Zimek Z., Dźwigalski Z.: Postępy Techniki Jądrowej,42, 9-17 (1999), in Polish.

[17]. Grodkowski J., Mirkowski J., Płusa M., Getoff N.,Popov P.: Radiat. Phys. Chem., 69, 379-386 (2004).

(5)

(6)

(7)


In the DFT quantum chemical calculations [10] weobtained geometries and electronic structures ofsulphur-centered radical cations derived from eachof the investigated transient species. (The represen-tative example for CMTSA is presented in Fig.1.)For CMTPA and CMTSA, the sulphur-centered

radical cations being precursor of α-carboxylate de-carboxylation could be stabilized by the formationof three-electron-bonded species with the oxygenatom of adjacent β-carboxylate group. (The geo-metries and electronic structures of such specieswe have extensively investigated previously [11,12].)

In order to analyze the structures of sulfur-cen-tered radical cations in terms of the Wagner-Meer-wein rearrangement mechanism we chose the angleξ (Fig.1) as a measure of distortion of the σ bondtoward the radical-cation centre. Indeed, the com-putational results show a quasi-linear dependenceof relative yield of decarboxylation on ξ (Fig.2).The decarboxylation yield increases with growing

leaning of σ bond towards the radical-cation centrethat seems to confirm the assumed mechanism.

This work described herein was supported bythe Polish Ministry of Education and Science(grant No. 3 T09A 066 26). The computations wereperformed employing the computer resources ofthe Interdisciplinary Centre for Mathematical andComputational Modelling, Warsaw University(ICM G24-13).

References[1]. Clennan E.L.: Acc. Chem. Res., 34, 875-884 (2001).[2]. Jensen F., Greer A., Clennan E.L.: J. Am. Chem. Soc.,

120, 4439-4449 (1998).[3]. Sharov V.S., Ferrington D.A., Squier T.C., Schöneich

C.: FEBS Lett., 455, 247-250 (1999).[4]. Celuch M., Enache M., Pogocki D.: Singlet oxygen-

-induced oxidation of alkylthiocarboxylic acids. In:INCT Annual Report 2005. Institute of Nuclear Chem-istry and Technology, Warszawa 2006, pp. 26-28.

[5]. Celuch M., Pogocki D.: Singlet oxygen-induced decar-boxylation of carboxyl substituted thioethers. In: INCTAnnual Report 2004. Institute of Nuclear Chemistryand Technology, Warszawa 2005, pp. 27-29.

[6]. Bartosz,G.: Druga twarz tlenu. Wolne rodniki w przy-rodzie. Wydawnictwo Naukowe PWN, Warszawa2003, pp. 1-447 (in Polish).

[7]. Williams A.: Concerted organic and bio-organicmechanisms. CRC Press, Boca Raton 2000, pp. 1-286.

[8]. Rauk A.: Orbital interaction theory of organic chem-istry. John Wiley & Sons, Inc., New York 2001, pp.1-343.

[9]. Chanon M., Rajzman M., Chanon F.: Tetrahedron,46, 6193-6299 (1990).

[10]. Frisch M.J. et al.: Gaussian 03. (Rev. B.03). GaussianInc., Pittsburgh PA 2003.

[11]. Pogocki D., Schöneich C.: J. Org. Chem., 67, 1526-1535(2002).

[12]. Pogocki D., Serdiuk K., Schöneich C.: J. Phys. Chem.A, 107, 7032-7042 (2003).

Fig.2. Relative yield of 1O2-induced decarboxylation in alkyl-thiocarboxylic acids vs. the ξ angle.

Fig.1. The DFT (B3LYP/6-31G(d)) calculated structure ofsulfur-centered radical cation in CMTSA. The angleξ has been chosen as a measure of distortion of thedonor σ bond (Cα-CO2) toward the electron accep-tor radical cation.

Table. Alkylthiocarboxylic acids, structures and relativeyields of 1O2-induced decarboxylation.


The reduction of Cu(Im)42+ by thioethers was

investigated in oxygen- or argon-saturated aque-ous solution containing 1.5×10–3 M CuCl2, 7.5×10–3

M Im, and (0.75; 1.5 or 3.0)×10–3 M of thioethersat neutral pH, incubated at 50oC. The progress ofreaction was monitored using three independentmethods: high performance ion chromatographyexclusion (HPICE) [15] was applied for quantitativedetermination of products and substrates. Decay ofCuII was monitored by electron spin resonance(ESR) spectroscopy (in the redox pair CuII/CuI onlyCuII cations are paramagnetic). The formation ofCuI was followed using UV-VIS absorption spec-

troscopy of 2,2’-bicinchoninic acid (BCA) complexwith Cu+ cations (Cu(BCA)2

3–: λmax≈562 nm, ε≈7700M–1cm–1) [16].

Fig.1. The ESR signal changes vs. incubation time in ar-gon-saturated (solid symbols) and oxygen-saturated(open symbols) solutions containing: 1.5×10–3 MCuCl2, 7.5×10–3 M Im and 0.75×10–3 M (square) or3.0×10–3 M (triangle) of MTAA.

The presence of cupric ions is essential for propermetabolism of many organisms. The best recognizedand appreciated function of cupric ions is their par-ticipation in the active centers of numerous enzymes[1]. On the other hand, the faults in copper homeo-stasis in humans are frequently related to disorderswith neurological symptoms [2,3]. For example,copper is bind by β-amyloid peptide (βA), the mostabundant constituent of senile plaques observed inAlzheimer’s disease (AD) brains [2,3]. The βA-boundcopper can be involved in the cycle of Fenton likereactions, in which free radicals and other reactiveoxygen species (ROS) presented in pathology of ADmay be formed [4].

In this work, we continue investigation of themechanisms that may explain the ability of βA toreduce copper in reaction:

MetS + βA(CuII) ↔ βA(CuI) + MetS·+ (1)Such process seems thermodynamically unfavor-

able [5], since in normal conditions the differencebetween the reduction potentials of βA(CuI/CuII)(0.5-0.55 V vs. Ag/AgCl) [6] and MetS·+/Met(1.26-1.5 V vs. Ag/AgCl) [7-10], is about ca. 0.7-1.0V, thus equilibrium (1) should be shifted to the farleft-hand side [5].

However, reaction (1) may occur if coupled withthe other exergonic reaction. One of possible scen-ario is the removing of MetS·+ from the equilibriumby the formation of α-(alkylthio)alkyl radicals(αS·) in exergonic, general base catalyzed reaction:

MetS·+ + B → Met(αS)· + BH+ (2)Therefore, in this work we studied, on the model

systems, reactions that may spontaneously lead tothe formation α-(alkylthio)alkyl radicals, potentiallyinfluencing equilibrium (1) and accelerating oxi-dation of the methionine (Met) residue in peptides.

We examined a molecular system, in whichthe complex of CuII

with imidazole mimics cupricsite of βA. The fifth fold excess of imidazole (Im)over Cu2+ guarantee that at least 95% of copperis in the form of Cu(Im)4

2+-type complex of knownproperties: λmax≈590 nm (ε=53 ±2 M–1cm–1) [11]and E0(CuII/CuI)≤0.2 V and E0(CuI/Cu0)≤0.6 V vs.SCE [12]. The methionine residue was mimickedby organic α-substituted thioethers: 2,2’-thiodi-acetic acid (TDEA, HO2C-CH2-S-CH2-CO2H),and 2-(methylthio)acetic acid amide (MTAA,CH3-S-CH2-CO2-NH2). In both cases the reductionof Cu(Im)4

2+-complexes should be accompanied bya simultaneous formation of the resonance sta-bilized α-(alkylthio)alkyl radicals. For TDEA, en-tropy driven decarboxylation is the main source ofα-(alkylthio)alkyl radicals, whereas for MTAA thefacilitated deprotonation, due to the captodativeeffect stabilizing α-(alkylthio)alkyl radicals, willdominate [13]. Contrary to fast decarboxylation ofTDEA, deprotonation in MTAA should be sus-ceptible to the presence of proton acceptors [14].

OXIDATION OF THIOETERS BY ORGANIC COMPLEXES OF COPPERMonika Celuch, Katarzyna Serdiuk1/, Jarosław Sadło, Mirela Enache2/, Dariusz Pogocki

1/ Jan Długosz University of Częstochowa, Poland2/ Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest, Romania

Fig.2. The concentration of Cu(BCA)23– complexes vs. in-

cubation time for argon-saturated solutions contain-ing: 3.0×10–3 M of thioether (MTAA – squares, TDEA– triangles), 1.5×10–3 M CuCl2 and 7.5×10–3 M Im.


For the all samples containing TDEA, and forargon-saturated samples containing MTAA we ob-served the decay of ESR signal. Whereas for oxy-gen-saturated samples of MTAA the intensity ofESR signal remained on the same level for morethan 300 h of incubation (see example in Fig.1).Also, the HPICE measured changes of MTAAconcentration during incubation in oxygen-satu-rated solutions were insignificant. Similarly, theformation of Cu(BCA)2

3– complexes was observedin the presence of both thioethers in argon-satu-rated samples (Fig.2). Generally, the significantdifferences in kinetics between thioethers were ob-served. For the same concentrations of TDEA andMTAA, both the ESR and the UV-VIS experiments

show faster changes for TDEA, which reduces CuII

with more than two times higher efficiency thanMTAA. On the other hand, we obtained the evi-dence that the process of CuII-complexes reduction,induced by deprotonating thioether such as MTAA,could be accelerated in general acid-base catalysisby phosphate ions (Fig.3). The mechanism shownin Scheme is a preliminarily attempt to rationalizecurrent observation for MTAA. It requires, how-ever, additional consideration especially on themechanistic details of the conversion of peroxylradicals regenerating the mother compounds.

This work described herein was supported bythe Polish Ministry of Education and Science (grantNo. 3 T09A 066 26).

References[1]. Holm R.H., Kennepohl P., Solomon E.I.: Chem.

Rev., 96, 2239-2314 (1996).[2]. Strausak D., Mercer J.F., Dieter H.H., Stremmel W.,

Multhaup G.: Brain Res. Bull., 55, 175-185 (2001).[3]. Gaggelli E., Kozłowski H., Valensin D., Valensin G.:

Chem. Rev., 106, 1995-2044 (2006).[4]. Halliwell B., Gutteridge J.M.: Free radicals in biology

and medicine. Oxford University Press, Oxford 1999,pp. 1-936.

[5]. Schöneich C.: Arch. Biochem. Biophys., 397, 370-376(2002).

[6]. Huang X. et al.: J. Biol. Chem., 274, 37111-37116(1999).

[7]. Merényi G., Lind J., Engman L.: J. Phys. Chem., 100,8875-8881 (1996).

[8]. Engman L., Lind J., Merényi G.: J. Phys. Chem., 98,3174-3182 (1994).

[9]. Huie R.E., Clifton C.L., Neta P.: Radiat. Phys. Chem.,92, 477 (1991).

[10]. Sanaullah, Wilson S., Glass R.S.: J. Inorg. Biochem.,55, 87-99 (1994).

[11]. Edsall J.T., Falsenfeld G., Goodman D.S., GuardF.R.N.: J. Am. Chem. Soc., 76, 3054-3061 (1954).

[12]. Li N.C., White J.M., Dood E.: J. Am. Chem. Soc., 76,6219-6223 (1954).

[13]. Wiśniowski P.: Wpływ grup funkcyjnych na inicjowaneradiacyjnie procesy rodnikowe w tioeterach (The in-fluence of functional groups on the radiation initiatedradical processes in thioethers). Ph.D. thesis. InstytutChemii i Techniki Jadrowej, Warszawa 2001 (in Polish).

[14]. Mönig J., Goslich R., Asmus K.-D.: Ber. Bunsen-Ges.Phys. Chem., 90, 115-121 (1986).

[15]. Weiss J.: Ion chromatography. VCH, Weinheim 1995,pp. 1-465.

[16]. Boyd-Kimball D., Mohmmad A.H., Reed T., Sultana R.,Butterfield D.A.: Chem. Res. Toxicol., 17, 1743-1749(2004).

Fig.3. The influence of phosphate ions (H2PO4–/HPO4

2–) onthe kinetics of CuII reduction by MTAA in argon-satu-rated solutions containing: 0.75×10–3 M thioether,1.5×10–3 M CuCl2, 7.5×10–3 M Im and (solid symbols)0.15×10–3 M phosphate buffer, (open symbols) phos-phate free solution.

Scheme.

During radiolysis of solutions containing silversalts, Ag+ cations are reduced to Ag0 atoms whichinitiate silver agglomeration process. The solventradicals formed radiolytically compete with Ag0 toreact with Ag+ cations. Just after irradiation at 77K in frozen solution of methanol containing silverperchlorate the electron paramagnetic resonance

(EPR) measurements reveal a doublet with silverhyperfine splitting in the range 60-70 mT represent-ing Ag0 atoms [1]. During thermal annealing, adoublet with much smaller splitting Aiso(Ag)=13.6mT appears together with a less intense triplet withA(Ag)=30.0 mT. Based on the electron spin echoenvelope modulation (ESEEM) result, the doublet

ORGANOSILVER RADICALS IN ZEOLITESJerzy Turek, Jarosław Sadło, Jacek Michalik


was assigned to an adduct of Ag+ cation and hy-droxymethyl radical (·CH2OH) with a one-electronbond between silver and carbon.

In gamma-irradiated silver zeolites exposed tomethanol vapour the doublet of silver hydroxy-methyl radical is also observed, but hyperfine split-ting values vary very much for different zeolite struc-tures [2]. The goal of our studies was to define thenature of bonding between Ag+ cation and smallcarbon radicals and to determine the factors thataffect the value of A(Ag) hyperfine splitting fororganosilver radicals.

After dehydration at 200oC, the zeolite sampleshave been oxidized with O2 under pressure of 300Torr for one hour. Next, oxygen was pumped outand the methanol was adsorbed at room tempera-ture. The samples were gamma-irradiated at 77 Kin a 60Co source. The EPR spectra were measuredusing a Bruker ESP-300 spectrometer equippedwith a cryostat operating in the temperature range100-350 K.

Typical EPR doublets of [Ag·CH2OH]+ adductlabelled as Ag·C are shown in Fig. for Ag-NaA andAg-ferrierite zeolites exposed to methanol. Thehyperfine splitting values for various zeolite struc-tures are presented in Table 1. They differ from12.0 mT for 4A zeolite to 19.5 mT for ferrierite.The dependence of Aiso(Ag) constant on the Si/Alratio is strong in big cation capacity zeolites andprobably is linear. However, the cation capacityaffects A(Ag) value of [Ag·CH2OH]+ only to a mi-nor degree as was proved by the experiments withAg-ZSM-5 zeolites with Si/Al ratio in the range30 to 200 and MCM-41 zeolites with Si/Al ratiofrom 10 to 30. To verify our experimental conclu-sions concerning the zeolite lattice influence on the

Ag·C radical structure, we performed density func-tional theory (DFT) calculations for a system of Ag+

cation interacting with hydroxymethyl radical. Thosecalculations confirmed that the one-electron bondbetween silver and carbon is able to stabilize the[Ag·CH2OH]+ adduct. The formation of the adductcauses a substantial shift of spin density from carbonto silver. An EPR doublet cannot originate fromthe Ag·O one-electron bond because such configu-ration gives a very low spin density on silver.

The results of DFT calculations show that theA(Ag) of [Ag·CH2OH]+ radical depends stronglyon the interaction of Ag+ with the surroundingsespecially with electronegative atoms. Theoreticalvalue of hyperfine splitting of the free silver hydroxy-methyl radical is equal to 16.4 mT. If one takes intoconsideration the interaction of one methanolmolecule with the metallic centre of [Ag·CH2OH]+

radical, the A(Ag) value calculated by the DFTmethod decreases to 14.2 mT which is very closeto the experimental value observed in gamma-ir-radiated frozen solutions of silver perchloride inmethanol. But when the radical forms a hydrogenbond A(Ag) this value increases to 216 G.

Comparing DFT results with the data of EPRexperiments, it was proved that in zeolites with bigcation capacity the silver hydroxymethyl radicalinteracts with a silicaallumina network by the me-tallic centre of the radical. The decrease of cationcapacity modifies the radical surroundings chang-ing electronic density distribution. In zeolites withsmall cation capacity, the formation of hydrogenbonds with zeolite network is postulated as a domi-nating interaction of silver hydroxymethyl radical.

The theoretical calculations showed also a sub-stantial influence of the functional group on the Aghyperfine splitting for different adducts with theAg·C one-electron bond (Table 2). It depends onthe ability of the functional group to attract or re-pulse electrons. Electron donor functional groups

increase spin density on the Ag nucleus which re-sults with large values of hyperfine splitting rang-ing from 13 to 20 mT. In contrast, A(Ag) for Ag·Corganosilver radicals with electron acceptor groupsare in the range 5-8.5 mT because they decrease thespin density on silver.

Fig. The EPR spectra at 160 K of (a) Ag-ferrierite and (b)Ag-NaA zeolites exposed to methanol vapour andgamma-irradiated at 77 K. Ag·C dublets representsilver hydroxymethyl radicals.

Table 1. Experimental values of A(Ag) hyperfine splittingfor [Ag·CH2OH]+ in different zeolites.

Table 2. Theoretical values of A(Ag) for different organo-silver radicals.


radiated massive bones renders the percentage ofhydroxyapatite through bone cross-section. Theradical concentration is higher in bone pieces con-taining more hydroxyapatite.

For one-sided irradiation, the distribution ofradicals is similar to dose depth dependence: maxi-mum concentration is at the depth of one centi-meter. Concentration difference between the upperand lower part is about 60% indicating that the ap-plied dose does not guarantee sterility of the bone(Fig.2A). In case of two-sided irradiation, the dis-tribution of radical concentration is much more flatand the difference between the highest and lowestvalues is about 30% (Fig.2B).

The dose distribution during electron beam irra-diation was estimated using a PVC foil dosimeter(spectrophotometric method) as well as a powderalanine dosimeter (EPR dosimetry). In both casesthe dosimeters were placed between two biggerbone parts and then one-sided irradiated. The ala-nine powder was placed in small flat bags. The ala-nine from each bag was measured separately. Theresults confirmed that the profile of distributionis rather complex because of the complicated shape

Fig.1. EPR spectrum of CO2– radical induced in irradiated

bone.

The bone transplantation method, a useful tool oforthopedic surgery, requires advanced and fullycontrolled methods of sterilization, mainly usingionizing radiation sources. Radiation can fast pro-vide sufficient energy to sterilize a whole volumeof bone pieces. Small volume grafts – like bonepowder fillers or pieces of compact bone like platesor poles, have been sterilized in the Institute of Nu-clear Chemistry and Technology (INCT) by accel-erators for many years.

Recently, tissue banks offer also massive grafts– the whole fragments of bone. In that case, becauseof complicated shape and composition of compactand spongy bone types, it is necessary to controlthe dose distribution as well as the distribution ofradiation-induced radicals. It should be stressedthat dose distribution must not be identical withradical distribution because of inhomogeneity ofbone structure.

For experiments, the human tibia bones wereused. A massive fragment was cut into thin slicesassembled back into the anatomical shape. Next,it was one-sided irradiated by a 10 MeV electronbeam (Elektronika, INCT) with a dose of 30 kGy.A similar fragment was two-sided irradiated witha dose of 2x20 kGy. The fragment of the same con-figuration was irradiated by 60Co gamma rays(Issledovatel, INCT, 30 kGy). Next, all the sliceswere cut into about 100 small pieces and thencrushed into powder to avoid anisotropic effects.Electron paramagnetic resonance (EPR) measure-ments were carried out using an X-band BrukerESP 300 spectrometer. The measured EPR signal,an anisotropic singlet with g⊥=2.003 and gll=1.997(Fig.1), origins from mineral part of the bone wasassigned earlier to CO2

– radical. The signal is stableand its intensity increases linearly with absorbeddose.

The highest difference in the concentration ofCO2

– radicals in small pieces of the bone irradiatedin a 60Co source does not exceed 18%. That type ofradiation can easily penetrate the bone fragmentsin the whole volume because of high penetrabilityof gamma rays. Thus, the radicals concentrationshould be similar in the whole cross-section of thebone. However, the experimental results are differ-ent because of inhomogeneity of bone structure and,in practice, the radical concentration in gamma-ir-

EPR STUDY ON RADIATION-INDUCED RADICAL DISTRIBUTIONIN MASSIVE BONE GRAFTS

Jarosław Sadło, Jacek Michalik, Grażyna Strzelczak, ,Artur Kamiński1/

1/ Central Tissue Bank, Medical University of Warsaw, Poland

References[1]. Symons M.C.R., Janes R., Stevens A.D.: Chem. Phys.

Lett., 160, 386 (1989).[2]. Michalik J., Sadlo J., van der Pol A., Reijerse E.: Acta

Chem. Scand., 51, 330 (1997).

It is worthy of stressing that the functionalgroups which decrease or increase A(Ag) splittingare similar to those which, in a similar way, affectelectron density on π orbitals of benzene ring. Thus,we can speculate that resonance structures similarto the structures in the chemistry of aromatic hy-drocarbons are responsible for the observed effect.

Anna Dziedzic-Gocławska1/


of irradiated object and the presence of bone chan-nels. For both dosimeters, the maximum dose wasequal to about 120% of the initial value, and thedose distribution was very similar to radical con-centration distribution.

It is concluded that for massive bone fragmentsone-sided irradiation does not guarantee steriliza-tion of the whole fragments, therefore two-sidedirradiation should be applied as a routine in thatcase.

Fig.2. Dose distribution in one-sided (A) and two-sided (B) massive bone grafts.

The year 2006 was the last full year of my partici-pation as the member of Managing Committee inthe European action in chemistry COST D27 (Pre-biotic chemistry and early evolution), as the onlyradiation and radiochemist in the Committee. Thefield is closely connected to the so-called astro-biology, which deals with life and prebiotic chemi-cal compounds present anywhere in the universe.Problems involve transportation of that materialin any directions, what can be involved in the ori-gin of life on earth.

The very old [1] concept of panspermia hypoth-esis may be traced to Greek philosophers. Even now,the idea that the transportation of spores from theuniverse is responsible for the origin of life onearth, is always widely accepted as long as it is notconfronted with conditions in the universe. Theseare characterized mainly by the existence of invis-ible, but chemically and biologically active ionizingradiations. Their intensity is sufficient to kill highlyorganized life and also primitive life, if the time ofinteraction is long enough. We have presented thequantitative relationships on practically all work-shops organized during COST D27 meetings andother conferences, e.g. on ISSOL 05 [2], stressingthe chemical mechanism of the irreversible radia-tion damage to dry spores. The best description ofpossibilities of spores to survive the transportationin the universe is the table published by BentonClark [3], then slightly modified [4]. Clarks paperis seldom quoted; it is simply non-existent amongenthusiasts of panspermia.

The doses which decide about very low prob-ability of panspermia are similar to doses appliedin technology of radiation sterilization, widely usedfor killing all microorganisms in medical devices andmedicaments [5]. The radiation should not damagethe sterilized material, which survives the irradia-tion with a minimal loss of active compound or re-mains with negligible degradation of material, usu-ally a polymer. The same applies to celestial bodies:if the sojourn in space is comparatively short, theonly change, however important, is the killing of life,e.g. of spores which otherwise would be the seedsof life transported to earth. As one can see fromthe Clark table, the time of travelling in space withresulting sterilization only, is astronomically speak-ing short. However, the real sojourn in radiationfields lasts very much longer and the absorbed, ad-ditive doses grow [6].

Clark’s table (in modified version see [4]) showsmore than when and in what object the spores willbe inactivated. What happens during longer stays,especially to objects of small size like cosmic dust,easily penetrated not only by electromagnetic ion-izing radiations like gammas, but also by particleslike protons and by heavier ions, present in galac-tic cosmic rays? These objects are absorbing mam-moth doses of radiation energy, which causes manychemical reactions. The next to sterilization doseis the dose not very much higher, causing abstrac-tion of parts of biopolymers or parts of organiccompounds. There are many examples of such re-actions, the most general is the fact common in

RADIATION CHEMISTS VIEW ON PANSPERMIA HYPOTHESISZbigniew P. Zagórski


dramatically lower in comparison to those at am-bient temperatures.

The common reaction of abstraction of hydro-gen, not limited to spores but of general occurrence[8], corroborates well with characteristic featureof organic compounds, identified spectroscopicallyin interstellar spaces of the universe. They are aspoor in hydrogen as possible, e.g. methyltriacetylene(C7H4), methylcyanodiacetylene (C6NH3), cyano-allene (C4NH4), ketenimine (C2NH3), cyclopro-penone (C6OH2) and many polyaromatics. Theremaining hydrogen atoms are difficult to detachduring absorption of ionizing radiation, becausethey usually belong to structures, mainly polyun-saturated and aromatic which possess the abilityto dissipate the absorbed ionization energy with-out ionization.

The question remains why the life on earth isnot destroyed after sufficiently long action of ion-izing radiation. The ionizing radiation which im-pregnates the universe is reaching the surface ofearth in much reduced intensity, due to the shieldof the atmosphere, equivalent to 3 meters of con-crete. Even the most penetrating galactic cosmicrays, which reach the earth in cascades of second-ary ionizing radiations are responsible for onlysmall contributions to mutations forming in livingorganisms. Other ionizing radiations coming fromouter space, like gamma bursts, proton beams fromevents in the Sun and other stars, are almost fullyabsorbed. Therefore, the contribution of spaceradiation to the radiation background on earth isonly similar to the present level supplied by radio-active material on earth. The deciding fact causingnot the inactivation of life on earth but, vice versa,even some positive effects, is the interaction ofradiation with living matter. Whereas the DNA inthe living species, i.e. in aqueous suspensions, whendamaged slightly by ionizing radiation can be re-paired, the DNA in dry spores is effectively, irre-versibly damaged by the very first doses of radia-tion. The effect is additive, and even low doses aredamaging, after accumulation of elementary acts,mainly of hydrogen abstraction, over ages. Repaireddamages to living populations do not accumulate.The by-product of low level radiation damage arepossible mutations, like many other factors in theenvironment. They occur only due to the action onliving organisms, they do not occur when sporesare irradiated, when irreversible changes take place.

The soon coming fifth anniversary of the COSTaction D27 asks for formulation of conclusions. In-tensive, also experimental investigation of the frag-ment of the action connected with panspermia andmore, i.e. the action of ionizing radiation in theuniverse on objects travelling in space, demandsrevision of some well established opinions. Theoreti-cal considerations as well as experimental simula-tions show that these objects are not only sterilized,what demands comparatively low doses, but alsodeprived of its homochirality, if any, and eventuallyeven freed from organic compounds. Therefore, hereare examples of defined conclusions:

The very thoroughly investigated Murchisonmeteorite, supposed to originate ca. 4 Giga years

radiation chemistry, i.e. the abstraction of a groupwhich leaves in the molecule a site with unpairedelectron.

Another example is the destruction of chirality.Abstraction of a group, e.g. of ammonia from theα-carbon in an amino acid, turns off the asymmetryof the remaining radical. The free radical can attacha group, and the new compound will be chiral, ifthe group is different from the remaining three.Therefore, if the original amino acid was a pureenantiomer, any products of the subsequent reac-tion will keep chirality, but will be racemic, 1:1 Dto L. Hypothetical homochirality of a compoundachieved (perhaps) far from the Earth will be lostduring the travel.

Moving to higher doses resulting from evenlonger stays in the universe, we are turning intothe zone of complete degradation, and sometimeseven to disappearance of an organic compound.The Scheme shows possible degradation reactions.

The final result can depend on the surrounding,whether oxidative presence of oxygen, or reducing,or vacuum. In both two last named cases, the finalproduct can be nano-sized carbon dust, and suchreaction is called radiation-induced carbonization.

Large objects staying for a long time in spaceobtain highest doses of ionizing radiation at thesurface, gradually diminishing towards the inside.The depth dose can be estimated from the Clarktable. The surface of the object is the most irradi-ated part and the best known object is the planet ofMars [7]. Its regolith is not only completely steril-ized but also relieved from organics. Perhaps partof organics has been degraded to elementary car-bon, present, if so, as black dust moved with theMartian thin CO2-wind. Anyway, chances for de-tection of organics on the surface of Mars are poor.Similar conclusions have been drawn by photo-chemists, assuming devastating chemical influenceof deep UV reaching the surface of Mars. Their ar-gument is poor, because supposed the Martian or-ganics show usually no absorption in UV, but evenin the presence of chromophoric groups the effectis of low importance, because the depth of penetra-tion is shallow. Therefore, the deciding influence ofionizing radiation is more important.

The low temperature of space on the route ofmoving objects is not a protecting factor, becauseradiation-induced reactions proceed with low ac-tivation energy and presented chemical effectsobserved at liquid nitrogen temperatures are not

Scheme.


ago and bringing to the earth samples of organiccompounds, including amino acids from the begin-ning of the solar system, could not be so old asclaimed. Such a long sojourn in space is connectedwith the deamination of amino acids and relatedloss of homochirality. The ancient origin of pres-ence of any organic compounds is highly doubtful.The lifetime of Murchinson meteorite should be es-timated in millions and not milliards (US – billions)of years. The identity of organic matter found inhundreds of published papers indicates that thisobject has been ejected from earth later than 200million years ago, that means not earlier thandeposites of coal have been formed on earth. Es-pecially polyaromatics and lignine related com-pounds indicate the origin in large coal deposits,covering a lot of earth surface. Specialists in con-siderations of ejection of meteorites from Mars,which have reached Earth agree that ejections fromEarth to Earth are a little bit less probable, but notimpossible [9]. The matching of location and timeof oblique strike of an asteroid on Earth demandsmore analysis and studies.

The second, but not last conclusion refers toMars, an object lasting under the ionizing radiationfor Giga years. Assuming that 4 Giga years or soago, Mars had oceans of water, the organic soupwas formed, not concluding into creation of life. Ifwater has evaporated and disappeared, the organicmatter should remain, but in the next millions of

years it was radiolysed down to inorganic remains.Therefore, there should be no hope to find organicmatter whatsoever on Mars. And really, no tracesof organics have been found yet. Actual efforts torefine methods of investigation for organic matterlook like waste of money.

The work was supported by the Polish Ministryof Scientific Research and Information Technol-ogy and by the European Project COST D27 (Pre-biotic chemistry and early evolution).

References

[1]. Luisi P.L.: The emergence of life, from chemical ori-gins to synthetic biology. Cambridge University Press,Cambridge 2006.

[2]. Zagórski Z.P.: Origins Life Evol. Biosphere, 36, 244-246(2006).

[3]. Clark B.C.: Origins Life Evol. Biosphere, 31, 185-197(2001).

[4]. Zagórski Z.P.: Postępy Techniki Jądrowej, 46, 42-52(2003), in Polish.

[5]. Zagórski Z.P.: Sterylizacja radiacyjna (Radiation ster-ilization). 2nd ed. Instytut Chemii i Techniki Jądrowej,Warszawa 2007 (in Polish).

[6]. Zagórski Z.P.: Radiat. Phys. Chem., 66, 329-334 (2003).[7]. Zagórski Z.P.: Nukleonika, 50, Suppl.2, S59-S63

(2005).[8]. Zagórski Z.P.: Indian J. Rad. Res., 3, 89-93 (2006).[9]. Artemieva N. (Institute for Dynamics of Geospheres,

RAS, Moscow, Russia): private communication(21.11.2006).

MODIFIED BENTONITE FILLERS IN POLYMER COMPOSITESZbigniew Zimek, Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski

In our previous work, maleic anhydride (MA) wasgrafted on the inorganic surface of bentonites con-taining montmorillonite (MMT) [1]. The main con-clusion driven from the studies was that maleic an-hydride reacts via the anhydride group with activeionic sites of bentonite forming a salt-like compound.Irradiation with electron beam leads to the break-age of double bond in maleic anhydride and to theproduction of new organic phases. The range of ion-izing radiation doses was found to optimize fillerproduction [2,3].

In the recent work, we have used the obtainedfillers to prepare composites with polypropylene (PP)and compare properties of the pure polymer andpolypropylene composites with bentonite modifiedammonium salts.

Isotactic polypropylene (iPP) Malen P J601 waspurchased from Basell Orlen Polyolefines. Unmodi-fied bentonite Tixogel VP (TVP) containing >90%montmorillonite in the form of sodium salt wasobtained from Riedel-deHaen. Two kinds of un-modified Polish bentonites were received fromMine “Zebiec”, Starachowice: “Special”, containingmore than 70% of pure montmorillonite and type“SW”, containing ca. 50% of pure montmorillonite.Samples of Polish bentonites “Special” modifiedwith ammonium salts (benzyldodecyldimethyl anddidecyldimethyl bromides) were obtained fromRzeszów University of Technology and extra pure

samples of montmorillonite were obtained fromWrocław University of Technology.

Maleic anhydride was absorbed on bentonitesfrom 10% w/w solution in acetone for half an hour.The solids were washed with acetone (to removeexcess of anhydride) and dried for 6 h under lowpressure at 30oC. The samples of MMT/MA wereirradiated with 10 MeV electron beam. The overalldoses were 26, 52, 78 or 104 kGy. All the samples,before testing and mixing with a polymer, wereground and sieved in order to select fraction of par-ticles below 70 μm, used for further processing.

The composites of polypropylene and modifiedbentonites were prepared in a Brabender mixer inthe temperature range of 185-210oC. After mixing,the samples were pressed in the form of foils of athickness of about 0.35 mm.

For scanning electron microscopy (SEM), thefoils were frozen in liquid N2 and broken. SEMphotos at different magnifications were obtainedusing a Zeiss SEM microscope after gold deposi-tion.

Structure of modified montmorillonite wasstudied by the WAXD (wide-angle X-ray diffrac-tion) method using a URD-6 X-ray diffractometerwith graphite monochromatized Cu-Kα radiation.SEM photos were obtained with a Jena DSM 942(Germany) scanning electron microscope with dif-ferent magnification.


The mechanical properties: tensile strength,yield stress and elongation at break were testedusing a universal testing machine Instron 5565. Allthe measurements were performed at ambient tem-perature according to PN/ISO-527 standard.

Infrared (IR) measurements were conducted ona Bruker FTIR spectrometer in single reflectionmode (ATR), using a Si prism.

WAXD diffractograms of pristine and modifiedwith maleic anhydride bentonite “Special” are shownin Fig.1. The results clearly confirm the presenceof montmorillonite in bentonites which is charac-terized by specific reflection to the planes (001) and

(002). The basal spacing of the montmorillonite is1.55 nm calculated from the peak on diffractograma (position 2θ=5.7o). Upon modification with ma-leic anhydride, a diffraction peak of bentonite isalmost at the same place (2θ=5.6o, d=1.58 nm)(Fig.1, diffractogram b) proving that the spacingbetween layers is not changed significantly and thatthe anhydride is not intercalated between intergallerylayers of montmorillonite. However, intensity of thelines becomes lower what must result from greaterdisorder of the layered silicates, while maintaining

a periodic distance. Diffractogram (b) of modifiedmontmorillonite reveals a new peak at the position2θ=21o what has to be assigned to the changes inthe structure in (002) plane and might suggest thatmaleic anhydride is attached to the surface of mont-morillonite layers.

IR spectra recorded for montmorillonite, ma-leic andydride modified montmorillonite before andafter irradiation with a dose of 75 kGy, do not showdetails of bond type between montmorillonite andmaleic anhydride forming before and after irradia-tion with electron beam (Fig.2). This is probablydue to low concentration of organic compounds inthe modified montmorillonite. Only the presenceof maleic anhydride is visible in the spectra of modi-

fied montmorillonite as a band in 1600 cm–1 region(C=O band of carbonyl compound).

SEM photos at different scale levels of polypro-pylene foils containing 2.9 wt% of “Special” mont-morillonite modified with maleic anhydride and

Fig.2. FTIR (Fourier-transform infrared) spectra of: (a) un-modified bentonite “Special”, (b) bentonite “Special”modified with maleic anhydride, (c) bentonite “Spe-cial” modified with maleic anhydride and irradiatedwith a dose of 78 kGy.

Fig.1. WAXD diffractograms of: (a) bentonite “Special”,as purchased, (b) bentonite “Special” after absorp-tion of maleic anhydride and irradiation with a doseof 26 kGy.

Fig.3. SEM images of polypropylene filled with bentonite “Special” modified by didecyldimethylammonium bromide(cross-section of thin foil) at different magnifications.


irradiated with a dose of 50 kGy (Fig.3) were com-pared with similar photos of foil obtained frompolypropylene containing 2.9 wt% of “Special” mont-morillonite modified with didecyldimethylammo-nium bromide (Fig.4). Photos of the selected com-posite confirm homogeneity of material obtainedfrom polypropylene and montmorillonite modifiedby maleic anhydride, and subsequently irradiated.At the micrometer level, images indicate that ag-gregates of a few micrometers are statistically dis-persed in the matrix. On the basis of the consistuentscorresponding to 5 μm one can conclude that thereare particles strongly interacting with the matrix.Their structure is indistinct, borders between com-ponents are blur, it seems that fragments of fillersare separated by a polymer. Such a picture indicateson apparent compatibility between fillers and thematrix. Some tactoids that contain montmorillonitelayers are not parallel thus, disorder of clay signifi-cantly increases during mixing of the polymer withfillers. SEM photos of polypropylene mixed withammonium salt modified montmorillonite show

excellent homogeneity of the obtained samples. Nomineral parts of dimensions above 500 nm are vis-ible. Magnification is too low to confirm exfolia-tion of montmorillonite, but on the basis of visiblestructure of the polymeric mixture it is very prob-able. Presented photos confirm that the laboratorymethod used by us for the preparation of compos-ite samples was correct.

Mechanical properties of the original polypro-pylene and composites of montmorillonite basedon polypropylene are collected in Table. Presenteddata are the average values calculated from threeindependent measurements. Since the addition topolymeric matrix more than 5% w/w of the fillercauses a significant growth of viscosity in meltedstate, the experiments were performed at a concen-tration of ca. 2.9% w/w of dispersed phase. Samplesof polypropylene mixed with unmodified bentonite,except for one composite from a very fine, labora-tory purified sample of montmorillonite, showedinsufficient mechanical properties: they were veryfragile and cracked at low elongation. One of the

Fig.4. SEM images of polypropylene filled with bentonite “Special” modified by maleic anhydride and irradiated with adose of 26 kGy (cross-section of thin foil) at different magnifications.

Table. Mechanical properties of polypropylenes filled with modified bentonites.


representative examples of these results is shownin Table.

In all the composites the yield stress is unaffectedor slightly increased in comparison with the pristinepolymer, while the tensile strength decreases forall the studied components. The elongation at breakdrops for Tixogel VP and “SW” composites from790 to 686% and 549%, respectively, and increasesto 808% when clay loading is bentonite “Special”.Generally speaking, the presence of the montmo-rillonite, even upon modification, does not have alarge effect on the mechanical properties of thecomposites, but the role of purity of montmorillo-nite is visible. Unexpectedly, poor results are ob-tained for composites of polypropylene and mont-morillonite “Special” modified with two types ofammonium salt, although the samples observed inSEM have shown excellent dispersion of the fillersin the polymer matrix.

The best mechanical properties exhibit polypro-pylene filled with extra fine, laboratory preparedmontmorillonite modified with maleic anhydrideand irradiated; quality of composites containing (inorder) “Special”, Tixogel VP, and “SW” bentonitesare lower. The melt transition of polypropylene is162oC and increases upon dispersion of montmo-rillonite in the matrix.

Modification of the different types of bento-nite by absorption of maleic anhydride, followed by

irradiation with electron beam shows that particlesobtained in this process are good fillers for the pro-duction of composites on the basis of polypropy-lene. Some properties of final materials are betterthan those of initial polypropylene, especially forcomposites obtained from modified and irradiatedmontmorillonite with low impurity level.

Ionizing radiation facilitates compatibilizationof MMT/MA fillers with the matrix due to intro-duction of organophilic bridges between dispersedminerals and polypropylene. However, anhydridesare not able to intercalate significantly into inter-layer galleries increasing d-spacing. The proposedprocessing might reduce the contribution of maleicanhydride and inhibit the degradation associatedwith the presence of larger amount of anhydride.

This work was supported by the State Com-mittee for Scientific Research (KBN) – grantPBZ-KBN-095/T08/2003.

References

[1]. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K.:Modification of montmorillonite fillers by ionizingradiation. In: INCT Annual Report 2005. Institute ofNuclear Chemistry and Technology, Warszawa 2006,pp. 34-35.

[2]. Polish Patent Application P. 379779 (2006).[3]. Filho F.G.R., Jeferson T., Melo A., Rabello M.S., Silva

M.L.: Polym. Degrad. Stabil., 89, 383-392 (2005).

POLY(SILOXANEURETHANE) UREASBASED ON ALIPHATIC AND AROMATIC DIISOCYANATES

MODIFIED BY IONIZING RADIATIONEwa M. Kornacka, Grażyna Przybytniak, Janusz Kozakiewicz1/, Jarosław Przybylski1/

1/ Industrial Chemistry Research Institute, Warszawa, Poland

Ionizing radiation is often used to sterilize medicaldevices made from polymeric materials. However,except lowering the level of bioburden, irradiationaffects physicochemical and mechanical propertiesof polymers leading usually to degradation or/andcrosslinking. A proportion between both processesdetermines final effect. Among products that aresupposed to be sterilized are polyurethanes used asscaffolds for culturing of biological (e.g. human)cells for tissue engineering purposes. Recently, seg-mented polyurethanes have been studied exten-sively due to their biocompatibility and excellentmechanical properties [1]. One of the interestingexamples of such a material is polyurethane con-taining siloxane soft segments that provide hydro-lytic stability, elasticity and chemical inertness. It

seems that during irradiation urethane-based prod-ucts can undergo chain scission at urethane hardregions as well as at siloxane segments. The charac-ter of isocyanates used for polymerization, propor-tions between NCO and OH groups and the lengthof siloxane chains determine resistance of materialstowards ionizing radiation. Data obtained from therecent investigations show that radical processes inaliphatic poly(siloxaneurethane) ureas (PSURURs)proceed predominantly in siloxane segments [2].Nevertheless participation of urethane domains alsomust have an influence on direction and yield ofradiation-induced reactions. Their contribution isdetermined by NCO/OH ratio as the excess of NCOgroups is converted to urea bonds in a moisture-cur-ing processes. The length of isocyanate sequences

Scheme.


in hard segments increases with concentration offree isocyanate units in a prepolymer [3]. Hard andsoft segments create two distinct microphases (orin some cases even macrophases). On the otherhand, it is generally accepted that urethane or ureagroups form extensive hydrogen bonding systems.Yilgör et al. found that the strength of hydrogenbonds between urethanes is much weaker than be-tween urea links due to highly polar character ofthe later group [4]. Thus NCO/OH ratio changesproperties of urethane based polymers and is sup-posed to modify their radiation resistance. On theother hand, quantum mechanical calculations indi-cated the absence of interaction between siliconesand urea groups [5].

The polyurethane based materials were pre-pared from methylene di(p-phenyl isocyanate) orisophorone diisocyanate, oligosiloxanediol andwater used as a chain-extending agent (Scheme).The synthesis was performed with the prepolymermethod [1].

Samples of structures shown in Table were in-vestigated by electron paramagnetic resonance(EPR) after exposure to a dose of 6 kGy in a 60Cogamma source (Issledovatel) under cryogenic con-ditions, i.e. at 77 K, since free radicals appeared tobe unstable at ambient temperature.

EPR measurements were performed on anX-band Bruker ESP 300 spectrometer. Spectrawere recorded directly upon irradiation of thesamples and after their annealing to indicated tem-peratures.

Samples of PSURURs investigated by gas chro-matography were irradiated with a 10 MeV elec-tron beam generated in a linear electron accelera-tor Elektronika 10/10 to indicated doses. The totaldoses were obtained by multipass exposure (30 kGyper one pass).

The yield of hydrogen in the gas phase vola-tilize from irradiated at room temperature poly-mers was determined with a gas chromatographShimadzu-14B. The thermoconductivity methodwas used for detection.

The EPR spectra recorded under cryogenicconditions for PSURURs of structures presentedin Table are shown in Fig.1.

A triplet of hyperfine splitting near 2.2 mT isthe dominant component of all experimental sig-nals. A centerfield absorption varies and dependspredominantly on the proportions between NCOand OH groups and a length of –[Si(CH3)2O]n–units. Previous studies revealed that the triplet is

associated with the occurrence of methylene radical,≡SiCH2· that was identified also in oligosiloxanediolsapplied as substrates in PSURUR synthesis [2].

One representative EPR spectrum recorded foroligosiloxanediol of n=10 is shown in Fig.2(a). Theproportion 1:2:1 among lines characteristic of in-teraction of two equivalent protons is perturbeddue to sharp singlet situated in the middle of thespectrum that has been attributed to the siliconradical ≡Si·. Thus, the methylene radical is pro-duced by hydrogen abstraction whereas the sili-cone one by losing the methyl group. An evidencefor Si-C bond scission might be also found in somespectra detected upon irradiation. Enlargement ofthe scale leads to the disclosure of quartet charac-teristic of the methyl radical, A(3H)=2.3 mT. Thegaseous product decays just at 77 K, therefore onlytraces of CH3· were detected in some samples(Fig.2(c)). The efficiency of methylene radical pro-duction in siloxane segments was determined onthe basis of analysis high field peak indicated inFig.1 with an arrow in all experimental spectra. Thisexternal line does not represent superposition ofsignals but exclusively a side peak of the triplet.Depending on the structure of PSURURs, eitherspectrum shown in Fig.2(a) or a signal of its ana-logue for n=30 were used for quantitative analysis.

Relative concentration of methylene radicals de-pends on –[Si(CH3)2O]n– size; for n=30 the contri-bution is significantly higher than for n=10, both inaromatic and aliphatic urethanes (Fig.3). Introduc-tion of aromatic rings determines also relative con-centration of siloxane radicals. Aliphatic PSURURsshow a smaller relative contribution of paramagnetic

Table. Composition of PSURUR.

Fig.1. EPR spectra of listed in Table PSURURs irradiatedto a dose of 6 kGy at 77 K.


quence 1>3>4, for NCO/OH=2, 2.5, 3, respec-tively. When the ratio NCO/OH increases, unpairedspins more frequently are localized at urethane andurea bonds. Character of the intermediates is un-known as the EPR spectra that could be assignedto such radicals take the shape of unresolved singlet(Fig.2(b)). The signal represents radicals of unpairedspin localized at heteroatoms.

Lost of hydrogen atoms is expected in both seg-ments, hard and soft. Yields of the product measuredby the gas chromatography method are shown inFig.4. Emission of H2 in aliphatic PSURURs, 2 and6, significantly prevails over that found for aromaticpolyurethanes. The results directly indicate thatdeposited radiation energy initiates radical pro-cesses more effectively if polymeric chains compriseisophorone ring instead of phenyl groups.

The yield of hydrogen abstraction for aromaticPSURURs is above three times smaller than fortheir aliphatic analogues as can be concludedfrom the comparison of G(1) and G(2), as well asG(5) and G(6) values. Dissipation of radiation en-ergy by aromatic rings involves protection againstradical processes not only in urethane segments butalso in siloxane domains. The G values of aromaticPSURUR are comprised in the narrow range from0.20 to 0.36/100 eV. It seems that the influence ofNCO/OH ratio plays an insignificant role in hydro-gen release.

species in siloxane units than aromatic ones sinceenergy deposited in soft domains and aliphatic re-gions of hard segments rather induces radicals thanis transformed into heat, as it takes place in aromatichard segments. Thus, comparison of the results ob-tained for samples 1-2 and 5-6 (Fig.3) leads to theconclusion that the ability to dissipation of ioniz-ing radiation energy by phenyl groups diminishesthe population of radicals.

Distribution of radical centers varies dependingon NCO/OH proportions; the amount of methyleneradicals for n=10 decreases in the following se-

Fig.3. Relative concentrations of methylene radical ≡SiCH2·determined on the basis of analysis of EPR signals(see text).

Fig.4. Radiation yield of hydrogen determined by gas chromatography (A) and consumption of oxygen resulting fromradical processes (B).

Fig.2. EPR spectrum of (a) oligosiloxanediol, n=10, irra-diated at 77 K; (b) signal obtained by subtraction ofspectrum (5) from (3) presented in Fig.1 assigned toradicals that unpaired spins are localized at hetero-atoms; (c) experimental evidence for production ofCH3·.


Simultaneously, with radiation yield of H2, theconsumption of oxygen from the space above thesample inserted in the vial was estimated (Fig.4(b)).Considerable scattering of results makes detailedanalysis impossible. However, all G(O2) values foraliphatic PSURURs are in a similar range as G(H2)data found for aromatic analogues. Thus, unex-pectedly, O2 consumption in aliphatic PSURURsis much lower than the hydrogen yield. Such a dis-proportion between results might be tentativelyinterpreted as a result of very efficient recombi-nation between carbon centered radicals leadingto crosslinking. It seems that in aliphatic PSURURsthe yield of oxidation processes is very limited,however this suggestion needs further investiga-tions.

In aromatic PSURURs, the concentration ofradicals situated at hard segments is lower than inaliphatic ones due to efficient dissipation of ioniz-ing radiation energy. Therefore, the relative con-centration of methylene radicals is higher and theyield of dehydrogenation is much smaller than in

polyurethanes prepared from isophorene cyanate.To some extent the protection effect spreads overthe whole polymeric material. Proportion betweenurethane and urea groups do not influence hy-drogen abstraction processes that proceed only inhydrocarbon regions or in methyl groups of siloxaneunits. It seems that aliphatic PSURURs have a ten-dency to efficient crosslinking.

References[1]. Kozakiewicz J.: Advances in moisture-curable siloxane-

-urethane polymers. In: Advances in urethane scienceand technology. Eds. K.C. Frisch, D. Klempner. Lan-caster-Basel: Technomic Publ. Co. Inc., 2000, vol. 14,pp. 97-149.

[2]. Kornacka E.M., Kozakiewicz J., Legocka I., PrzybylskiJ., Przybytniak G., Sadło J.: Polym. Degrad. Stabil.,91, 82 (2006).

[3]. Kwiatkowski R., Włochowicz A., Kozakiewicz J., Przy-bylski J.: Fibres Text. East. Eur., 11, 5, 107 (2003).

[4]. Yilgör E., Yilgör I.: Polymer, 42, 7953 (2001).[5]. Yilgör E., Burgaz E., Yurtsever E., Yilgör I.: Polymer,

41, 849 (2000).

RADIATION EFFECTS IN POLYPROPYLENE/POLYSTYRENE BLENDSWojciech Głuszewski, Zbigniew P. Zagórski

Several applications of polymers demand resistancetowards ionizing radiation, e.g. for disposablemedical devices sterilized by radiation, for appli-cations in nuclear industry and in nuclear reactors,also for outer space localizations etc. Dependingon the nature and extent of radiation damage, sol-ution of the problem consists in application of ad-ditives, produced for general application of poly-mers. They work often very well also as a protectionfrom radiation damage, especially when they con-tain aromatic groups which act as energy sink viaenergy transfer mechanism. Some additives are notacceptable, especially in medical applications andone of the aims of this investigation was to answera question if an aromatic polymer as an additivecan limit the extent of radiation damage. However,the main topic of the project is basic research onclassic aliphatic/aromatic energy transfer, this timeextended from small molecules to polymers.

Freeman [1] first has found that in irradiatedsimple system of cyclohexane/benzene, radiolytichydrogen was not formed in proportion to the com-position, i.e. benzene was reducing the hydrogenyield to a higher degree than was expected. Theeffect was investigated later in several laboratoriesand was called “deviation from the mixture law”.It was investigated also in frozen systems, gaininginteresting facts connected with the solid crystal-line state. Deviation from the mixture law was neverinvestigated systematically in the field of radiationchemistry of polymers. Albano et al. investigatedthe polypropylene/polystyrene (PP/PS) 20/80%blends, at low doses [2] and high doses [3] (70-400kGy) with resulting full protection of polypropylene,to be expected.

As in the case of cyclohexane/benzene system,the hydrogen production was used as a basic indi-

cation of radiolysis extent, but in the chosen sys-tem of polypropylene/polystyrene, also formationsof methane and carbon monoxide (after oxidativeexperiments) in the function of dose and compo-sition were studied, as well as kinetics of oxygenconsumption in the presence of air. Further stagesof oxidative degradation of polypropylene werestudied by diffuse reflection spectrophotometry(DRS) [4,5].

Introduction of small molecule additives intopolymer composition is simple, but preparation ofaliphatic/aromatic polymer blends is more com-plicated and demanded new procedures. The caseof polypropylene/polystyrene, i.e. of a semicrystal-line, nonpolar thermoplastic polymer with a polar,amorphous polymer is known to be immiscible.Mechanical mixing proved formation of unsatis-factory blend from the point of view of energytransfer, but other approaches resulted in a propermixture.

Sample “A” was prepared by mixing commercialpolymers: polypropylene Malen P J-400Z*1632/01from Basell-Orlen and polystyrene from Owispol--Dwory. The proportions were: 0, 10, 25, 50, 75,100% of polystyrene. In spite of the most thoroughblending injection and pressing in a mechanicalway, the surface area of contact between both poly-mers was assumed not to be as most favourablefor energy transfer and, therefore, two other pro-cedures of sample preparation have been developed.Sample “B” was prepared from virgin polypropy-lene (F 401) in the shape of powder, collected fromthe Orlen-Olefins production line, without addi-tives, next impregnated with polystyrene dissolvedin a styrene monomer (fresh distilled, free fromstabilizers) in proportion of polypropylene/poly-styrene as above. Afterward, the styrene was removed


tion against radiolysis of polypropylene by poly-styrene (Figs.1 and 2). Mechanical methods can-not secure sufficiently large interphase for energytransfer. Classical case of previously investigated,protection phenomena, i.e. benzene/cyclohexanewas effective only in liquid state or frozen from thegas phase. Application of grafting of styrene onpolypropylene, by two slightly different proceduresresulted in a proper response to expected protec-tion effect. It extended, according to a vague esti-mate to be a distance of 9-12 mers of polypropy-lene. Thus, the classical case of radiation protectioneffect in the benzene/cyclohexane system has beenextended into the field of polymers. The solid statesystem benzene/cyclohexane shows energy transferonly if it is crystallized from the gas phase to secureclose contact of constituents. In the case of polymericsystem of polypropylene/polystyrene, the mechani-cal mixing is not sufficient and the effect of energytransfer occurs only in the case of impregnated andgrafted samples. Chains of both polymers, aliphaticand aromatic must have sufficient area of contact-ing, or exhibit low distance sites for energy transferto the aromatic structure, which is the sink of en-ergy.

This investigation was supported by a grant No.0989/T08/2005/28 from the Polish Ministry of Edu-cation and Science.

References

[1]. Freeman G.R.: J. Chem. Phys., 33, 71 (1960).[2]. Albano C., Reyes J., Ichazo M., Gonzáles J., Hernán-

dez M., Rodrígues M.: Polym. Degrad. Stabil., 80, 251(2003).

[3]. Albano C., Reyes J., Ichazo M.N., González J., Rodrí-guez M.: Nucl. Instrum. Meth. Phys. Res. B, 208, 485(2003).

[4]. Zagórski Z.P.: Int. J. Polimer. Mater., 52, 323 (2003).[5]. Zagórski Z.P.: Rafalski A.: Radiat. Phys. Chem., 48,

595 (1996).[6]. Zagórski Z.P.: Radiat. Phys. Chem., 22, 409 (1983).

by evaporation during gentle heating. Sample “C”was prepared by soaking polypropylene powder withstabilizer – free styrene and polymerization/graft-ing in the gamma field from cobalt-60 at a doserate of 1.5 kGy/h. All added styrene has polymerizedtotally, but the adjusted percentage was checkedgravimetrically as in sample ”B”. Polymerizationgrafting of styrene proceeds in a chain mechanismin the presence of polypropylene, with high radia-tion yield (12 000 effects/100 eV), due to the gen-erous supply of free radicals by irradiated polypro-pylene. Styrene alone (the same batch), gamma- orelectron beam irradiated, polymerizes very slowlyand the progress of reaction can be followed by theincrease of viscosity only. All proportions of bothpolymers were checked by weighing the final prepa-rations. All irradiations, except gamma exposurementioned above, were done with electron linacs,“Elektronika” 10/10 (10 MeV, 9 kW) or “LAE 13/9”(up to 13 MeV, 9 kW straight beam, or 6 kW bentbeam of improved monoenergetic spectrum) [6].Determination of hydrogen, methane, and second-ary product carbon monoxide as well as of oxygenconsumption were done by gas chromatographyusing a Shimadzu GC 2040 and GC 2010, molecu-lar sieves 5A, in carrier gas argon.

The applied methods of analysis and investiga-tion, i.e. gas chromatography together with diffusereflection spectrophotometry have shown to beeffective in recognition of protection effects in ali-phatic/aromatic blends of polymers. Key interme-diates and final products of radiolysis have beendetermined, i.e. hydrogen, methane and carbonmonoxide.

For the preparation of blends and mixtures ofaliphatic/aromatic polymers three methods havebeen proposed. Conventional blending of polypro-pylene and polystyrene in Brabender and/or byinjection does not give desired results of protec-

Fig.1. Radiation yield of hydrogen in the function ofpolypropylene/polystyrene composition. A curvedoes not start at the same point as curves B and C,because a commercial polypropylene containing al-ready additives was in this case used. Curves B andC start from virgin polypropylene. Dose – 25-100kGy.

Fig.2. Radiation yield of methane in the function of polypro-pylene/polystyrene composition. A curve does notstart at the same point as curves B and C, because acommercial polypropylene containing already addi-tives was in this case used. Curves B and C start fromvirgin polypropylene. Dose – 25-100 kGy.


Oxidation of polymers in the atmospheric envi-ronment is responsible for the degradation of prop-erties. These processes are initiated by increasedtemperature and/or by UV light. Conventional pre-vention of these undesired phenomena in appli-cation of commercial polymers is the addition ofphotostabilizers and antioxidants. Radiation pro-cessing, e.g. radiation sterilization by electron beamor gamma radiation causes additional oxidation ofpolymers already during irradiation (polyethylene– PE, polypropylene – PP and many others), as wellas oxidation by oxygen after irradiation, by a chainmechanism, in particular in the case of polypropy-lene. The last mentioned reaction prevents theapplication of common polypropylene for produc-tion of medical objects to be sterilized by ionizingradiation. Conventional additives mentioned abovedo not help in full extent, therefore additional com-ponents are looked for, in particular among spe-cific aromatic compounds.

Observation of dynamics of oxidation processesin polymers is comfortable by the gas chromato-graphic method [1]. One record secures determi-nation of abstracted hydrogen, carbon monoxideand methane (Fig.1). The present report shows alsothe advantages of oxygen determination, in particu-lar the loss of oxygen, consumed in oxidation of a

polymer. Therefore, the determination of oxidationrate is easily measured, as well as the formation ofone of the oxidation products (Fig.2).

The integration of irradiation and gas chroma-tography determination, for the case of solids in-volved a special approach to the specific techniqueof electron beam irradiation of cells closed withsepta, and consideration of different solubility ofhydrogen in a variety of polymers, resulted in newprocedures. Three milliliter glass vials, closed bysepta, are filled only in one third with a sampleand only this part is irradiated with a straight beamof electrons from the linear electron acceleratorLAE 13/9, leaving the rubber septa intact. Thistechnique allows the application of small doses ofradiation energy, by triggering single pulses [2].

The use of straight beam of electrons has cre-ated some problems with dosimetry. The increased

inhomogeneity (in comparison to scanned beam)of the radiation field is neutralized by a special ala-nine – powder dosimetry, with the diffuse reflec-tion spectrophotometry (DRS) measuring method[3]. The method is using the fact that the free radi-cal derived from alanine shows an optical absorp-tion spectrum. The use of straight electron beam issimilar to its use in the first versions of our pulseradiolysis system. Application of higher, kilograydoses proved to be more convenient by conven-tional, technological irradiation on a conveyor, by

the bent beam of electrons. The septa are coveredwith a thick hood made of lead in this case. Experi-ment with an empty vial did not show the presenceof hydrogen, what has demonstrated no signifi-cant irradiation of septa made from rubber. Thistechnique was applied for high doses only; appli-cation of this mode for low doses of radiation yieldserratic doses, because of the structure of the beam.That limitation has been recognized already be-fore the construction of the machine and cannotbe avoided due to the pulsing regime of the accel-erator action and scanning frequency of 5 Hz. Lowerdoses were applied in a 60Co gamma source, withdue analysis of differences of radiation quality incomparison to the electron beam, if any.

A gas chromatograph Shimadzu GC 2014 hasbeen installed in an air conditioned and thermo-statted (23.5oC) room. The column was 1 m longpacked with molecular sieves 5A, the detector wasthermo-conductivity (TCD-2014) element by Shi-madzu. The carrier gas was argon (99.99%). Op-erations were done with syringes (volume – 10, 25and 500 μL). The system was working at 220oC, onthe column kept at 40oC and the detector at 120oC.The rate of flow of carrier gas was 10 mL/min.Parameters of separations are as follows:- H2: retention time – tR(H2)=1.48 min, coefficient

of oxygen – R(H2-O2)=2.7, coefficient of peaksymmetry – As(H2)=1.1, number of theoreticalshelves – N(H2)≈86;

APPLICATION OF GAS CHROMATOGRAPHY TO STUDYPOSTIRRADIATION PROCESSES OF POLYMER OXIDATION

Wojciech Głuszewski, Zbigniew P. Zagórski

Fig.1. Chromatographic retention (column packed withmolecular sieves 5A): H2, O2, N2, CO and CH4.

Fig.2. Radiation yields of H2, O2 and CO in the function ofpostirradiation time (polypropylene).


The gas chromatographic method has beenapplied also in the study of postirradiation oxida-tion processes of ageing polymers (Fig.5). The lossof oxygen helped to trace the oxidation process, andthe parallel production of hydrogen has helped toestimate the participation of aromatic compoundsin the process of blocking peroxide groups andcrosslinking with the polypropylene chain. Theseprocesses interrupt the cycle of polymer degrada-tion and can help in branching of chains, thus im-proving properties of the material. Analysis of theinfluence of polystyrene (PS) content on the oxi-dation process shows that the protection effect ishigher in the case of samples undergoing a longerageing process. One can explain that by the improvedcontact of aromatics with the polypropylene matrix.

These few examples have shown that a simpleand sensitive at the same time analytical methodhelps to investigate not only radiation oxidationphenomena but also photo- and thermooxidation.

The investigation was supported by a grant No.0989/T08/2005/28 from the Polish Ministry of Edu-cation and Science.

References[1]. Zagórski Z.P., Głuszewski W.: Application of gas chro-

matography to the investigations on polypropyleneradiolysis. In: INCT Annual Report 2005. Institute ofNuclear Chemistry and Technology, Warszawa 2006,p. 42

[2]. Głuszewski W, Zagórski Z.P.: Tworzywa Sztuczne i Che-mia, 3 (Suppl.), 28 (2006), in Polish.

[3]. Zagórski, Z.P.: Int. J. Polym. Mater., 52, 323 (2003).[4]. Głuszewski W., Zagórski Z.P.: Radiation effects on

PP/PS blends as model of aromatic protection effects.Nucl. Instrum. Meth. Phys. Res. B, submitted.

- O2: retention time – tR(O2)=2.77 min, coefficientof hydrogen – R(O2-H2)=2.5, coefficient of ni-trogen – R(O2-N2)=3.7, coefficient of peak sym-metry – As(O2)=1.2, number of theoretical shelves– N(O2)≈488.

The described method has proved its efficiencyin the description of protective action of naphtha-lene towards degradation of polypropylene [4](Fig.3). That method helped also to show that therate of radiation-induced oxidation of polypropy-lene at low temperature (under liquid nitrogen) ishigher than at ambient temperature (Fig.4). Thatis the first exception of the rule of rather loweredradiation yields of radiation-induced reactions atcryogenic temperatures. Further investigations in

this fragment of radiation chemistry will show towhat extent physical conditions in the system areresponsible for that exceptional behaviour.

Fig.3. Relation between naphtalene concentration inpolypropylene and radiation yield of oxygen.

Fig.4. Relation between polystyrene concentration inpolypropylene/polystyrene blends and radiation yieldof oxygen in temperature: -196oC, +22oC.

Fig.5. Relation between polystyrene concentration inpolypropylene/polystyrene blends and radiation yieldof postirradiation oxidation processes (postirradia-tion time: 24-108 h).

CHEMICAL-RADIATION DEGRADATIONOF NATURAL POLYSACCHARIDES (CHITOSAN)

Andrzej G. Chmielewski, Wojciech Migdał, Urszula Gryczka, Wojciech Starosta

Naturally occurring polysaccharides have a widerange of applications in agriculture, medicine andcosmetics, food industry and water waste treatment.

Chitin is second, next to cellulose, most abundantpolysaccharide on the earth. It is present in crusta-cean shells, insect exoskeletons and fungal cell walls.


Chitosan, (1-4)-2-amino-2-deoxy-β-D-glucan, isdeacetylated derivative of chitin. Commerciallyavailable chitosan possesses high molecular weightand low solubility in most solvents what limits itsapplications. The solubility of chitosan can be im-proved by decreasing its molecular weight [1].Water soluble chitosan can be prepared throughoxidative degradation with hydrogen peroxide inconcentration higher than 1 M [2]. Low molecularweight chitosan can be prepared by chemical, ra-diation or enzymatic degradation of a high molecu-lar weight polymer. Radiation is one of the mostpopular tools for modification of polysaccharides.For decreasing of the polymerization degree, com-bined chemical-radiation methods can also be used.Chitosan oligomers were obtained through irradia-tion of chitosan dissolved in acetic acid [3]. Anotherpopular method is also chemical degradation withhydrogen peroxide which even in small quantityreduces gradually molecular weight of chitosan [2].Treating plants with oligochitosan increase theirdisease resistance and also plant growth is stimu-lated. Degraded polysaccharides such as alginate,chitosan or carrageenan can increase tea, carrot orcabbage productivity by 15 to 40% [4]. Chitosan ir-radiated with 70-150 kGy strongly affect the growthof wheat and rice plant and reduces damages causedby vanadium. [5]. Alginate degraded with radiationat concentration 20-50 ppm promotes the growthof rice seedlings, at a concentration of 100 ppm itcauses an increase of peanut shoots by about 60%compared to control [6]. Foliar application ofchitosan on pepper plants reduces their transpira-tion and water use and the biomass-to-water ratiois significantly better in the treated plants comparedto the control plants [7]. Chitosan can also be usedin plant protection from diseases because it is astrong antimicrobial agent [8].

The goal of this work was to use radiation forpolysaccharide structure modification. Depolymer-ization of chitosan can be carried out by radiationor oxidative degradation with hydrogen peroxide

combined with irradiation with electron beam.Efficiency of degradation methods was verified byviscometric measurements using an Ubbelohdecapillary viscometer k=0.01073. Average molecu-lar weights were calculated from the equation:

[η] = K·Mwa

where: [η] – intrinsic viscosity; Mw – averagemolecular weight; K and a – constants for chitosanindependent of molecular weights, K=1,81·10–3

cm3/g and a=0.93 determined in 0.1 M acetic acidand 0.2 M sodium chloride solution at a tempera-ture of 25oC [9]. Results of vicometric measure-ment of chitosan modified with ionizing radiationare shown in Fig.1.

Results shown in Fig.2 indicate that irradiationof a dry powder of chitosan lead to the reductionof molecular weight. The Mw decreased remark-ably with increasing dose up to 200 kGy. For higherdoses, there was no significant change in molecu-lar weight. Hydrogen peroxide caused breaking of1,4-β-D-glucoside bonds, used at small concentra-tion caused a rapid decrease of molecular weight.Increasing concentration or reaction time did notaffect the further decrease of polymerization de-gree. Chitosan degraded with the chemical-radia-tion method attained 95% mass reduction. Usinghydrogen peroxide at the first stage of degradationthe required doses of radiation can be decreasedwhat is much more appropriate from the economi-cal point of view.

Figure 3 shows the X-ray diffraction patternsof initial chitosan and modified chitosan. Initialchitosan and after radiation exhibited two charac-teristic peaks at 2θ=8.9o and 2θ=20.2o. There is nochange in intensity of the peaks. Radiation degra-dation did not destroy crystal structure of chitosan.

Fig.1. Results of vicometric measurement of chitosan modi-fied with ionizing radiation.

Fig.2. Radiation and chemical-radiation degradation ofchitosan.

Fig.3. X-ray diffraction patterns of (a) initial chitosan, (b)chitosan after radiation degradation with a dose of250 kGy and (c) chitosan after chemical-radiationdegradation.


DSC STUDIES OF GAMMA IRRADIATION EFFECT ON INTERACTIONOF POTATO STARCH WITH THE SELECTED FATTY ACIDS

AND THEIR SODIUM SALTSKrystyna Cieśla, Hubert Rahier1/

1/ Department of Physical Chemistry and Polymer Science, Vrije Universiteit Brussel, Belgium

Differential scanning calorimetry (DSC) appearedto be the appropriate method for detection ofgamma irradiation influence on starch interactionwith lipids [1-3]. Structural modification of macro-molecules and possible changes in the lipid sur-rounding induced by gamma irradiation, as wellas possible modification of the lipid molecules,were found to affect the properties of the inclusionamylose-lipid complexes formed with naturallyoccurring lipids on heating wheat starch and flour(A-type) [1,2]. Our preliminary DSC studies havealso shown differences between the complexesformed by irradiated and the non-irradiated potatostarch (B-type) and admixed 1-mono-lauroyl glyc-erol [3].

Currently, the effect of potato starch irradia-tion with 60Co gamma rays using a 30 kGy dosewas studied on its interactions with two fatty acids(lauric and palmitic) and their sodium salts.

Irradiations with 60Co gamma radiation werecarried out in a gamma cell “Issledovatel” in theDepartment of Radiation Chemistry and Technol-ogy, Institute of Nuclear Chemistry and Technology.DSC studies were carried out using a DSC calori-meter of TA Instruments instaled in Vrije Univer-siteit Brussel (Belgium). DSC studies were carriedout during several heating-cooling-heating cycleswith a heating and cooling rate of 10oCmin–1. TheUniversal Thermal Analysis Package was appliedfor data analysis. The suspensions placed in herme-tically closed pans were characterized by the sur-factant : polysaccharide : water ratio of 1:10:10.This corresponds to 0.498 mmol of lauric acid,0.390 mmol of palmitic acid, 0.458 mmol of sodiumlaurate and 0.359 mmol of sodium palmitate per1 g of starch. DSC studies were carried out duringseveral heating-cooling-heating cycles with a heat-ing and cooling rate of 10oCmin–1. Additionally,some complementary studies were continued witha heating and cooling rate of 5oCmin–1 applyingthe smaller lipid to starch ratios. These values cor-respond to 0.274 and 0.137 mmol of sodium laurate

or sodium palmitate per 1 g of starch and 0.274and 0.68 mmol of palmitic acid per 1 g of starch.

Melting of dry solid lauric and palmitic acidsare accompanied by endothermal effects withpeaks at 45.2 and 65.5oC. Melting of both sodiumsalts occurs at a considerably higher temperatureand is accompanied by double thermal effects withpeaks at ca. 122 and 135oC. No influence of waterpresence was noticed on the temperature range ofmelting of both fatty acids, while melting of bothsodium salts occur under such conditions at a con-siderably lower temperature. During the first heat-ing, melting of lauric acid and sodium laurate inwater takes place in a temperature range lower

[4]. Kume T., Nagasawa N., Yoshii F.: Radiat. Phys. Chem.,63, 625-627 (2002).

[5]. Tham L.X., Nagasawa N., Matsuhashi S., Ishioka N.S.,Ito T., Kume T.: Radiat. Phys. Chem., 61, 171-175(2001).

[6]. Hien Q.N., Nagasawa N., Tham L.X., Yoshii F., DangV.H., Mitomo H., Makuuchi K., Kume T.: Radiat.Phys. Chem., 59, 97-101 (2000).

[7]. Bittelli M., Flury M., Cambell G.S., Nichols E.J.: Agric.For. Meteorol., 107, 167-175 (2001).

[8]. Zheng L.Y., Zhu J.F.: Carbohydr. Polym., 54, 527-530(2003).

[9]. Roberts G.A.F., Domszy J.G.: Int. J. Biol. Macromol.,4, 374-377 (1982).

For chitosan after chemical-radiation degradation,the first peak is not observed and the peak at2θ=20.2o is much less intensive. The results showthat chemical-radiation degradation of chitosancaused destruction of the crystal structure.

References[1]. Mao S., Shuai X., Unger F., Simon M., Bi D., Kissel T.:

Int. J. Pharm., 281, 45-54 (2004).[2]. Tian F., Liu Y., Hu K., Zaho B.: Carbohydr. Polym.,

57, 31-37 (2004).[3]. Choi W.S., Ahn K.J., Lee D.W., Byun M.W., Park H.J.:

Polym. Degrad. Stabil., 78, 533-538 (2002).

Fig.1. Thermal effects attributted to the melting of amy-lose-lipid complexes recorded during the first andthird heating of the system containing lauric acidadmixed to the non-irradiated and irradiated starch(at weight ratio equal to 1:10).


than gelatinization (the example in Fig.1; thermaleffect recorded at a temperature below 60oC).Melting of sodium palmitate starts also at a lowertemperature but continues during gelatinizationwhile sodium palmitate melts in the same tempera-

ture range as starch gelatinizes. Formation of theinclusion complex (exothermal) occcurs duringgelatinization of starch (endothermal). Accord-ingly, the lower total enthalpy was determined onthe basis of the second thermal effect than thatexpected for gelatinization of pure starch presentin the system containing simultaneously lauric acid,sodium laurate or sodium palmitate. Transition ofthe resulting amylose-lipid complex occurs in therange of higher temperatures. In the case of palmiticacid addition, decrease of joint enthalpy of gelati-nization and melting of lipid, in relation to the

separate enthalpies of both processes was, how-ever, less evident.

During the subsequent cooling and heatingcycles, the processes of crystallization and meltingof the amylose-lipid complexes and of free lipid,present in excess in the system, took place.

The differences were noticed between thermaleffects recorded for the non-irradiated and irradi-ated starch during the first cooling and during thesubsequent heating and cooling routes. However,only on addition of lauric acid the results correspondwell to those obtained previously for the complexesformed in wheat starch with naturally occurredlipids, or in the complexes formed by potato starchwith mono-lauroyl-glycerol [1-3]. Transformationsof starch lipid complexes occur then at lower tem-perature in the irradiated than in non-irradiatedsamples containing lauric acid as well on heatingand on cooling (Figs.1 and 2) and are accompaniedby a smaller enthalpy. Melting and crystallizationprocesses taking place during the course of ther-mal analysis induces in both cases ordering in thecomplex structure (proved by an increase in theenthalpy and temperature of the complex transi-tions). However, that effect is considerably largerin the case of non-irradiated starch than in the caseof irradiated starch.

Fig.2. Thermal effects attributted to the crystallizationamylose-lipid complex recorded during the first andthird cooling of the system containing lauric acidadmixed to the non-irradiated and irradiated starch(at weight ratio equal to 1:10).

Fig.3, Thermal effects recorded during the third heating andthe third cooling of the system containing sodiumpalmitate admixed to the non-irradiated and irradi-ated starch (at weight ratio equal to 1:10).

Fig.4. Thermal effects recorded during the first, second andthird cooling of the system containing sodium palmi-tate admixed to the non-irradiated and irradiatedstarch (at weight ratio equal to 1:10). The enthalpiesdetermined for the first, second and third crystalliza-tion of the free-lipid phase in the non-irradiated sys-tem are equal to -6.0, -4, 8, -3,7 and the irradiatedsystem -3.8, -7.0, -8.6. The enthalpy determined formelting of this phase during heating was equal to 9.4and 9.2 both on the third and second heating of thesesystems.


In contrary to the previously examined systems,thermal effect that can be attributed to melting ofthe amylose-lipid complex occurs at higher tem-perature during heating of the system containingsodium palmitate and the irradiated starch as com-pared to that containing the non-irradiated one(Fig.3). However, similarly as in the previous cases,crystallization of the complex was observed at con-siderably lower temperature in the case of irradi-ated starch as compared to the non-irradiated oneand was accompanied additionally by the endother-mal process occurring in a low temperature range(Fig.3). Moreover, the differences were noticed be-tween the route of melting and crystallization of freelipid phase (examples in Fig.4). Therefore, meltingoccurs at lower temperature in the case of non-ir-radiated than irradiated starch. This can be attrib-

uted to the differences in the structure of the inter-mediate phase containing lipid and the non-irradi-ated and those containing lipid and the irradiatedstarch. Furthermore, after thermal treatment anincrease in the enthalpy of crystallization is observedin the system containing the irradiated starch, whilea decrease in enthalpy of crystallization occurs inthat containing the non-irradiated starch (Fig.4).This points out the weaker interaction between freelipids and non-irradiated starch as compared to theirradiated starch with additional weakening causedby thermal treatment of the irradiated system, incontrary to the strengthening induced in the non--irradiated starch. Simultaneously, no differenceswere noticed between enthalpies determined forthe second and the third melting of this phase inboth systems (Fig.4, the caption).

Similar results as in the system containing sodiumpalmitate were obtained in heating the system con-taining sodium laurate with that difference thatexothermal process accompanies melting of thecomplex formed in the mixtures containing the ir-radiated starch (Fig.5). This process probably con-

Fig.7. Thermal effects recorded during the first, second andthird cooling of the system containing palmitic acidadmixed to the non-irradiated and irradiated starch(at weight ratio equal to 1:10). The enthalpies deter-mined for the first, second and third crystallizationof the free-lipid phase in the non-irradiated systemare equal to -6.0, -4, 8, -3,7 and in the irradiated sys-tem -3.8, -7.0, -8.6. The enthalpy determined for melt-ing of this phase during heating was equal to 9.4 and9.2 both on the third and second heating of thesesystems.

Fig.5. Thermal effects attributed to the melting of amy-lose-lipid inclusion complexes recorded during thesecond and third heating of the system containingsodium laurate admixed to the non-irradiated andirradiated starch (at weight ratio equal to 1:10).

Fig.6. Thermal effects attributed to the melting of amy-lose-lipid inclusion complexes recorded during thesecond and third heating of the system containingpalmitic acid admixed to the non-irradiated and ir-radiated starch (at weight ratio equal to 1:10).


sist in crystallization of the complex phase duringmelting (resulting probably in the increased peaktemperature) and was not detected in non-irradi-ated starch. The other difference is that crystalliza-tion taking place at the first, second and third cool-ing of the complexes formed in both irradiated andnon-irradiated starch was always accompanied bysingle exothermal effects with a peak at 89-90oC.A similar conclusion concerning the irradiationeffect on weakening the starch interaction with thefree lipid phase can be, however, derived as in thesystem containing sodium palmitate.

Formation of the inclusion complex occurs withlow efficiency in palmitic acid addition and duringthe third heating small effects of the complex melt-ing were detected only in the non-irradiated starch(Fig.6). However, a strong interaction were noticedbetween the starch and free-lipid phase (Fig.7). Thisconcerns probably formation of the so-called sur-face complex. In fact, the homogeneous residueswere obtained after thermal analyses performedwith a small palmitic acid content. These interac-

tions were considerably smaller in the irradiatedstarch as compared to the non-irradiated starch.

Although the differences were noticed betweenstructural properties of the connections formedbetween the irradiated and non-irradiated starchwith all the examined ligands, the effect of irradia-tion differs depending on the ligand. Moreover, thedifferences were detected between the influence ofthermal treatment on these properties.

The work was sponsored in the frame of Ministryof Scientific Research and Information Technologyresearch grant No. 2P06T 026 27.

References

[1]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 68,933-940 (2003).

[2]. Cieśla K., Eliasson A.-C.: J. Therm. Anal. Calorim.,79, 19-27 (2005).

[3]. Cieśla K., Eliasson A.-C.: DSC studies of gammaradiation effect on the amylose-lipid complex formedin wheat and potato starches. Acta Aliment., in press.

SURFACE TENSION STUDIESOF BINDING CETYLTRIMETHYLAMMONIUM BROMIDE

TO GAMMA IRRADIATED AND NON-IRRADIATEDPOTATO AMYLOPECTIN

Krystyna Cieśla, Henrik Lundqvist1/, Ann-Charlotte Eliasson1/

1/ Department of Food Technology Engineering and Nutrition, University of Lund, Sweden

Decrease in molecular weight and the order instarch granules affects gelatinization processes inboth A and B types of starch [1-4]. Accordingly,the influence of gamma irradiation was discoveredon the interaction of A-type starches with naturallyoccurring lipids [2,3]. In regard to the structuralmodification of macromolecules and the formationof short molecular products, differences were alsofound between the possibilities for binding at am-bient temperature of iodine by the irradiated andnon-irradiated starch and the structure of the result-ing products [4]. Accordingly, gamma radiation isalso expected to modify interaction of B-type starcheswith admixed surfactants: binding of the ligands andthe product properties.

Surface tension measurements have appeareduseful in studying the interaction of iodine and sur-factants with starch polysaccharides [5,6]. This isbecause that surface tension can be considered asa measure of the monomer surfactant in solution.Therefore, the more the monomer of surfactant insolution, the more the surface tension will decreasebefore micelles of surfactant start to form. At pres-ent, our preliminary results are shown dealing withthe effect of irradiation on binding of cetyltrimethyl-ammonium bromide (CTAB) on starch polysaccha-rides. The method was applied for examination ofthe process taking place at only slightly elevated tem-perature enabling to obtain homogeneous CTABsolution.

Waxy potato starch (a pure potato amylopectin)was obtained due to genetic engineering methods

and was kindly supplied by Lyckeby Stärkelsen(Sweden). The native dry amylopectin was irradi-ated with 60Co gamma rays with a 30 kGy dose in agamma cell “Issledovatel” installed in the Depart-ment of Radiation Chemistry and Technology,Institute of Nuclear Chemistry and Technology.Moreover, commercial potato starch was used forthe complementary experiments using a Brookfieldvoscometer. Native dry potato starch or 1% starchgels were irradiated with doses of 10, 20 and 30 kGy.

Axisymmetric drop shape analysis (ADSA) witha Tracker instrument (IT Concept, Longessan,France) installed at the University of Lund (Sweden)was applied for surface tension studies. A syringewith a u-shaped needle was lowered into the samplecell and an air bubble was produced from the syringe.The dynamic surface tension was measured by film-ing the rinsing buble and analysing the contour ofthe bubble. The experiments were performed at27oC (above the Kraft temperature of CTAB). CTABwas gradually introduced to 0.25% polysaccharidegel solutions and the effect of addition each por-tion of surfactant was studied on their surface ten-sion. The dynamic surface tension was monitoredfor one hour in each measurement and the equi-librium surface tension was determined as thevalue when a stable level was reached. The curvesrepresenting dependence of equilibrium surfacetension on CTAB concentration were then con-structed accordingly to the method described byLundquist et al. [6]. Appearance of the free CTABinduces a decrease in surface tension, while stabi-


lization of surface tension indicates the formationof micelles. The amount of CTAB bound to thesolution is thus shown by the difference betweenthe total amount of CTAB added and the amountof free CTAB. Micelles start to form at such CTABconcentration when the free energy of the surfac-tant in the micelles is less than in the surfactant –polysaccharide aggregates or as free monomer insolution. The critical association concentration ofCTAB is very low and in the present experimentbinding of CTAB to polysaccharides starts at themoment when the first portion of CTAB is added[6]. It was also discovered [6] that the same amountof CTAB can be bound to starch polysaccharides,independently on its structure (34 mmol CTAB permol glucose units). Four sets of experiments wereperformed for each irradiated and non-irradiatedstarch.

Differences were observed between the route ofsurface tension changes taking place due to CTABaddition to the non-irradiated and irradiated amy-lopectin solutions (Fig.). Binding of CTAB to theirradiated starch appeared more “co-operative” thanbinding of CTAB to the reference non-irradiatedstarch. The “more co-operative type of binding isshown by the more sigmoidal shape of the curve

representing the dependence of surface tension onCTAB concentration (Fig.). This occurs despitethe fact that binding of CTAB to potato amylopec-tin was proved to be, in general, of Langmuir type(apart from the first stage of process when elec-trostatic interaction of CTAB with starch phos-phate groups takes place) [6]. This means thatbinding occurs to a number of the equivalent siteson polysaccharides and the process is not influ-enced by the fraction of bound ligands. In oppo-site, binding of CTAB to amylose was found to bea cooperative process. This means that the forma-tion of the individual complexes is coupled to eachother. The increase in co-operative type of bindingafter irradiation might be thus explained in termsof appearance of the polysaccharide fraction con-

taining less branched molecules or even straightamylose chains as a result of radiation-inducedscission of the strongly branched polysaccharidechains.

Complementary studies were conducted usinga Brookfield viscometer for the gels prepared onthe way of prolonged heating at 90oC of commer-cial potato starch (non-irradiated and irradiatedusing various doses) with CTAB (at starch : CTABmass ratio equal to 1:0.08). Irradiation with a doseof 30 kGy of dry native starch induces ca. a 45-folddecrease in viscosity of its gel formed with CTABaddition (from 47.5 to 1.1 cP determined in thecase of 1.2% solutions) and ca. an 11-fold decreaseafter irradiation with a dose of 10 kGy (to 4.27 cP).This correspond to 12-fold decrease discoveredafter irradiation with the same dose of 10 kGy ingels formed using starch alone (from 105 to 8.8 cPdetermined for 2% solutions). The differencesbetween viscosities of both types of gels preparedusing the irradiated and control starch result dueto decrease in swelling power (by 2.5 times) andthe essential increase in the amount of the solublepolysaccharide (at least 4 times) induced by irra-diation [4]. Therefore, no particular conclusionconcerning the irradiation effect on capability ofstarch for CTAB binding can be drawn on the basisof the experiment performed for potato starch athigh temperature, similarly as on the basis of thesurface tension studies carried out at low tempera-ture for potato amylopectin. However, the capa-bility for further binding of CTAB was significantlyreduced when gel solution was submitted to irra-diation before addition of CTAB. This was shownby the presence of the crystallites of CTAB in theproducts obtained after addition of CTAB to theirradiated gels, while no free CTAB can be detectedin the case of those obtained under the same condi-tions but using the non-irradiated gels. Irradiationof the gels result in the more evident decrease inthe viscosity of the starch-CTAB system. A 50-folddecrease in the viscosity was found already afterirradiation with a 10 kGy dose (to 1.1 cP), with noparticular influence on further dose increase to 20and 30 kGy.

The work was done in the frame of the PolishMinistry of Scientific Research and InformationTechnology research grant No. 2P06T 026 27.

References[1]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 64,

137-148 (2002).[2]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 68,

933-940 (2003).[3]. Cieśla K., Eliasson A.-C.: J. Therm. Anal. Calorim.,

79, 19-27 (2005).[4]. Cieśla K., Eliasson A.-C.: DSC studies of gamma radia-

tion effect on the amylose-lipid complex formed in wheatand potato starches. Acta Aliment., in press.

[5]. Svensson E., Gudmundson M., Eliasson A.-C.: Colloid.Surfaces B: Biointerfaces, 6, 227-233 (1996).

[6]. Lundqvist H., Eliasson A.-C., Olofsson G.: Carbohydr.Polym., 49, 43-55 (2002).

Fig. Equilibrium surface tension of CTAB – 0.25% potatoamylopectin solution non-irradiated and irradiatedusing a 30 kGy dose.


GAMMA IRRADIATION INFLUENCEON STRUCTURE OF POTATO STARCH GELS STUDIED BY SEM

Krystyna Cieśla, Bożena Sartowska, Edward Królak1/, Wojciech Głuszewski1/ Analytical Centre, Warsaw Agricultural University, Poland

Decrease in molecular weight and ordering instarch granules induced by gamma irradiation in-fluences its gelling properties. An essential decreasein swelling power occurs after irradiation of starchand flour [1,2] and the resulting gels reveal signifi-cantly decreased viscosities as compared to thoseof the reference non-irradiated gels. This suggeststhat irradiation modifies structural properties of thegels. Accordingly, at present the studies dealing withthe influence of gamma irradiation on the structureof starch gels were initiated applying scanning elec-tron microscopy (SEM). Several procedures of gelspreparation were tested in purpose to select properconditions that could enable to observe differencesbetween the SEM images obtained for the non-ir-radiated gels and those irradiated applying variousdoses. The influence of each procedure on the re-sulting images was analysed. The differences be-tween the photos taken for the particular gels wererelated to the differences between their physicalproperties.

Solid potato starch (laboratory extracted) wasirradiated with 60Co gamma rays in a gamma cell“Issledovatel” installed in the Department of Ra-

diation Chemistry and Technology, Institute ofNuclear Chemistry and Technology (INCT). Thedoses of 5, 10, 20 and 30 kGy were used. Swellingpower of these samples were examined using themodified procedure of Eliasson et al. described indetails in [3]. Moreover, viscosity of the gels (2 wt%)were determined using a Brookfield viscometer.

Gels containing 10 wt% dry matter were pre-pared on the way of heating starch suspensions for45 min in glass tubes placed in a heating chamberstabilized at 100oC. These gels were submitted tofour experimental procedures. The first series of gelswas rapidly frozen in liquid nitrogen and examineddirectly at depressed temperature. The second se-ries was also rapidly frozen in liquid nitrogen butafterwards lyophilized. The third series was obtainedon the way of rapid freezing, further storage at -18oCfor two weeks followed by chemical staining andcritical point drying. The fourth series was preparedon the way of chemical staining and critical pointdrying of the gels obtained after slow cooling andstorage at 4oC for 2 days. Chemical staining wasperformed accordingly to the modified procedureof Kaczyńska et al. [4].

Fig.1. Images recorded (at magnification x600) at depressed temperature for the gels frozen in liquid nitrogen: upperrow – fractures, non-irradiated and irradiated; lower row – surfaces, non-irradiated and irradiated.

0 kGy 30 kGy

0 kGy 20 kGy


Fig.2. Typical areas of the gels recorded after rapid cooling at liquid nitrogen and further lyophilization: upper row –fractures, lower row – surfaces. Magnification of all images is x1000.

0 kGy 0 kGy

30 kGy 30 kGy

5 kGy 5 kGy

10 kGy 10 kGy

20 kGy 20 kGy


Fig.3. Typical images obtained for the gels recorded after chemical staining followed by the critical point drying: upperrow – fractures of the gels obtained on the way of rapid freezing (all at magnification x1000), lower row – gelsslowly cooled and stored at 4oC (at magnification x500).

0 kGy 0 kGy

5 kGy 5 kGy

10 kGy 10 kGy

20 kGy 20 kGy

30 kGy 30 kGy


SEM studies were conducted using a DSM 942Scanning Electron Microscope (Zeiss-Leo produc-tion) for measurements carried out at ambienttemperature of dried samples covered with a thingold layer. The instrument is installed in the INCT.The rapidly frozen gels were examined at depressedtemperature (-15oC) at low vacuum using a Quanta200 Microscope (FEI) installed at the AnalyticalCentre, Warsaw Agricultural University. The frac-tures and surfaces of gels were examined.

Images of all the non-irradiated gels indicate ahoney-comb structure, independently of the way offurther treatment, with that difference that lyophiliza-tion induces thinning of the comb walls, as com-pared to the samples examined directly after freez-ing or those submitted to the chemical staining.

Smooth areas, but with oriented fractures, haveappeared after irradiation of the rapidly frozen gelsexamined at depressed temperature both at thefractures and at the surfaces (Fig.1). Smoothingshows a higher homogeneity of the irradiated gels.Orientation results probably due to the preparationprocedure and is caused by the weak internal forcesof the soft irradiated gels as compared to the gravi-tation force or to the applied mechanical stress.Both homogeneity of the gels and the weakeningof their internal forces was proved by a decrease inviscosity. Therefore, a 12-fold decrease in viscositywas found already after irradiation with a dose of10 kGy (from 105 cP determined for the non-irra-diated 2% gel to 8.8 cP). Swelling power decreaseslinearly with irradiation dose applied. The amountof gel formed after irradiation with a 30 kGy doseis equal to ca. 0.35% of that formed before irra-diation [1].

Similarly, irradiation induces the appearanceof flat and smooth structural elements in the caseof rapidly frozen but lyophilized gels (Fig.2). Thiswas observed already after irradiation performedusing a dose of 5 kGy. Moreover, further crackingof these smooth surfaces led to the appearance oflamellar structure. Further increase in the size oflamellas, and, consequently, the formation of largeblocks (observed in the gels fractures) as well asthe secondary porosity detected on their surfacesresult with increasing irradiation dose.

Similar observation concerning orientation andthe lamellar structure formation can be done for

the fractures of the rapidly frozen and chemicallystained gels (with orientation starting from a 10kGy dose radiation) (Fig.3) as in the case of theselyophilized after freezing. Smoothness of the sur-faces and a lamella size increased with irradiationdose alike in the case of lyophilized gels, while sur-face porosity of secondary type was avoided in con-trary to these gels owing to the chemical staining.

Fragile, brittle gels were obtained after storageat 4oC followed by chemical staining (Fig.2).Smoothing of the gels can be stated after irradia-tion with 5 kGy, while the lamellar structure resultsat higher doses (10 kGy) with further rupture ofthe lamellas (20 and 30 kGy). The radiation effectwas, however, less evident than in the other cases.This occurs probably because of the influence ofstaining procedure on the final structure of thesesoft gels.

Our results show that SEM enable to observe thedifferences between the structure of the non-irra-diated potato starch gels and those irradiated apply-ing various doses. The appropriate preparation pro-cedures were selected enabling to detect structuralmodification of gels. Moreover, the relationshipwas found between modification of gel structureand the applied dose. Similar irradiation influenceon gel surfaces and fractures can be stated on thebasis of SEM images obtained after rapid freezingof gels independently of their further treatment.The radiation effect on the images of the gels slowlycooled and stored at 4oC was, however, less evident.The differences in structural properties of gelsshown by SEM result due to the radiation-inducedweakening of the internal forces in gels and in-crease in their homogeneity.

The work was sponsored in the frame of thePolish Ministry of Scientific Research and Informa-tion Technology research grant No. 2P06T 026 27.

References[1]. Cieśla K., Eliasson A.-C.: DSC studies of gamma radia-

tion effect on the amylose-lipid complex formed inwheat and potato starches. Acta Aliment., in press.

[2]. Cieśla K.: J. Therm. Anal. Calorim., 74, 1271-1286(2003).

[3]. Eliasson A.-C.: Starch/Stärke, 37, 411-415 (1985).[4]. Kaczyńska B., Autio K., Fornal J.: Food Struct., 12,

217-224 (1993).

Intensive growth of various industrial branches andthe use of chemicals in agriculture results in increas-ing flux of anthropogenic toxic pollutants to natu-ral environment. A significant group of these pol-lutants are pesticides, because of the wide use in

contemporary agriculture, their toxicity and in manycases slow degradation in natural environment.Pesticide residues are detected both in the environ-ment (waters, soil), and also in vegetables and fruits,as well as in processed food. Hence, constant need

RADIOLYTIC DEGRADATION OF FUNGICIDE CARBENDAZIMBY GAMMA RADIATION FOR ENVIRONMENTAL PROTECTION

Anna Bojanowska-Czajka, Przemysław Drzewicz, Zbigniew Zimek, Bogdan Szostek1/,Henrietta Nichipor2/, Marek Trojanowicz

1/ DuPont Haskell Laboratory for Health and Environmental Sciences, Newark, USA2/ Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus,

Minsk, Belarus


for improvement and simplification of analyticalmethods for the determination of pesticides in vari-ous samples is obvious, as well as development oftechnologies for their effective removal from in-dustrial wastes and environmental media.

Fungicides and chemicals used for the destruc-tion of unwanted fungi in various applications, areemployed on a large scale since the 1960s, and sincethen their use constantly increases. Species of mostcommon use for this purpose are thiabendazole,fuberidazole, benomyl, methyl thiophanate andcarbendazim (MBC – methyl-2-benzimidazole car-bamate) [1]. Carbendazim is also a product of hy-drolysis of benomyl and methyl thiophanate. Thestructure of carbendazim is shown in Fig.1. It is usedfor protection of crops, fruits and vegetablesagainst fungal diseases, and also for protection ofharvested products during their storage and trans-portation. Its toxicity is well documented [2], henceits residues are considered as environmental pol-lutants.

Methods of decomposition of carbendazim, de-scribed so far in the literature are based on photo-lysis by UV irradiation in various chemical condi-tions [3-7]. The main subject of those works wasthe determination of yield of carbendazim pho-tolysis at different pH of irradiated solutions andvarious concentrations of dissolved oxygen. Theefficiency of carbendazim decomposition is facili-tated by alkaline pH, where the non-dissociatedform of the substrate is present (protonation con-stant for carbendazim pKa=4.2), and in the pres-ence of oxygen in irradiated solution [6].

The aim of this study was to develop a highpressure liquid chromatography (HPLC) methodfor simultaneous determination of carbendazimand its decomposition products, identification ofproducts of gamma radiolysis of carbendazim andexamination of different factors affecting the effi-ciency of radiolytic degradation of carbendazim,including dose rate, initial concentration and pHof irradiated solutions.

For monitoring the effectiveness of radiolytic de-composition of carbendazim and studies of mech-anism of this process, investigation on the develop-ment of HPLC method enabling simultaneousdetermination of carbendazim and products of its

degradation observed in similar processes has beencarried out. These products include benzimidazole,2-aminobenzimidazole, aniline, o-phenylenedi-amine and 2-hydroksybenzimidazole. It was foundthat pH of the eluent affects significantly reten-tion time of the determined compounds and shapeof chromatograms. The pH 8.0 and wavelength 277nm were selected as optimum for separation in fur-ther measurements.Effect of the initial concentration and pH

It was found that the radiation dose needed for90% degradation of carbendazim increases almostlinearly with the value of initial concentration offungicide in the examined concentration range20-100 μmol L–1 (Fig.2). The reported measure-ments have been carried out in aqueous solution atpH 7.

In preliminary experiments with carbendazimthe effect of pH on the yield of decomposition ofcarbendazim was examined in solutions non-ir-radiated and gamma-irradiated. It is reported inthe literature and confirmed experimentally inthis work that aqueous solutions of carbendazimin acidic and neutral media are stable for at least3-4 months, while slow hydrolytic decompositionoccurs at highly alkaline solutions (Fig.3), where2-aminobenzimidazole has been detected byHPLC.

Fig.2. The effect of initial concentration of carbendazim in gamma-irradiated aqueous solutions on (A) yield of decom-position at different irradiation doses and (B) the magnitude of the dose required for 90% decomposition ofpesticide.

Fig.1. Structure of carbendazim.


In gamma-irradiated aerated solutions of car-bendazim 100 μmol L–1 in the pH range from 3 to10 practically complete decomposition has been ob-served at small doses up to 0.6 kGy (Fig.4). In alka-

line solutions it occurs slightly faster and this can beattributed to simultaneous hydrolysis. It is oppo-site to observations reported for photochemical de-composition, which was strongly affected by pH ofthe initial solution of carbendazim [6].

Radiolytic decomposition in oxidatingand reducing conditions

Irradiation of aqueous solutions of carbendazimhas been carried out in different conditions, wheresolutions were saturated with air, argon or nitrogenmonoxide, and without or with added tert-butanol,hence the different products of water radiolysis pre-dominate in further reactions with the target com-pound (see Table in Fig.5). In solutions saturatedwith nitrogen monoxide, efficient scavenging of sol-vated electrons and hydrogen radicals takes place [8]:H· + N2O → N2 + ·OH k = 2.1 x 106 mol–1 L s–1

eaq + N2O → N2 +OH·– k = 9.1 x 109 mol–1L s–1

and as result of that, the largest yield of hydroxylradicals is obtained. The addition of tert-butanolto irradiated solutions is used to scavenge hydroxylradicals according to the reaction [9]:OH·+ (CH3)3COH → H2O + ·CH2C(CH3)2OH

k = 6 x 108 mol–1L s–1

So, in such case reducing conditions exist and radi-cal reactions with solvated electron or hydrogen radi-cals predominate. In solution containing tert-butanolin acidic media additionally solvated electron isscavenged, hence the reaction with hydrogen radi-cals predominates. In solutions saturated with argonin neutral media all three main oxygen containingradicals can react with the target pesticide.

In experiments carried out at different irradia-tion doses it was found that in conditions wherehydroxyl radical predominates the yield of carben-dazim decomposition is the largest, that means theirradiation does need for more complete decom-

Fig.5. Radiolytic decomposition of aqueous 100 μM solutions of carbendazim in different conditions: N2O-saturated solutionat pH 7.0 ( ), saturated solution at pH 7 ( ), argon-saturated solution at pH 1.5 with added 106 μM tert-butanol( ) and argon-saturated solution at pH 7.0 with added 106 μM tert-butanol ( ).

Fig.4. The effect of pH of irradiated solutions of carben-dazim on yield of decomposition at initial concen-tration 100 μM.

Fig.3. Protonation equlibrium and hydrolysis of carbendazim [6].


anism of occurring processes. In photochemicalprocesses as the main product of decomposition ofcarbendazim, 2-aminobenzimidazol has been iden-tified [7], while when the process was carried out inthe presence of hydrogen peroxide hydroxy deriva-tives of carbendazim were postulated [3]. In our ex-periments carried out in different conditions, withHPLC measurements using mass spectrometry de-tection different products of decomposition werefound in different conditions (Fig.6). When oxida-tion with hydroxyl radicals predominate as the prod-ucts of radiolysis hydroxybenzimidazol and two iso-mers of hydroxycarbendazim were identified, whilein reducing conditions the main product in the ap-plied conditions benzimidazole was found.

position of fungicide is the smallest (Fig.5). Muchless efficient is the decomposition in reducing con-ditions, where both reactions with solvated elec-tron or hydrogen radical predominate. At a 0.6 kGydose, only 50% yield of carbendazim decomposi-tion is observed, while in oxidizing conditions de-composition occurs with 100% yield. In aeratedsolutions at a dose of 0.6 kGy also satisfactory 90%yield of decomposition is observed, which is im-portant from eventual practical applications, wheresaturation with nitrogen monoxide would be toodifficult and expensive.

The identification of products formed in radiolyticdecomposition of carbendazim, in various condi-tions is important for the determination of mech-

Fig.7. Comparison of experimental results with kinetic modelling for radiolytic decomposition in different conditions: (A)effect of initial concentration, (B) irradiation of aqueous 100 μM solutions of carbendazim: N2O-saturated solutionat pH 7.0 ( ), saturated solution at pH 7 ( ), argon-saturated solution at pH 1.5 with added 106 μM tert-butanol( ) and argon-saturated solution at pH 7.0 with added 106 μM tert-butanol ( ). Full points – experimental results,open points – calculated data.

Fig.6. Chromatograms obtained for 100 μM aqueous solutions of carbendazim at pH 7.0 gamma-irradiated with 0.2 kGydose: (A) before irradiation, (B) irradiated in the presence of 106 μM tert-butanol saturated with argon, and (C)saturated with nitrogen monoxide. Eluent – 10 mM amonium acetate pH 8.0 with acetonitrile-gradient program.Column – Phenomenex C18(2) Luna 5 μM (250×4.6 mm). Flow rate – 1 mL/min. Detection at 277 nm. Peakassignment: (1) benzimidazole, (2) product of reaction with tert-butanol, (3) carbendazim, (4) product of reactionwith tert-butanol, (5) 5-hydroxycarbendazim, (6) hydroxybenzimidazole, (7) 6-hydroxycarbendazim.


At present, the main food products being suspectedas treated with the use of ionizing radiation arespices. Thermoluminescence (TL) examination ofminerals isolated from spices is the best, most sen-sitive method for the detection of irradiation inthese substances. However, mineral separation istime-consuming and needs special care. Therefore,the accomplishment of one TL analysis lasts usuallya few days. The second analytical method adaptedfor the detection of radiation treatment in spices ispulsed photostimulated luminescence (PPSL). Incontrast to the latter, the method is simple and fastbut has some limitations. In general, it is less sen-sitive than the TL method and is not capable ofmeasuring the luminescence in all kinds of spices.

Having both methods in the Laboratory ofDetection of Irradiated Food, Institute of NuclearChemistry and Technology (INCT), we performeda series of parallel experiments to prove the appli-cability of the PPSL method to detect irradiationin the variety of spices, herbs, composites with spicesand herbs admixed, and some other food products.Current research programme covers the PPSLanalysis of archival samples examined earlier by theTL method followed by the evaluation and com-parison of the results obtained with both methods.

Mineral debris of silicates and bioinorganiccomposites (calcite and hydroxyapatite) are thenatural contaminants of spices, herbs and season-ings. Mineral in food is composed mainly of quartzand feldspar, as proved earlier [1]. These debris arecapable of storing steadily the energy of ionizingradiation in charge carriers trapped at structural,interstitial or impurity sites. Charge carriers stableat ambient temperatures, are freed from mineraldebris by increasing the temperature (TL method)and/or under IR (infrared) illumination (PPSLmethod) [2]. Both methods enable to record thereleased energy, but methodological differencebetween them lies in the state of samples examined:TL measures isolated mineral fraction, i.e. silicate

minerals only, while PPSL IR stimulated lumines-cence the light released from all mineral and/orcrystalline components of the sample [3].

The detailed analytical procedure of samplepreparation for TL measurements are based onPN-EN 1788:2001 [4]; the sample treatment to pro-ceed PPSL measurements, in turn, are described inPN-EN 13751:2003 (U) [5].

TL examination is achieved with the use of PCoperated TL reader, type TL/OSL, model TL-DA-15(Risø National Laboratory, Denmark) under thefollowing measuring conditions: initial tempera-ture – 50oC, final temperature – 500oC, heating rate– 6oC/s.Routinely, the normalizing irradiation with 1 kGyof gamma rays from a 60Co gamma source is de-scribed in [4].

The routine preparation of samples [6] compilesgrinding, washing, density separation of a debris ofminerals contained in investigated products. Thisprocedures is time-consuming and takes normallya full workday.In TL, two criteria for the confirmation of radia-tion treatment are in force: glow ratio (glow 1/glow2) and the shape and maximum of radiation in-ducing TL within the temperature range 150-250oC.The details can been found elsewhere [4,5].

In contrast to TL, the preparation method ofsamples for PPSL examination is simple: the prod-uct is dispersed in Petri dishes used for the PPSLmeasurement. Some samples require earlier treat-ments like cutting or grating.PPSL measurement for customers is being doneby the calibrated measurement, equivalent to theTL normalizing procedure (re-irradiation withgamma rays). Such treatment delivers more ad-equate results, while luminescence measurementsare accomplished before and after exposing thesample to a defined dose of ionizing radiation. Therecommended calibrating dose as adapted in theLaboratory is from 1 to 4 kGy [5,7].

COMPARISON OF PPSL AND TL METHODS FOR THE DETECTIONOF IRRADIATED FOOD AND FOOD COMPONENTS

Grzegorz P. Guzik, Wacław Stachowicz

[2]. Tomlin C.: The pesticide manual. 10th ed. British CropProtection Council, Bracknell, London 1994.

[3]. Mazellier P., Leroy E., De Laat J., Legube B.: Environ.Chem. Lett., 1, 68-72 (2003).

[4]. Mazellier P., Leroy E., De Laat J., Legube B.: New J.Chem., 26, 1784-1790 (2002).

[5]. Fleeker J.R., Lacy H.M.: J. Agric. Food Chem., 25,51-55 (1977).

[6]. Pandés R., Ibarz A., Esplugas S.: Water Res., 34,2951-2954 (2000).

[7]. Boudina A. Emonelin C., Baaliouamer A., Grenier-Lou-stalat M.F., Chovelon J.M.: Chemosphere, 50, 649-655(2003).

[8]. Buxton G.V., Greenstock C.L., Helman W.P., Ross A.B.:J. Phys. Chem. Ref. Data, 17, 513-531 (1988).

[9]. Wojnárovits L., Takács E., Dajka K., Emmi S.S., RussoM., D’Angelantoniano M.: Radiat. Phys. Chem., 69,217-219 (2004).

Further research will be focused on compari-son of experimental data for irradiation in differ-ent conditions with modelling based on availablereaction rate constants for radical reactions, and alsoa study of similar processes in natural matrices ofindustrial wastes. Some preliminary results on com-parison of kinetic modelling with experimentaldata for the effect of initial concentration and ir-radiation of carbendazim solutions in different con-ditions are shown in Fig.7. The observed correla-tion is especially satisfactory for irradiation in dif-ferent conditions with different doses.

References[1]. Modern selective fungicides. Ed. C.J. Delp. Wiley,

London 1987, pp. 233-244.


Typically, irradiated samples indicate only a smallincrease of the PPSL signal, whereas in the non-irra-diated ones the increase is markedly higher.

A lower threshold (T1=700 counts/60 s) and anupper threshold (T2=5000 counts/60 s) are usedto classify the sample as non-irradiated (below 700counts/60 s) or irradiated (above 5000 counts/60s) [7-9].

Signal levels between the two thresholds are clas-sified as intermediate, and, if appear, the sampleneeds further investigations by means of the TLmethod [5,10].The total number of samples examined was 100.Consistent results were obtained with 64 samples(about 2/3), while non-consistent with 36 samples(about 1/3) of the total number of samples (Fig.).

There are three types of divergences of the PPSLmethod with TL results (Table 1). Nineteen samples(52.7% of the total number, i.e. above 1/2) couldnot be classified by means of PPSL. Three samples(8.3% of 36 samples in question) were qualified asnon-irradiated (resultant screening measurementis intermediate, while calibration measurement ispositive) or should not be investigated by meansof the PPSL method. For 14 samples (38.8% of 36samples in question i.e. above 1/3), the divergenceswere caused by too low sensitivity of the PPSLmethod. However, for a vast majority of the samples(almost 2/3), the results obtained by both PPSLand TL methods were found consistent.

Each type of the three divergences discussedabove compiles the variety of products that are clas-sified in Table 2.For example, the type “samples nonmeasurable bymeans of PPSL; TL only” is represented by severalproducts classified as: seasonings and spices, plantextracts, pharmaceuticals, processed food productsand food colouring dyes, respectively.

The type ”samples non-irradiated and/or needingto be approved by TL” gathers the products classi-fied as pharmaceuticals and processed food prod-ucts only.And finally, the type ”too low sensitivity of PPSLmethod; TL approval recommended” is representedby the products classified as: seasonings and spices,row seasoning herbs, plant extracts, pharmaceuti-

Table 2. The products investigated in the Laboratory.

Table 1. Qualification of samples as measured by the PPSL method.

Fig. Comparison of the results obtained by means of thePPSL and TL methods.


cals, fresh fruits and vegetables, dried vegetablesand mushrooms, respectively.

As seen, despite the fact that some differencesbetween the types do appear, it is not possible tosay in advances that a given product will delivereda given response in PPSL. In other words, each prod-ucts needs individual treatment.

In conclusion it can be said that PPSL is a veryuseful method for the qualification of food samplessuspected to be irradiated, but from the practicalpoint of view it seems reasonable to construct thelist of food products which can be easily examinedby PPSL and those which should be rather subjectedin advance to TL examination.

The results of TL examination of investigatedsamples, as used for present comparison, were de-livered by M. Laubsztejn, M.Sc. and Mrs G. Liśkie-wicz.

References[1]. Sanderson D.C.W., Slater C., Cairns K.J.: Radiat.

Phys. Chem., 34, 915-924 (1989).[2]. The SURRC Pulsed Photostimulated Luminescence

(PPSL) Irradiated Food Screening System. Usersmanual. Royal Society of Chemistry, Cambridge 2004,17 p.

[3]. Soika Ch., Delincée H.: Lebensm.-Wiss. Technol., 33,440-443 (2000), in German.

subsequently normalized having actually the statusof European standard PN-EN 13708 [5]. In thevalidation procedure the Laboratory for Detectionof Irradiated Food, Institute of Nuclear Chemistryand Technology (INCT), participated, too [6].

The aim of the present study was to prove theeffectiveness of the detection of irradiation in thevariety of sugar-containing food by the proceduregiven in PN-EN 13708 with the use of an EPR spec-trometer – EPR-10 MINI installed in the Labora-tory. This is the only acceptable way to adapt themethod for routine control of food in the INCT.

The investigated products were dried pineapple,banana, date, fig, papaya, and raisin. Each productwas divided into four samples irradiated with 0.5,1 and 3 kGy with 60Co gamma rays from an “Issle-dovatel” irradiator. The fourth sample was a con-trol.

The EPR measurements have been done inX-band with the use of the EPR-10 MINI mentionedabove and were conducted during 12 months.The measuring conditions were as recommendedin PN-EN 13708.Both the irradiated and non-irradiated sampleswere measured together with Mn2+ and DPPH stan-dards to evaluated the g factor in the centre of spec-tra and spectral width.

The selection of the resultant spectra recordedthrough the study is given in enclosed Figs.1-3.Figure 1 presents the spectra of dehydrated pine-

The method for the detection of irradiated food-stuffs containing crystalline sugar by the electronparamagnetic resonance spectrometry (EPR) isbased on the detection in the investigated productof stable free radicals evoked by radiation treatment.The majority of radicals produced by radiation infood is short lining and decays within a few secondsor minutes. However, if irradiated product containscrystalline sugar as one of the composites, the pres-ence of relatively stable radicals in the product isquite probable. The same concerns other food prod-ucts containing cellulose or bone, both character-ized by the presence of micro-crystalline structure.The crystalline domains in food, as proved in nu-merous experiments, are very effective in stabiliza-tion of radiation induced radicals that can survivefor months or years.

Due to the fact that in sugar-containing foods,the variety of mono- and disaccharides appear andthat in various products different proportion be-tween them occur, the EPR spectra recorded maydiffer, too. On the other hand, they differ from theEPR signals of single mono- and/or disaccharides.The intensity of signals, in turn, depends on thecontent of crystalline sugar in the product. So, theEPR detection of irradiation in sweet foods dependson the sufficient content of sugar crystals in the food[1-4].

The method of the detection of irradiation in foodcontaining crystalline sugar has been validated and

[4]. PN-EN 1788:2001: Foodstuffs – Thermoluminescencedetection of irradiated food from which silicate min-erals can be isolated.

[5]. PN-EN 13751:2003 (U): Artykuły żywnościowe – Wy-krywanie napromieniowania żywności za pomocąfotoluminescencji.

[6]. Research procedures PB-SLINŻ 03: Research pro-cedures and analysis of the results of the examinationof irradiated food by TL method (Wykonanie badańi analiza wyników badania napromieniowania żyw-ności metodą termoluminescencji). No. 3/2006 (inPolish).

[7]. Research procedures PB-SLINŻ 04: Research pro-cedures and analysis of the results of the examinationof irradiated food by PPSL method (Wykonaniebadań i analiza wyników badania napromieniowaniażywności metodą luminescencji stymulowanej świat-łem). No. 2/2006 (in Polish).

[8]. Guzik G.P., Stachowicz W.: Pomiar luminescencji sty-mulowanej światłem, szybka metoda identyfikacjinapromieniowania żywności. Instytut Chemii i Tech-niki Jądrowej, Warszawa 2005. Raporty IChTJ. SeriaB nr 3/2005 (in Polish).

[9]. Sanderson D.C.W, Carmichael L., Fisk S.: Food Sci.Technol. Today, 12(2), 97-102 (1998).

[10]. Sanderson D.C.W., Carmichael L.A., Naylor J.D.:Food Sci. Technol. Today, 9(3), 150-154 (1995).

DEVELOPMENT AND ACCREDITATION OF EPR METHODFOR DETECTION OF IRRADIATED FOOD CONTAINING SUGAR

Katarzyna Lehner, Wacław Stachowicz


apple, banana, date, papaya and raisin. The differ-ence in the shape of the spectra reflects the variousproportion and composition of sugars in the prod-ucts. However, gc factor is in all spectra similar,about 2.0035, while the spectral width varied from7.4 to 9.2 mT. Figure 2 shows the EPR spectra ofnon-irradiated pineapple, fig and banana. Thespectra are recorded at a high gain (see high noiselevel) and differ entirely from those of irradiatedstuffs. The signal, if present, is a narrow singletwith g about 2.0040. Distinction between irradi-ated and non-irradiated samples is very simple.Figure 3 shows the EPR spectra of the same sampleof papaya recorded 1 month and 1 year after radia-tion treatment. The shape of the signal did not

change, while its intensity decreased by about 35%(different attenuation of both spectra). Neverthe-less, the identification of irradiation is still simpleafter 1 year of storage, too.

The detection level of irradiation in dehydratedfoodstuffs was as follows: after exposure of samplesto 0.5 kGy of gamma rays, the radiation treatmentwas reliably detected with pineapple, fig, papayaand raisin. In banana and date the dose of 0.5 kGyis not detectable within experimental error. Theexposure to 1 kGy is detectable satisfactory. Thestability of the EPR signals after 12 months of stor-age was, in general, satisfactory, too. In additionto banana and date (see above), the dose of 0.5kGy could be detected at the lowest level of detec-tion with raisin only.

A reasonable reproducibility of the spectra wasachieved with the incidentally selected samples offig, papaya and raisin. No influence of the orienta-tion of samples inside the resonant cavity was ob-served.

Fig.3. EPR spectra of papaya 1 month (a) and 1 year (b)after radiation treatment. Dose – 0.5 kGy.

Fig.2. EPR spectra non-irradiated fruits: a) pineapple, b)fig, c) banana.

Fig.1. EPR spectra irradiated 3 kGy of dehydrated fruits:a) pineapple, b) banana, c) date, d) fig, e) papaya, f)raisin.


In view of the two European Union (EU) directiveson food irradiation (1999/2/EC [1] and 1999/3/EC[2]) the labelling of radiation treated food is obliga-tory. This regulation concerns food ingredients too,independently of their content in the product. Forthat reason, more and more frequently such prod-ucts as dried vegetal extracts and pharmaceuticalscontaining vegetal ingredients are delivered to theLaboratory for Detection of Irradiated Food, Insti-tute of Nuclear Chemistry and Technology (INCT),for examination. The standardized methods for thedetection of irradiation of foods were typically vali-dated with the use of selected products or groupsof products as spices, herbs, crystalline cellulose andsugars contained in food, etc.So, the reliability of these methods is related to theseselected products only.The aim of research activity of the Laboratory dur-ing the year 2006 was to prove the ability of the useof both thermoluminescence – TL (PN-EN 1788:2002)[3] and electron paramagnetic resonance spectros-copy – EPR (PN-EN 13708:2003) [4] methods forthe detection of irradiation in pharmaceuticals whichcontain vegetal components and typically mono-and polysaccharides as cohering agent.The experiments have been done with the samplesof 5 pharmaceuticals containing all these ingredi-ents. They are available in drugstores and resemblethe samples delivered for examination to the Labo-ratory. The product appears in the form of coated

pills (4 samples) and capsules (one sample). A partof the samples was irradiated with a dose of 5 kGyof gamma rays in November 2003, while the otherremained non-irradiated. It is supposed that theinvestigated samples contained garlic powder andvegetal dry extracts, talc, magnesium stearate, mono-and polysaccharides, colloidal silica and dyes liketitanium dioxide.Irradiated and non-irradiated samples were regis-tered as model samples and labelled in a way adaptedin the Laboratory (Table 1).

Samples for thermoluminescence (TL) exami-nation were subjected to analytical procedure ac-cording to PN-EN 1788:2002 in order to attain ef-fective isolation of mineral fraction from the remain-ing vegetal slurry. Subsequently, the mineral frac-tion was submitted to TL measurements with theuse of a computer operated TL reader under thefollowing conditions: initial temperature – 50oC,final temperature – 500oC, heating rate – 6oC/s. Tem-perature dependent glow curves were doubly mea-sured: once at the beginning and the second timeafter normalized irradiation with a dose of 1 kGywith gamma rays. The intensity of TL integratedover the temperature range 150-250oC and the TLglow ratio for irradiated and non-irradiated samplesare shown in Table 2.The criterion of the classification of irradiatedfoodstuff is based, according to PN-EN 1788:2002,on the evaluation of the TL glow ratio (glow 1/glow

* Sample irradiated with a dose of 5 kGy of gamma rays.

DETECTION OF IRRADIATION IN HERBAL PHARMACEUTICALSWITH THE USE OF THERMOLUMINESCENCE

AND ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRYMagdalena Laubsztejn, Kazimiera Malec-Czechowska, Grażyna Strzelczak,

Wacław Stachowicz

Table 1. Composition of investigated samples – main constituents.

The study was a basis for further validation ofthe method followed by its accreditation by thePolish Centre of Accreditation.

References[1]. Raffi J., Angel J.-P.: Radiat. Phys. Chem., 34, 6, 891-894

(1989).[2]. Raffi J., Angel J.-P., Ahmend S.H.: Food Technol.,

3/4, 26-30 (1991).[3]. Stachowicz W., Burlińska G., Michalik J., Dziedzic-Goc-

ławska A., Ostrowski K.: Radiat. Phys. Chem., 46, 4-6,771-777 (1995).

[4]. Stachowicz W., Burlińska G., Michalik J., Dziedzic-Goc-ławska A., Ostrowski K.: EPR spectroscopy for the de-

tection of foods treated with ionising radiation. In: De-tection methods for irradiated foods, current status. Eds.C.H. McMurray et al. The Royal Society of Chemistry,Information Service, 1996. Special Publication No. 171,pp. 23-32.

[5]. PN-EN 13708: Artykuły żywnościowe – Wykrywanie na-promieniowania żywności zawierającej cukry krysta-liczne metodą spektroskopii ESR. Polski Komitet Nor-malizacyjny, Warszawa 2003 (in Polish).

[6]. Raffi J., Stachowicz W., Migdał W., Barabassy S., Kal-man B., Yordanov N., Andrade E., Prost M., CallensF.: Establishment of an eastern network of laboratoriesfor identification of irradiated foodstuffs. Final reportof Copernicus Concerted Action CIPA-CT94-0134.CCE, 1998.


2) and on the analysis of the shape of the glow curverecorded within the temperature range 150-250oCfrom the mineral fraction isolated from food. TLglow ratio of irradiated food sample are typicallygreater than 0.1. However, in addition to the de-termination of glow ratio it is advised – in the Labo-ratory obligatory – to analyse the shape of the glowcurves (TL vs. temperature relationship) recordedfor both preliminarily isolated mineral fractions,and the same mineral fraction exposed to normal-

ized irradiation. Generally, the glow 1 curve forirradiated foodstuff has its maximum near to 200oC(±50oC). The mineral fraction isolated from foods

shows quite often a relatively strong TL at highertemperature with a maximum or maxima above300oC. This luminescence is presumably releasedfrom deep structural traps in a mineral and origi-nates from natural radionuclides (i.e. potassium,thorium, actinium) which appear in rocks and soil.

For example, the glow 1 curves recorded forsamples: SL/T3/A/06 (irradiated) and SL/T4/A/06(non-irradiated) are shown in Fig.1. The shape andthe temperature of the maxima (about 240oC), aspresented for selected sample, is typical of irradi-ated products. In comparison, the presented curvewith a low intensity and maximum defined near to350oC is typical of non-irradiated samples [3,5].The glow ratios calculated for all, irradiated andnon-irradiated samples are compared in the graph(Fig.2). The TL glow ratios for irradiated samplesare higher than 0.1, whereas the ratios for non-irra-diated samples are in all cases lower than 0.1.

The results obtained in the above described testexamination of pharmaceuticals with TL methodindicate conclusively that it is possible to proceedthe classification of this products whether irradi-ated or non-irradiated with the use of the criteriaapplicable to other food products, i.e. consistentwith PN-EN 1788:2002.

Samples for electron paramagnetic resonance(EPR) examination were prepared as follows: pillsand a capsule were mechanically crushed and thenthe samples weighing about 200 mg each were pouredinto thin wall sample tubes for EPR measurement,4 mm in diameter. For each sample three parallelaliquots were prepared.

Table 2. Thermoluminescence intensity of mineral fraction isolated from irradiated and non-irradiated pharmaceuticalsintegrated over the temperature range 150-250oC with the corresponding TL glow ratios.

Fig.1. Comparison of glow 1 thermoluminescence curves ofmineral fraction isolated from irradiated (SL/T3/A/06)and non-irradiated (SL/T4/A/06) pharmaceutical.


The samples were measured in the EPR spectro-meter Bruker ESP 300 under measuring conditionsrecommended in PN-EN 13708:2003 for examina-tion of foodstuffs containing crystalline sugar.The EPR spectra of the investigated samples areshown in Fig.3.

The recorded spectra of irradiated pharmaceu-ticals superpose on several complex spectra that,

in the majority, can be assigned to sugar born radi-cals. The width of the spectra was 7.2-7.6 ±0.2 mT,while the g factor in the centre of the spectra was2.0028 ±0.0002. The shape of the spectra is simi-lar, although a slight difference appears in the reso-lution and intensities of some spectra components.The signals resemble that of pure crystalline sugar.The observed EPR signals are stable. This was provedby the examination of all five samples two years

ago and then every month during half a year. Noevident decrease of intensity and/or change of shapeof the signals were observed.The EPR examination of non-irradiated pharma-ceuticals results in the recording of a weak single,symmetric line with g=2.0035 ±0.0035. Similarsingle lines are observed in non-irradiated foodstuffscontaining crystalline sugars.

The results of the presented experiments are agoal recommendation for the application of the rela-tively simple and fast EPR method for preliminaryexamination of pharmaceuticals to prove their ir-radiation prior to the obligatory TL examination.

Thermoluminescence examination of mineralfraction isolated from various pills and capsulesof herbal pharmaceuticals can be useful for theevaluation whether these products were irradiatedor not. The essential condition to proceed correctlythe TL examination of herbal pharmaceuticals inthe form of pills and capsules is a very careful analy-sis of results and looking deeper in the shape of theresultant glow curves than in the case of typical food-stuffs.

The EPR examination, in turn, enables the de-tection of radiation treatment of pharmaceuticalsin pills, if they contain as a binding-flavouring agentcrystalline mono- and/or poly-sugars.

The experiments show conclusively that the nextto TL method used for the evaluation of radiationtreatment of this product, if contains sugars, is theEPR method.

Present results prove the reliability of bothmethods for the detection of irradiation in herbalpharmaceuticals and are an important step of theirvalidation, opening perspective of their future ap-plication in practice. The examination of other prod-ucts of this type, containing vegetal components andsugars, is worthwhile of future including this com-bined detection method as one of those accreditedin the Laboratory today.

References[1]. Directive 1999/2/EC of the European Parliament and of

the Council of 22 February 1999 on the approximationof the Member States concerning foods and foodingredients treated with ionising radiation. Off. J.European Communities L 66/16-23 (1999).

[2]. Directive 1999/3/EC of the European Parliament and ofthe Council of 22 February 1999 on the establishmentof a Community list of food and food ingredientstreated with ionising radiation. Off. J. EuropeanCommunities L 66/24-25 (1999).

[3]. Standard PN-EN 1788:2002: Foodstuffs – Thermolu-minescence detection of irradiated food from whichsilicate minerals can be isolated.

[4]. Standard PN-EN 13708:2003: Foodstuffs – Detectionof irradiated food containing crystalline sugar by ESRspectroscopy.

[5]. Malec-Czechowska K., Stachowicz W.: Nukleonika,48, 3, 127-132 (2003).

Fig.3. EPR spectra (first derivative) of non-irradiated andirradiated pharmaceuticals.

Fig.2. Thermoluminescence glow ratios of investigatedpharmaceuticals calculated within the temperaturerange 150-250oC.


In 2006, the activity of the Laboratory for Detec-tion of Irradiated Food, Institute of Nuclear Chem-istry and Technology (INCT) was focused on thefollowing topics:- development of the methods for detection of

irradiated food implemented and accreditedearlier in the Laboratory;

- implementation and accreditation of two stan-dardized detection methods to be included tothe group of methods adapted for routine ana-lytical service for customers;

- analytical service to fulfil the growing require-ments of the customers representing firms andorganizations in the country and from abroad.The task is to classify the variety of more or lesscomplex food products delivered for examina-tion whether treated with ionizing radiation ornot.The development of detection methods accred-

ited in the Laboratory considers, generally speak-ing, the enlargement of the ability of the methodsto identify radiation treatment in food products ofa more and more complex composition as deliveredvery often by the customers for examination. The

reason of the growing interest of food trade in theexamination of complex products containing typi-cally only a small admixture of irradiated ingredi-ent (e.g. spices) has its source in the regulation thatare in force in all EU Member Countries now.These are stated in the Directive 1999/2/EC of theEuropean Parliament and of the Council [1]. Thedocument says that if a foodstuff contains irradi-ated ingredient constituting even less than 2.5%of the product, it is treated in the same way as afoodstuff that was irradiated in whole, in 100%.Taking into consideration the requirements of theLaboratory customers, we proceed research worksleading to the extension of the applicability of ourdetection methods to more complex foodstuffs, too.The survey of this works can be found in [2-4].

Now-a-day five detection methods implantedearlier in the Laboratory received PCA (PolishCentre for Accreditation) Accreditation Certifi-cate of Testing Laboratory Nr AB 262 issued on25.10.2006 and valid until 24.10.2010.

The list of detection methods, all addressed tospecific groups of foodstuffs is included in the Scope

of Accreditation Nr AB 262 and concerns the de-tection of radiation treatment in:- food containing bone, e.g. meat, poultry, fish and

egg shell (PN-EN 1786:2000) [5];- food containing crystalline cellulose, e.g. shelled

nuts, selected spices and some fresh fruits, asstrawberries (PN-EN 1787:2001) [6];

- food from which silicate minerals can be iso-lated, i.e. in the variety of spices, herbs, heirblends, dried and fresh vegetables, fresh shrimps(PN-EN 1788:2002) [7];

- food containing crystalline sugar, e.g. dried fruitslike dates, figs, raisins etc. (PN-EN 13708:2003)[8];

- food giving rise to photostimulated luminescence(PPSL), e.g. herbs, spices and their composities(PN-EN 13751:2003) [9].Article 7 (3) of the Directive 1999/2/EC says: “the

EU Member States shell forward to the Commis-sion every year the results of checks carried out atthe product marketing stage and the methods usedto detect irradiated foods”.Poland, the EU Member State, is obliged to fol-low the above regulation since 2004. Thus, the

country wide control and monitoring system offood to prevent illegal trade of irradiated prod-ucts has been established by the Chief SanitaryInspector of Poland. The samples of food prod-ucts available in the market are delivered to theLaboratory from the 16 provincial (voivodeship)sanitary-epidemiological inspections every year.

In Table, the number of both thermolumines-cence (TL) and electron paramagnetic resonance(EPR) examinations accomplished in the Labora-tory within this programme from 2004 to 2006 in-cluding foodstuff examined and classification ofsamples whether irradiated or not are compiled.

The results of 2004 monitoring is included inthe Report from the Commission on food irradia-tion for the year 2004 (3.20. Poland) [10].

In 2006, except for the above 39 samples, 339examinations of foodstuffs delivered by the Labo-ratory customers from abroad (Germany, Italy,United Kingdom, Denmark, Switzerland, France,Thailand – 315 samples) and from domestic firms(24 samples) have been done. The total number ofsamples examined for the customers in 2006 was

Table. The total number of samples in the Laboratory for Detection of Irradiated Food from 2004 to 2006 under ChiefSanitary Inspector of Poland programme.

ACTIVITY OF THE LABORATORY FOR DETECTIONOF IRRADIATED FOOD IN 2006

Wacław Stachowicz, Kazimiera Malec-Czechowska, Katarzyna Lehner, Grzegorz P. Guzik,Magdalena Laubsztejn


478. 87.9% of the total number of samples wereexamined by the TL method (PN-EN 1788:2002)while 12.1% by the EPR methods (PN-EN 1786:2000and PN-EN 1787:2001).

Among all food samples examined in 2006,93.7% were found not to be irradiated, while 6.3%samples were irradiated (Fig.1).

The assortment of foodstuffs that were examinedin 2006 (Fig.2) compiles:- spices, herbs and their blends that may contain

small admixture of irradiated spices as a flavouringredient (40.2%);

- seasonings, fresh and dried vegetables (5.4%);

- shrimps (18.6%);- herbal pharmaceuticals, herbal extracts (21.7%);- poultry and fish (3.6%);- nuts in shell (7.3%);- fresh fruits – strawberries (1.5%);- others, i.e. instant soups, red fermented rice, all

purpose savoury seasoning (1.7%).

References

[1]. Directive 1999/2/EC of the European Parliament andof the Council of 22 February 1999 on the approxi-mation of the Member States concerning foods andfood ingredients treated with ionising radiation. Off.J. European Communities L 66/16-23 (13.3.1999).

[2]. Guzik G.P., Stachowicz W.: Comparison of PPSL andTL methods for the detection of irradiated food andfood components. In: INCT Annual Report 2006. In-stitute of Nuclear Chemistry and Technology, War-szawa 2007, pp. 56-58.

[3]. Laubsztejn M., Malec-Czechowska K., Strzelczak G.,Stachowicz W.: Detection of irradiation in herbalpharmaceuticals with the use of thermoluminescenceand electron paramagnetic resonance spectrometry.In: INCT Annual Report 2006. Institute of NuclearChemistry and Technology, Warszawa 2007, pp. 60-62.

[4]. Lehner K., Stachowicz W.: Development and accre-ditation of EPR method for detection of irradiatedfood containing sugar. In: INCT Annual Report 2006.Institute of Nuclear Chemistry and Technology, War-szawa 2007, pp. 58-60.

[5]. PN-EN 1786:2000: Foodstuffs – Detection of irradi-ated food containing bone. Method by ESR spectros-copy.

[6]. PN-EN 1787:2001: Foodstuffs – Detection of irradi-ated foods containing cellulose Method by ESR spec-troscopy

[7]. PN-EN 1788:2002: Foodstuffs – Thermoluminescencedetection of irradiated food from which silicate min-erals can be isolated.

[8]. PN-EN 13708:2003: Foodstuffs – Detection of irradi-ated food containing crystalline sugar by ESR spec-troscopy.

[9]. PN-EN 13751:2003: Foodstuffs – Detection of irradi-ated food using photostimulated luminescence.

[10]. Report from the Commission on food irradiation forthe year 2004. Off. J. European Communities EN C230/28 (23.09.2006), 3.20. Poland.

Fig.2. Assortment of foodstuffs examined in 2006.

Fig.1. Classification of food samples taken for examina-tion in 2006.

RADIOCHEMISTRY

STABLE ISOTOPES

NUCLEAR ANALYTICAL METHODS

GENERAL CHEMISTRY

67RADIOCHEMISTRY, STABLE ISOTOPES,NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

103Ru/103mRh GENERATORBarbara Bartoś, Ewa Kowalska, Aleksander Bilewicz, Gunnar Skarnemark1/

1/ Department of Chemical and Biological Engineering, Chalmers University of Technology,Göteborg, Sweden

The possibility of using electron emitters to curecancer metastasis depends on the energy of theemitted electrons. Electrons with high energy givea high absorbed dose to large tumors, but the doseabsorbed by small tumors or single tumor cells islow, because the range of the electrons is too long.The fraction of energy absorbed within the tumordecreases with increasing electron energy and de-creasing tumor size. For tumors smaller than 1 g,the tumor-to-normal-tissue mean absorbed dose-rateratio (TND) will be low, e.g. for 131I and 90Y, becauseof the high energy of the emitted electrons. Forradiotherapy of small tumors, radionuclides emit-ting charged particles with short ranges (a fewmicrometers) are required. The short path lengthof particles also may limit toxicity to neighboringnormal tissue.

Using various selection criteria like electronenergy, suitable half-life, low photon/electron ratioand availability, Bernhardt and co-workers foundthat the Auger emitter 103mRh meets these criteria[1]. 103mRh has a short half-life (56 min) and is pro-duced via β– decay of 103Ru or EC decay of 103Pd.These mother nuclides have half-lives of 39 and 17days, respectively, and can be used as generators for103mRh. So far, however, only 103Ru has been testedas the generator, mainly because it is easy to pro-duce in large amounts, either by fission of uraniumor by neutron activation of ruthenium. For thera-peutic applications, the 103mRh would be attachedto, e.g. a peptides or monoclonal antibodies to findthe cancer cells.

The goal of the present work is the elaborationof a 103Ru/103mRh generator for milking therapeuticquantities of 103mRh. 103Ru. The mother nuclide of103mRh, was obtained by neutron irradiation of anatural ruthenium target at a neutron of flux 3x1014

n cm–2 s–1 in the nuclear reactor MARIA at Świerk.After 36 h irradiation of a 9.6 mg target, 130 MBqof 103Ru was obtained. The target was then dissolvedin a mixture of NaOH and KIO4. After completedissolution of the target, the solution was acidified,and RuO4 formed was extracted to an organic(CCl4) phase. To avoid reduction of RuO4 to RuO2,the organic phase was contacted with a solution

generating Cl2 molecules: 1 M HCl+KIO4. The Cl2molecules, formed in this solution are distributedamong the two liquid phases keeping RuO4 in theorganic phase. Milking of 103Rh was performed byshaking the organic phase with 0.01 M solution ofH2SO4 containing 0.2 mg ml–1 of KIO4.

In this pro-cess 103mRh is totally transferred to the aqueousphase together with small amounts of 103Ru. The

aqueous phase was purified from tracers of 103Ruby three times extraction with CCl4, and finally bypassing through an anion exchange resin. The re-sults of stepwise extractions are presented in Table.

If the ruthenium remained as RuO4 there wouldbe no problem; it would be easy to wash the rhodiumfraction a few times with a pure organic solvent toremove the contamination. Unfortunately, a smallfraction of the ruthenium in the aqueous phase isreduced to RuO4

– or RuO2, which are difficult toremove. The RuO4 was removed by few washingswith CCl4. The residue of 103Ru in the aqueous phasewas absorbed as RuO4

– on the anion exchange resin.The separation process involving three solvent

extractions with CCl4 and adsorption on an anionexchange resin gave separation factors between103mRh and 103Ru of more than 5x103.

The work was carried out in the frame of MarieCurie Action for the Transfer of Knowledge – con-tract No. MTKD-CT-2004-509224 with the Euro-pean Commission.

References[1]. Bernhardt P., Forssell-Aronsson E., Jacobson L.,

Skarnemark G.: Acta Oncol., 40, 602-608 (2001).

Table. Distribution coefficient for extractions of 103Ru and103mRh.

ZOLEDRONIC ACID LABELED WITH 47Sc AND 177LuFOR BONE PAIN THERAPY

Maria Neves1/, Ines Antunes1/, Agnieszka Majkowska, Aleksander Bilewicz1/ Nuclear and Technological Institute, Sacavém, Portugal

Bisphosphonates (BPs) have a strong affinity forcalcium phosphates and for hydroxyapatite. Be-cause of their chemical structure and the charac-teristic P-C-P- bond, which is non-biodegradableand non-hydrolysed in vivo, bisphosphonates have

been the chosen molecules for bone scanning im-aging. Some bisphosphonate compounds exhibitshort side chains, such as clodronate andetidronate;others have aliphatic chains of different lengths bear-ing terminal amino groups (pamidronate, alendro-

RADIOCHEMISTRY, STABLE ISOTOPES,NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY68

stronger complexes with zoledronate than 177Ludoes. This results from much smaller ionic radiusof Sc3+ than Lu3+.

The zoleodronates labeled with 46Sc and 177Lu inmolar ratio 100:1 was used for studies of adsorp-tion of labeled bisphosphonates on hydroxyapa-tite. Adsorption of bisphosphonates on hydroxy-apatite is commonly used as model for adsorptionof bisphosphonate radiopharmaceuticals on min-eral components of the bones. The dependence ofadsorption percent on the mass of hydroxyapatitesamples are shown in Fig.2.

The maximum adsorption, higher than 98%,was achieved by 177Lu-zoledronate using more than5 mg of hydroxyapatite, and by 46Sc-zoledronatefor more than 20 mg of hydroxyapatite.

The obtained results showed that 46Sc formsmore stable complexes than 177Lu zoledronate com-plexes, while the adsorption of 177Lu complexes onhydroxyapatite is higher than that of 46Sc-zoleodro-nate.

The work was carried out in the frame of MarieCurie Action for the Transfer of Knowledge – con-tract No. MTKD-CT-2004-509224 with the Euro-pean Commission.

References[1]. Neves M., Gano L., Pereira N., Costa M.C., Costa M.R.,

Chandia M., Rosado M., Fausto R.: Nucl. Med. Biol.,29, 329 (2002).

nate, and neridronate) or substituted amino groups(olpadronate and ibandronate). Among the lastgeneration of bisphosphonates with cyclic sidechains, zoledronate with a nitrogen atom in theimidazole ring, is the most potent bisphosphonatedescribed so far to inhibit bone resorption. Bis-phosphonates labeled with technetium-99mTc aremain radiopharmaceuticals used for bone scanningimaging. Bisphosphonates are also able to coordi-nate β-emitter as 153Sm and 186Re, and found ap-plication in clinical nuclear medicine for bone me-tastasis therapy (Re-186-HEDP-Metastron andSm-153-EDTMP-Quadramet). Until now, bis-phosphonates were labeled with β-emitters of rela-tively high energy like 153Sm, 188Re and 166Ho. Dueto a long distance interaction of hard β-particles,the degradation of bone marrow is observed. Toavoid this harmful effect we plan to apply bisphos-phonates labeled with soft β-emitters, e.g. 47Sc and177Lu instead of hard β-emitters. The distance ofparticles emitted by soft β-emitters in bone is muchshorter, less than 1 mm, therefore bone marrowwould not be affected.

The sample of sodium salt of zoledronic acid(1-hydroxy-2-imidazol-1-yl-phosphonoethyl) was agift from Novartis Pharma AG. Due to the shorthalf-life of 47Sc, the labeling of bisphosphonateswas studied using the γ-emitting 46Sc (t1/2=83.8 d)radiotracer.

46Sc and 177Lu radiotracers were obtained by neu-tron irradiation of Sc2O3 and Lu2O3 targets at a neu-tron flux of 3x1014 n cm–2s–1 for 6 h. The specificactivities of the radionuclides obtained were 100MBq/mg for 46Sc and 700 MBq/mg for 177Lu. Thetargets were dissolved in 0.1 M HCl solution. Theradiolabeling efficiency and stability evaluation ofthe radiocomplexes were accomplished by ascend-ing instant thin layer chromatography (ITLC) us-ing ITLC-SG (Polygram, Macherey-Nagel) stripsdeveloped with the mobile phase: H2O/NH3 (25:1).

The hydroxyapatite-binding assay was perform-ed according to the procedure described previouslyafter a slight modification [1]. In brief, to vials con-taining 1.0, 2.0, 5.0, 10.0 and 20.0 mg of hydroxy-apatite, were added 2 ml of saline solution at pH7.4 and the mixtures were shaken for 1 h. Then, 50μl of each radioactive preparation was added andthe mixtures was shaken for 24 h at room tem-perature. All suspensions were centrifuged and theradioactivity of the supernatant was measured withwell γ-scintillation counter. Control experimentswere performed using a similar procedure in theabsence of hydroxyapatite beads. The percentagebinding of 46Sc and 177Lu to hydroxyapatite (HAP)was calculated according to HA=(1 – A/B)*100,where A is the final and B – the initial activity ofsolution.

In ITLC studies, 46Sc and 177Lu zoledronate com-plexes migrate (Rf 0.8-1.0), while the ionic and col-loidal radioactive forms of 46Sc and 177Lu remain atthe origin. The labeling efficiency of zoledronate with177Lu and 46Sc, obtained from the ITLC studies, ispresented in Fig.1. As shown in Fig.1, 46Sc forms

Fig.2. Percent of 46Sc and 177Lu adsorption on hydroxyapa-tite as a function of hydroxyapatite mass sample.

Fig.1. Dependence of labeling efficiency of zoledronate onthe ligand-to-metal mole ratio.


Alpha-targeted therapy is a significant method fortreatment of small solid tumors and hematologicmalignancies (e.g. leukemias and lymphomas). Re-cently, these diseases are treated with convention-ally 131I or 90Y radiolabelled immunoconjugates, butwithout great success. These radionuclides emit beta--particles with ranges much larger than the diameterof a cancer cell. The maximum beta-energies varyfrom 0.5 to 2 MeV and the corresponding rangesare from 1-10 mm. This results in undesirable ir-radiation of normal cells such as stem cells in themarrow, even if the cancer cell is successfully tar-geted.

The alpha-particles are more suited for tiny clus-ters of cancer cells and micrometastases, becauseof their high energy (enable to make double strandbreaks in DNA) and short range, contributing totheir high linear energy transfer (LET) and radio-biologic effectiveness (RBE).

211At is one of the most promising alpha-emittersthat has, so far, been studied for cancer therapy.This isotope is artificially produced in a cyclotronvia the 209Bi(α,2n)211At reaction and has a 7.2 hhalf-life that allows sufficient time for its produc-tion, synthetic chemistry, quality control, transpor-tation and medical application. It decays by doublebranch pathway with a mean alpha-energy of 6.7MeV. As a consequence of its electron capturebranching to its daughter 211Po, X-rays of 71 to 92keV are emitted, enabling external imaging (includ-ing SPECT) and gamma counting of blood samplesas an additional advantage.

The current study was focused on finding a stablelabelled prosthetic group for the use in labellingof biomolecules with 211At. Our idea was to attachthe astatide anion using its halogen properties tosoft metal cations, which are complexed by a bi-functional ligand. We decided to use rhodium andiridium, because they are moderately soft metalcations, which should form very strong bond withthe soft astatide. The high kinetic inertness of thelow-spin d6 Rh(III) and Ir(III) complexes is also avery important advantage for the formation ofstable conjugate.

Macrocyclic sulphur ligand 1,5,9,13-tetrathia-cyclohexadecane-3,11-diol (16aneS4) was chosenfor model studies because it forms stable complexwith Rh(III) and can be modified to a bifunctionalchelate ligand [1]. Complexes between 211At, Rh(III)or Ir(III) and thioether ligand were synthesized inan aqueous ethanolic solution. The formation ofcomplexes was studied by heating the solution atdifferent time periods (15-120 min) and over a widerange of temperature (30-90oC). The pH was variedfrom 2 to 7.5 by addition of HNO3 or NaOH. Thequantity of Rh(III)/Ir(III) and 16aneS4 was changedin the range of 0.125-125 nmol and 2.5-250 nmol,respectively. All control experiments were carriedout under identical conditions with the exception

that thioether ligand was absent. First optimiza-tion of reaction conditions was performed with125I/131I isotopes and later repeated for 211At. For-mation and the radiochemical yield of the com-plexes were estimated by paper electrophoresis, ionexchange and high performance liquid chromato-graphy (HPLC) methods. Electrophoresis was per-formed using Whatman #1 paper strips. Reversedphase HPLC was carried out using a Beckman

Coulter device and a Waters Xterra RP18 columncoupled to a beta-detector for radiometric analy-sis. The gradient elution system utilized mobilephase A (deionized H2O) and mobile phase B(100% acetonitrile) and flow rate of 1 ml/min,started with 95%A/5%B for 5 min at which timethe linear gradient was initiated over 30 min inter-val to 100%B. Both mobile phases contained 0.1%trifluoroacetic acid (TFA). An example of HPLCradiochromatogram is shown in Fig.1. RP HPLCand the Waters Sep-Pak (C18) columns were alsoused to isolate the complexes from synthesis sol-ution for further stability studies. The in vitro sta-bility of complexes was determined in phosphate--buffered saline (PBS) at 37oC with the 131I isotopeas an analogue of astatine.

Fig.1. HPLC chromatogram of Rh[16aneS4]211At complexrecorded directly after formation: 1 – free unboundedastatide, 2 – peak of Rh[16aneS4]211At complex.

Rh[16aneS4]211At AND Ir[16aneS4]211At COMPLEXESAS PRECURSORS FOR ASTATINE RADIOPHARMACEUTICALS

Marek Pruszyński, Aleksander Bilewicz, Michael R. Zalutsky1/

1/ Department of Radiology, Duke University Medical Center, Durham, USA

Fig.2. Dependence of the complex formation on the Rh(III)and Ir(III) concentration.


cated the expected cationic character of the com-plexes. Both Rh(III) and Ir(III) complexes with 131Ishowed a good stability at pH 7.4 PBS after 51 hof incubation. The stability studies in human serumand biodistribution of complexes in normal miceare in progress.

Part of the work was carried out in the frame ofMarie Curie Action for the Transfer of Knowledge– contract No. MTKD-CT-2004-509224 with theEuropean Commission.

References[1]. Venkatesh M. et al.: Nucl. Med. Biol., 23, 33 (1996).

Dependence of the Rh3+ and Ir3+ mixed ligandcomplex formation on the metal cations and sulphurligand concentration are shown in Figs.2 and 3. In

Figure 4, the influence of pH of the solution onthe reaction yield is presented. Maximum complexformation yields 75 and 80% for Rh[16aneS4]211Atand Ir[16aneS4]211At, respectively, were obtainedat pH 3-5 after heating for 1-1.5 h at 75-80oC. Theoptimal concentration of Rh(III)/Ir(III) was 62.5and 250 nmol for sulphur ligand. The yield of thereaction with 211At was high, but less than with itsanalogue 131I. Paper electrophoresis analysis indi-

Fig.4. Yield of the complexes vs. pH of reaction.

Fig.3. Dependence of the complex formation on the16aneS4 concentration.

FORMATION KINETICS AND STABILITY OF SOMETRI- AND TETRAAZA DERIVATIVE COMPLEXES OF SCANDIUM

Agnieszka Majkowska, Aleksander Bilewicz

Radionuclides with medium energy beta-emissionand a several day half-life are attractive candidatesfor radioimmunotherapy. Among the most promis-ing in this category is 47Sc [1]. It has desirable nuclearproperties since it is a beta-emitter (Eβ1=600 keV,Eβ2(max)=439 keV) with a 3.35 d half-life. In ad-dition, 47Sc has a primary gamma ray at 159 keVthat is suitable for imaging. The methods for pro-duction high activities of 47Sc was described byKolsky et al. [2]. Enriched 47TiO2 target was irradi-ated with high energy neutrons (En>1 MeV) toproduce 47Sc via the 47Ti(n,p)47Sc reaction. Theseauthors also developed a new separation schemebased on cation exchange on a Dowex AG 50Wresin with elution of 47Sc using HCl/HF solution.

Sc3+ of ionic radius 74.5 pm (CN=6) is chemi-cally similar to Ga3+, In3+, Y3+ and to the heaviest

lanthanides, therefore ligands developed for thesecations should be suitable for chelating 47Sc. Inorder to find the best chelators for attaching 47Sc tobiomolecules the formation of Sc3+ complexes with1,4,7,10-tetraazacyclododecane-1,7-bis acetic acid(DO2A), 1,4,7,10-tetraazacyclododecane-1,4,7,10-te-traacetic acid (DOTA) and 1,4,7-triazacyclono-nane-1,4,7 triaacetic acid (NOTA), were studiedby capillary and paper electrophoresis and thinlayer chromatography (TLC). The formulae of theligands are presented in Fig.1.

The DOTA and DO2A ligands were purchasedfrom Macrocyclics. The NOTA ligand was synthe-sized by reaction of 1,4,7-triazacyclononane withbromoacetic acid. Chemical purity of the productwas checked by mass spectrometry (MS) and nu-clear magnetic resonance (NMR) methods. Stabil-

Fig.1. Ligands selected for complexation of Sc3+ cations.


ity constants of scandium macrocyclic complexeswere determined using capillary electrophoresis.The Sc3+ complexes were synthesized by mixing of1.5 mM aqueous solution of a given ligand with1.5 mM aqueous solution of Sc3+, at pH=3 forDOTA and NOTA, and at pH=5 for DO2A. Whenthe complexation process reached equilibrium (8days), small aliquots of the solution were injectedinto the capillary to determine the concentrationsof the complex, free Sc3+ and ligand, respectively.A typical electrophorogram is presented in Fig.2.

The conditional stability constants were calcu-lated based on the determined equilibrium con-centration of the free ligand using the proceduredescribed by Zhu and Lever [3]. Taking into ac-count the stepwise k1, k2, k3 and k4 protonationconstants of DOTA, the stability constants werecalculated. The results are presented in Table. Asshown in Table, Sc3+ forms most stable complexeswith the DOTA ligand similarly to the lanthanidesand Y3+.

The electrophoresis and ion exchange studiesindicate that Sc3+ forms complexes with differentcharge: anionic with DOTA, neutral with NOTAand cationic with DO2A. Therefore, we can con-clude that in DOTA complexes, Sc3+ has a coordi-nation number of 8, while in NOTA and DO2Aexhibit a coordination number of 6.

The kinetics of Sc3+ DOTA complex formationwas measured at pH=2, 3 and 4. The formation ofthe complex under this condition is quite rapid.The half-time of the equilibrium was reached in300 s at pH=2.04, in 236 s at pH=3 and in 106 s atpH=4.

The high thermodynamic stability and inertnessof the studied scandium chelates indicate that 47Sclabeled biomolecules could be an alternative to 90Yand 177Lu radiopharmaceuticals.

Part of the work was carried out in the frame ofMarie Curie Action for the Transfer of Knowledge– contract No. MTKD-CT-2004-509224 with theEuropean Commission.

References[1]. Mausner L.F., Kolsky K.L., Joshi V., Srivastava S.C.:

Appl. Radiat. Isot., 49, 285-294 (1998).[2]. Kolsky K.L., Joshi V, Mausner L.F., Srivastava S.C.:

Appl. Radiat. Isot., 49, 1541-1549 (1998).[3]. Zhu X, Lever S.Z.: Electrophoresis, 23, 1348-1356

(2002).

Table. Stability constansts of Sc3+ and Lu3+ complexes withDOTA, DO2A and NOTA ligands.

Fig.2. Electrophorogram of ScCl2 and DOTA mixture atbuffer pH 3, applied voltage – 10 kV, capillary – 50μm, length – 25 cm, detection wave length – 222 nm.Initial concentration ScCl2 and DOTA – 1.5 mM.

IN VITRO STABILITY OF TRICARBONYLTECHNETIUM(I) COMPLEXESWITH N-METHYL-2-PYRIDINECARBOAMIDE

AND N-METHYL-2-PYRIDINECARBOTHIOAMIDE – HISTIDINECHALLENGE

Monika Łyczko, Jerzy Narbutt

The strategy to design new 99mTc radiopharma-ceuticals involves incorporation of the radionuclideinto biologically active molecules, which requireschelating 99mTc at an appropriate oxidation stateand linking the obtained chelate to the biomolecule.The chelates should be stable, kinetically inert,small in size and moderately lipophilic. As a part ofour systematic studies [1-3] on tricarbonyltechnet-ium(I) chelates with the derivatives of picolinic andthiopicolinic acids: N-methyl-2-pyridinecarbo-amide (LNO) and N-methyl-2-pyridinecarbothio-amide (LNS); we studied the stability of these com-plexes using histidine challenge method. Histidineand cysteine challenge tests are often used to deter-mine in vitro stability of technetium complexes [4,5].

The 99mTc-LNO and 99mTc-LNS complexes wereobtained from their tricarbonyl precursor, fac--[99mTc(CO)3(H2O)3]

+, as described elsewhere [1].

Under conditions of the challenge experiments(0.07 M Cl–), two forms of the complexes were dis-tinguished, [99mTc(CO)3LNX(H2O)]+ and/or[99mTc(CO)3LNXCl] (X=O or S), the equilibriumbetween these two forms being dependent on theligand, LNX. The formation of each complex wasconfirmed by high performance liquid chromato-graphy (HPLC) analysis. Molecular structure of thecomplexes was confirmed by infrared (IR) studieson the analogous 99Tc and rhenium complexes fol-lowed by X-ray diffraction studies on the latter[1,6,7], and also by advanced quantum chemistrycalculations [2].

Histidine challenge experiments were performedby adding 0.5 mL of aqueous phosphate buffersolution (pH 7.4) containing 2·10–3 M histidine, to0.5 mL of the 99mTc complex solution containingexcess (2·10–3 M) of LNO or LNS. The samples were


complexes with bidentate ligands undergo signifi-cant substitution by tridentate histidine [8,9]. Inview of the above information, the 99mTc-LNO com-plex studied may be considered fairly stable, whilethe 99mTc-LNS complex is extremely stable. This dif-ference in the stability of both tricarbonyltechnet-ium(I) complexes well corresponds to that in theiryields [1]. On the other hand, the more negativeformation energy of the 99mTc-LNO complex calcu-lated for the gas state [2] can result from the dif-ferent configurations of the substrates and prod-ucts in the gas state and the aqueous solution, aswell as from different hydration energies of the LNOand LNS ligands in the solution [2].

Part of the work was carried out in frame ofMarie Curie Action for the Transfer of Knowledge– contract No. MTKD-CT-2004-509224 with theEuropean Commission.

References[1]. Łyczko M., Narbutt J.: Tricarbonyltechnetium(I) com-

plexes with neutral bidentate ligands: N-methyl-2-pyri-dinecarboamide and N-methyl-2-pyridinecarbothio-amide. In: INCT Annual Report 2005. Institute ofNuclear Chemistry and Technology, Warszawa 2006,pp. 71-74.

[2]. Narbutt J., Czerwiński M., Zasępa M.: Tricarbonyl-technetium(I) complexes with N,O- and N,S-donatingligands – theoretical and radiochemical studies. In:Proceedings of the DAE-BRNS Symposium on Nuclearand Radiochemistry NUCAR 2005, Amritsar, India,15-18.03.2005. Eds. K. Chander, R. Acharya, B.S. Tomarand V. Venugopal. BARC, Trombay, Mumbai 2005,pp. 64-67.

[3]. Narbutt J., Zasępa-Łyczko M., Czerwiński M., SchibliR.: Tricarbonyltechnetium(I) complexes with neutralbidentate ligands: N-methyl-2-pyridinecarboamideand N-methyl-2-pyridinecarbothio-amide. Experi-mental and theoretical studies. In: InternationalSymposium on Trends in Radiopharmaceuticals(ISTR-2005), Vienna, Austria, 14-18.11.2005. Book ofextended synopses. IAEA, Vienna 2005, pp. 61-62.

[4]. La Bella R., Garcia-Garayoa E., Bahler M., Blauen-stein P., Schibli R., Conrath P., Tourwe D., SchubigerP.A.: Bioconjugate Chem., 13, 599-604 (2002).

[5]. Alves S., Paulo A., Correia J.D.G., Gano L., SmithC.J., Hoffman T.J., Santos I.: Bioconjugate Chem., 16,438-449 (2005).

[6]. Fuks L., Gniazdowska E., Mieczkowski J., Narbutt J.,Starosta W., Zasępa M.: J. Organomet. Chem., 89,4751-4756 (2004).

[7]. Gniazdowska E., Fuks L., Mieczkowski J., Narbutt J.:Tricarbonylrhenium(I) complex with a neutral bidentateN-methyl-2-pyridinecarboamide ligand, as a precursorof therapeutic radiopharmaceuticals. In: InternationalSymposium on Trends in Radiopharmaceuticals(ISTR-2005), Vienna, Austria, 14-18.11.2005. Book ofextended synopses. IAEA, Vienna 2005, pp. 190-191.

[8]. Schibli R., La Bella R., Alberto R., Garcia-GarayoaE., Ortner K., Abram U., Schubiger P.A.: BioconjugateChem., 11, 345-351 (2000).

[9]. Bayly S.R., Fisher C.L., Storr T., Adam M.J., OrvigC.: Bioconjugate Chem., 15, 923-926 (2004).

incubated at 37oC and analyzed by means of HPLCafter 0.5, 2 and 24 h. After incubating the 99mTc-LNOcomplex for 0.5 h, a new peak of a moderate heightappeared in the chromatogram at 12.4 min (Fig.1),which corresponds well to the position of the[99mTc(CO)3histidine] complex. This means thathistidine partly replaces the LNO ligand in the com-plex. The relative magnitude of this 12.4 min peakafter incubating the 99mTc-LNO complex for 2 h isonly slightly greater than that after 0.5 h. On theother hand, in the chromatogram of the 99mTc-LNScomplex practically no peak of the histidine com-plex was observed even after incubation as long as24 h (Fig.2). Generally, tricarbonyltechnetium(I)

Fig.1. HPLC chromatogram of the [99mTc(CO)3LNO] com-plex after incubating (0.5 h, 37oC) with histidine sol-ution (the concentrations of histidine and LNO areequal to 1·10–3 M). Peaks: 1 – [99mTc(CO)3(H2O)3]+

(at 4.5 min) practically absent, 2 – TcO4–, 3a –

[99mTc(CO)3LNO(H2O)]+, 3b – [99mTc(CO)3LNOCl], 4– [99mTc(CO)3histidine].

Fig.2. HPLC chromatogram of the [99mTc(CO)3LNS] complexafter incubating (24 h, 37oC) with histidine solution(the concentrations of histidine and LNO are equalto 1·10–3 M). Peaks: 3a – [99mTc(CO)3LNS(H2O)]+

practically absent, 3b – [99mTc(CO)3LNSCl].


The “semi aqua-ion” fac-triaquatricarbonyltech-netium(I) (fac-[99mTc(CO3)(H2O)3]

+), 1, is a wellknown precursor of potential diagnostic radiophar-maceuticals labelled with 99mTc [1,2]. The carbonylligands are very strongly attached to the centralmetal ion due to dπ→pπ back-bonding. Substitu-tion of bi- or tridentate chelating ligands for thelabile water molecules leads to the formation ofnumerous complexes, both thermodynamicallystable and moderately kinetically inert. This inert-ness can be explained by the d6 electron configu-ration of the central metal ion in the octahedralenvironment [1]. Both 1 and its Re(I) analog (1a)are much more acidic than the aqua-ions of othermonovalent metals. Titration experiments withmacroamounts (10–3 M solutions of Re or 99Tc) re-sulted in: for 1a pKa≈7.5 [3], and for 1 pKa>8 [1]or pKa≈8.7 [4]. Oligomerization of the hydrolyzedspecies in macroamounts was also observed [1-4].In aqueous halide solutions the water molecules in1 are partly substituted by halide ions with the for-mation of rather weak neutral and anionic halidecomplexes [4,5]. The aim of the present work wasto study speciation of 1 at n.c.a. level in acidic aque-ous solutions, and in particular the ion exchangebehaviour of the various Tc(I) species.

The complex 1 was obtained following Alberto’smethod [1]. The yield exceeded 95%, the main im-purity being the non-reacted 99mTcO4

– anion (2) asdetected by high performance liquid chromato-

graphy (HPLC). Another impurity, 99mTcO2 (3) re-moved on a guard C-18 HPLC column, could notbe detected this way. To study the hydrolysis of 1 inwater at higher pH and to confirm the sign of theelectric charge on 1 we used paper electrophoresiswith radiometric detection of 99mTc. The pH of theinitial alkaline solution of 1 (soon after synthesis)was adjusted to a required value in the range of1.0÷10.7, by adding some HClO4 or NaOH, andthen 10 μL of the solution was brought on the centreof a paper stripe (1×15 cm) soaked with an electro-lyte of the same pH. The electrophoresis was carriedout at 100 V out for 20 min. A large broad peakwas observed on the electrophorograms, either mi-grating to the cathode in the pH range of 1.0÷8.65,or remaining in the origin at pH≥9.2 (Fig.1). Thepositively charged species was undoubtedly 1, whilethat remaining in the origin would be the neutral[99mTc(CO)3(H2O)2OH] complex (4) – the prod-uct of deprotonation of 1 at higher pH. Basing onthis, we estimate the pKa of 1 to be in the range of8.8÷9.0, which is consistent with the data for themacroamounts [1,4]. In the acidic and neutral sol-utions small amounts of impurities, probably 2 and3, were also detected, either remaining in the originor slowly migrating to the anode. At pH>9 thesesmall peaks were overlapped by the large, broad peakof 4.

The ion exchange studies were carried out withacidic (HNO3 and HCl) solutions, pH<2, at roomtemperature. Two different ion exchange resins wereused:- an amphoteric resin with aminophosphonic

groups, Purolite S-950, 35-65 μm;- a strongly basic anion exchanger, Dowex 1X4,

200-400 mesh.Strongly acidic cation exchanger of the gel type,Dowex 50WX4, appeared inconvenient for thisstudy because of rather low affinity for 1 and sig-nificant peak tailing.

In order to separate 99mTc(I) species from theimpurities 2 and 3, the amount of which increasedwith ageing the solution, the dynamic (chromato-graphic) method of study was applied. Glass col-umns (0.071 cm2 × 8 cm) were filled with the givenresin, and then washed with either 0.05÷2 M HNO3(Purolite S-950), or 0.1÷12 M HCl (Dowex 1X4).99mTc samples (50 μL each) in HNO3 or HCl sol-utions of the same concentration were introducedon the top of the resin bed, and then the 99mTcspecies were eluted from the column at the averageflow rate of 0.64 mL/min. Three 99mTc species werefound in the HNO3 effluent from the column filledwith the amphoteric resin: a small peak of 3 in thefree volume, the main peak of 1, and a peak of 2of varying magnitude (Fig.2).

The distribution ratio, Di, of the given species iwas determined from the position of its peak onthe chromatogram:

Fig.1. Electrophorograms of slightly alkaline aqueous sol-utions of 1: (A) pH 8.65 – the peak moved to thecathode – [99mTc(CO)3(H2O)3]+ (1); (B) pH 9.20 –the peak remained at the origin (75 mm from thecathode) – the neutral [99mTc(CO)3(H2O)2OH] com-plex (4).

ION EXCHANGE STUDIESON THE ORGANOMETALLIC AQUA-ION fac-[99mTc(CO)3(H2O)3]+

IN ACIDIC AQUEOUS SOLUTIONSZbigniew Samczyński, Monika Łyczko, Rajmund Dybczyński, Jerzy Narbutt


whole range of HNO3 concentrations studied, soDIV=0.

On the contrary to the HNO3 systems, only onelarge peak was observed in the HCl effluents fromthe anion exchanger columns. In this peak variouschemical forms of Tc(I) were eluted altogether:the precursor 1 and three chloride complexes –[Tc(CO)3(H2O)2Cl] (5), [Tc(CO)3(H2O)Cl2]

– (6)and [Tc(CO)3Cl3]2– (7), in dynamic equilibrium[4,5]. Although the equilibrium between 1, 5, 6 and7 establishes slowly in the NMR time-scale [5], itis very fast in the time-scale of the ion exchangeexperiment (minutes). The latter results in the elu-tion of all these Tc(I) species in the common singlebroad peak. In some experiments at DI>10, a smallpeak of 3 could be distinguished in the HCl efflu-ent, at the free volume (DIV=0). On the contraryto the Purolite S-950/HNO3 system, the peak of 2was never observed in the HCl effluent. That wasdue to a very high affinity of the pertechnetate ion,2, to the Dowex 1X4 resin in the chloride form.The expected DVII values for the Dowex 1X4/HClsystems were too large to be experimentally deter-mined.

Figure 4 shows the dependence of DI (deter-mined from equation 1) on the molar concentra-tion of HCl in the Dowex 1X4/HCl system. Letus denote the [Tc(CO)3(H2O)3–iCli]1–i formula asMCli

1–i and assume that the two anionic speciesformed, 6 and 7 adsorb on the Dowex 1X4 resin(R-Cl) according to the anion exchange equation:

(i – 1)RCl + MCli1–i iK⎯⎯→←⎯⎯ Ri–1MCli + (i – 1)Cl– (2)

where Ki denotes the equilibrium constant of theanion exchange reactions. Ki may be expressed bythe mass action law using thermodynamic activitiesof the participating species, provided the activityof water (solvant) does not change within the wholerange of concentrations studied (constant ionicstrength). This asumption, however, can hardly be

Di = (Vmax,i – V0)·mr–1 (1)

where Vmax,i – effluent volume at the peak maximumof the species i [mL]; V0 – sum of the dead volumeof the column and the free volume of the resin bed[mL]; mr – mass of the dry resin [g].

The use of the dynamic method at the slow kin-etics of redox reactions of 99mTc (see above) allowedus to determine the distribution ratios, Dm, of the99mTc compounds at each valence state of technetium,Tc(m). In the experiments with the HNO3 solutionswe dealt with only one chemical form of 99mTc(I),1. The slope of linear function logDI vs. log[HNO3],equal to -0.96 ±0.04 (Fig.3), combined with theresults of the electrophoretic studies, confirms the+1 charge of 1. The cation 1 is not very hydro-philic: in 1 M HNO3 we have DI=12 mL g–1. Theslope of linear function logDVII vs. log[HNO3],

equal to -1.00 ±0.05 (Fig.3), corresponds to the –1charge of 2. The anion 2 is rather strongly adsorbedon the amphoteric resin studied. On the other hand,99mTcO2 is not adsorbed on the resin within the

Fig.2. 99mTc species eluted with 0.3 M HNO3 from ampho-teric ion exchange resin, Purolite S-950, loaded withaged solution of [99mTc(CO)3(H2O)3]+. The numbersdenote the Tc(I) species defined in the text.

Fig.3. The dependence of the distributions ratios, DI andDVII, of two ionic 99mTc species on the HNO3 concen-tration in the system Purolite S-950/HNO3 solutions.

Fig.4. Distribution ratio of the [99mTc(CO)3]+ species, DI,

in the system anion exchange resin Dowex 1X4/HCl,as a function of HCl concentration.


satisfied in ion exchange experiments at a broadrange of the electrolyte (HCl) concentrations. As-suming that also the neutral form, 5, is adsorbed onthe Dowex-1 resin according to (2), we may expressthe distribution ratio of Tc(I) as follows:

(3)

where square brackets denote the molar concen-trations of the given species in the aqueous phase(index aq) and those in the resin phase (no index).Assuming Ki to be constant values, and includingthe constant value [RCl]i-1 into the Ki, we arrive at:

aqI 2 3

1 aq 2 aq 3 aq

A[Cl ]D

1 [Cl ] [Cl ] [Cl ]

−

− − −=+ β +β +β

(4)

where β1, β2 and β3 are the concentrational stabil-ity constants of the chloride complexes 5, 6 and 7in aqueous solution:

(5)

and A=K1β1+K2β2+K3β3. Considering A to be aconstant (which is a very rough assumption), andbasing on the experimental dependence of logDI(determined from equation 1) on log[HCl] in theDowex 1x4/HCl system (Fig.4; the solid line is the

tractants for the SANEX process, very selectivelyextracting actinides(III) over lanthanides from HNO3solutions [4,5]. Solvent extraction of Am(III) andEu from 1 M HNO3 by 6,6’-bis-(diethyl-1,2,4-tri-azin-3-yl)-2,2’-bipyridine (C2-BTBP, scheme 1),with high SFAm/Eu, has been reported [5].Very slowkinetics of extraction with these lipophilic N-tetra-dentate ligands, not acceptable in technology, canbe improved by the use of “phase transfer reagents”,but at the cost of somewhat lowered the An/Ln sepa-ration factor, SFAn/Ln [4].

In the present work, we investigated the effectof bidentate N-heterocyclic ligands, 5,6-dimethyl--3-pyridin-2-yl-1,2,4-triazine (PT, scheme 2) [6], and5,5',6,6'-tetraethyl-3,3'-bi-1,2,4-triazine (TT, scheme3) [6], on the efficiency of the Am(III)/Eu(III) sepa-ration by solvent extraction with C2-BTBP. Prelimi-nary liquid-liquid distribution studies have shownthat both C2-BTBP and TT are very lipophilic andexhibit very low basicity (pKa<<1), while PT is

13 31 i

I i 1 i i aqi 1 i 0

D [R MCl ] [MCl ]−

−−

= =

⎧ ⎫⎧ ⎫= ×⎨ ⎬ ⎨ ⎬⎩ ⎭ ⎩ ⎭∑ ∑

The research in the partitioning of long-lived radio-nuclides of minor actinides (An) from nuclear wastes,directed on their further transmutation, is an im-portant programme in Europe and in several nu-clear countries in the world. In particular, it is thesubject of an integrated project EUROPART real-ized in the 6th Framework Programme of EU withinEURATOM [1]. One of the numerous extractionsystems proposed for the selective separation ofminor actinides from lanthanide (Ln) fission prod-ucts (the SANEX process) was the subject of ourrecent studies [2,3].

N-tetradentate heterocyclic ligands, the deriva-tives of 6,6’-bis-(1,2,4-triazin-3-yl)-2,2’-bipyridine(BTBP), have been selected as most promising ex-

best-fit polynomial (4)) we evaluated for the threechloride complexes fac-[99mTc(CO)3(H2O)3–nCln]

1–n

the values: β1=0.45, β2=0.085, β3=0.0046 (dm3 mol–1

units). The values obtained are less (by the factorof 2.4÷3) than the literature values of the respec-tive concentrational stability constants, determinedby 99Tc-NMR for the macroamounts of Tc at a con-stant ionic strength (I=4) at 22oC [5]. Taking intoaccount that the ion exchange experiments werecarried out at varying ionic strength of the HClsolutions (I=0.1÷12) we consider our values forn.c.a. amounts of Tc at 25oC to be unexpectedlygood approximations for the literature stabilityconstants.

References[1]. Alberto R., Schibli R. , Waibel R., Abram U., Schubiger

A.P.: Coord. Chem. Rev., 190-192, 901-919 (1999).[2]. Alberto R.: Top. Curr. Chem., 252, 1-44 (2005).[3]. Egli A. et al.: Organometallics, 16, 1833-1840 (1997).[4]. Suglobov D.N. et al.: In: Technetium, rhenium and other

metals in chemistry and nuclear medicine. 6. Eds. M.Nicolini, U. Mazzi. SGEditoriali, Padova 2002, pp.123-126.

[5]. Gorshkov N.I., Lumpov A.A., Miroslavov A.E.,Mikhalev V.A., Suglobov D.N.: Czech. J. Phys., 53,A745-A749 (2003).

SYNERGISTIC EFFECTOF NEUTRAL BIDENTATE N-HETEROCYCLIC LIGANDS

ON THE SEPARATION OF Am(III) FROM Eu(III)BY SOLVENT EXTRACTION WITH

TETRADENTATE 6,6’-BIS-(DIETHYL-1,2,4-TRIAZIN-3-YL)-2,2’-BIPYRIDINEJerzy Narbutt, Jadwiga Krejzler

Scheme 2. 5,6-dimethyl-3-pyridin-2-yl-1,2,4-triazine (PT).

Scheme 1. 6,6’-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2’-bi-pyridine (C2-BTBP).

1 i 1 ii i aq aq aq[MCl ] [M ] [Cl ]− + − − −β = × ×


The enhancement of the extraction exerted bythe TT ligand is somewhat greater than that fromPT. All the experimental quantities, DAm, DEu andSFAm/Eu, observed after 180 min mild shaking in themixed-ligand systems seem to approach the equi-librium values. The fact that the DAm and DEu valuesare by 2÷4 times lower than the respective equilib-rium values reported for the system with C2-BTBPalone [5] may be interpreted as due to the higherC2-BTBP concentration in that reference system(0.068 M). Surprisingly, however, the highest sepa-ration factors, SFAm/Eu, in the C2-BTBP+PT andC2-BTBP+TT systems, 230 and 340, respectively,are significantly greater than the reported referencevalue, 160 ±16 [5]. On the other hand, all the DAm,DEu and SFAm/Eu values observed in our system withC2-BTBP alone are clearly non-equilibrium quan-tities, even after 180 min mild shaking.

If further studies confirm this preliminary ob-servation that 180 min mild shaking makes it pos-sible to reach equilibrium in the mixed-ligand ex-traction systems studied, while not in the systemwith C2-BTBP alone, we will be able to concludethat the synergism observed is of kinetic origin. Inthat case the bidentate ligands studied will be con-sidered the phase transfer regents which do notdecrease the SFAm/Eu value observed in the systemwith C2-BTBP alone, surely because of the selec-tivity of the ligands for Am(III) over Eu(III) ions.The other option, i.e. the thermodynamic syner-gism due to preferential formation of mixed-ligandAm(III) complexes, is less probable because bothtetradentate and bidentate ligands studied are neu-tral molecules of the same chemical character, whichcan hardly exert synergistic effects in solvent ex-traction of metal ions.

The work was carried out within the EuropeanCommission project EUROPART (contract No.FI6W-CT-2003-508854) and was co-financed by thePolish Ministry of Education and Science (decisionNo. 619/E-76/SPB/6). We thank our EUROPARTpartner, Dr. M.R.St.J. Foreman, for supplying uswith the extractants studied. We also thank Prof.S. Siekierski for discussion and Mrs. W. Daleckafor technical assistance.

moderately lipophilic and moderate weakly basic(pKa≈2.7). Dilute 1,1,2,2-tetrachloroethane sol-utions of C2-BTBP (and its mixtures with PT or TT)were used to extract carrier-free 152Eu and 241Amfrom 1 M HNO3. The test tubes with the two liquidphases were mildly (60 times per min) mechanically

shaken at a temperature of 25oC for various timeintervals (from 10 to 180 min). Other experimentaldetails are described elsewhere [3].

Figure 1 presents the dependence of the distri-bution ratios of the metal ions, DAm and DEu, onthe extraction time in all the systems studied. Inno system studied the extraction equilibrium wasattained even after 180 min of the slow shaking. Inthe system with 0.05 M C2-BTBP alone all the ex-traction parameters: DAm, DEu and SFAm/Eu are much

lower than the respective values reported for thesame system, but under vigorous 60 min shaking,e.g. SFAm/Eu=160 [5]. Moreover, the rate of Am ex-traction appears somewhat less than that of Eu.Therefore, the SFAm/Eu value also increases with thetime of extraction (Fig.2).

The 1,1,2,2-tetrachloroethane solutions of PTand TT alone, 0.2÷1.5 M, do not noticeably extractAm(III) ions from 1 M HNO3 (DAm<10–4), which isconsistent with the data by Hudson et al. [6]. Figure1 shows that the bidentate ligands, PT and TT,either improve the kinetics of solvent extraction ofAm(III) and Eu(III) ions with C2-BTBP or causea thermodynamic synergistic effect in extraction ofboth metal ions, much stronger for Am than for Eu.A great increase in the DAm values is observed whencomparing to the system with C2-BTBP alone, whilethe respective increase in the DEu values is relativelyless. This difference leads to a sygnificant increasealso in the SFAm/Eu values which grow with the timeof extraction more and faster than that in the sys-tem with C2-BTBP alone (Fig.2).

Fig.1. Kinetics of solvent extraction of Am(III) (full symbols)and Eu(III) (open symbols) in the systems: 0.05 MC2-BTBP (squares), 0.05 M C2-BTBP+0.5 M PT(circles) and 0.05 M C2-BTBP+0.5 M TT (triangles)in 1,1,2,2-tetrachloroethane/1 M HNO3 at 25oC.

Fig.2. The increase in the Am(III)/Eu(III) separation factorwith the time of solvent extraction of Am(III) andEu(III) in the systems: 0.05 M C2-BTBP (squares),0.05 M C2-BTBP+0.5 M PT (circles) and 0.05 MC2-BTBP+0.5 M TT (triangles) in 1,1,2,2-tetrachloro-ethane/1 M HNO3 at 25oC.

Scheme 3. 5,5',6,6'-tetraethyl-3,3'-bi-1,2,4-triazine (TT).


References

[1]. Madic C., Lecomte M., Dozol J.-F., Boussier H.: Ad-vanced chemical separation of minor actinides from highlevel nuclear wastes. In: Proceedings of the ConferenceEURADWASTE’04, Luxembourg, 29.03.-01.04.2004.EUR 21027.

[2]. Narbutt J., Krejzler J.: Separation of Am(III) fromEu(III) by mixtures of triazynylbipyridine and bis(dicar-bollide) extractants. The composition of the metal com-plexes extracted. In: INCT Annual Report 2005. Insti-tute of Nuclear Chemistry and Technology, Warszawa2006, pp. 74-76.

synthesis as well as the physicochemical and cyto-toxic characterization of the compounds with thenon-acridine thiourea derivatives. The main ob-jective of the presented study was to determine bio-logical, i.e. cytotoxic and antimicrobial activity ofplatinum(II) complexes with N-2-tetrahydrofurfuryl-thiourea (1) and N-2-methyltetrahydrothiophene-thiourea (2), see Scheme. MTT assay (test for mea-suring cell growth with colorimetric assay usingyellow colorimetric indicator: MTT – 3-(4,5-dime-thylthiazol-2-yl)-2,5-diphenyltetrazolium bromide)was performed as described by Gruber and Anu-szewska [9].

In addition to the cytotoxic properties, biologi-cal activity of the platinum complexes against dif-ferent microorganisms was tested. The antimicro-bial activity was expressed by minimal inhibitoryconcentration (MIC). Results of the MIC measure-ments are presented in Table 1.

The results are displayed on the bar char, whereL(O) and L(S) stand for the platinum(II) complexwith 1 and 2, respectively (Fig.1).

It can be seen that both complexes are especiallyefficient against Staphylococcus epiderminis: plati-num(II)-1 complex inhibited growth of the strainat a concentration of 5 mM, whereas platinum(II)-2was active against Staphylococcs epidermidis at 2.5mM. The latter was also active against Bacilluspumilus at a concentration of 5 mM. All otherbacterial strains were inhibited by platinum(II)-1complex at a concentration of 10 mM, and byplatinum(II)-2 at a concentration of 20 mM. Onthe other hand, the fungal strains were resistantto both compounds even at the highest concentra-tion, i.e. of 20 mM.

cis-Platin (cis-diamminedichloroplatinum(II),CDDP) is used in clinical practice as one of the mosteffective anticancer drugs. Unfortunately, its use-fulness is limited due to the growing resistance oftumor cells, and significant side effects of the drug.It has been found that direct structural analoguesof cis-platin, e.g. diaminocyclohexane (DACH)platinum(II) complexes, do not show the expectedimprovement of the clinical efficacy in compari-son with the parent drug. Thus, since a few yearsafter the discovery of CDDP a continuing effort isbeing made to develop other platinum complexes inorder to overcome the above shortcomings [1,2].

In the last two decades, the interest in plati-num(II) complexes with chelating ligands contain-ing both nitrogen and sulfur donor atoms has in-creased, because these complexes seem to exhibiteither higher anticancer activity or reduced toxicityin relation to known metal containing drugs [3].As a result of these studies, a number of novel plati-num(II) complexes sufficiently interesting for clini-cal trials have been synthesized. However, only afew of them have overcome the parent drug in theirefficacy [4]. On the other hand, several combinedchemotherapeutic procedures consisting in theapplication of various platinum(II) complexes to-gether with compounds containing S-donor groups(in this case called chemoprotectants) have beentested with the aim of reducing the platinum-basedside effects.

As a result of our previous studies [5,6], a ques-tion arises whether complexes containing thePtII(R1R2tu) fragment, where (R1R2tu) denotes adifferently substituted thiourea (tu) molecule,might exhibit the desired biological activity. Lit-erature data suggest, that platinum(II) complexeswith certain thiourea derivatives (in particular con-taining the acridine fragment, called ACRAMTUs[7,8]) can really be potential pharmaceuticals. Themode of their therapeutic action differs, however,from that established for the cis-platin. Our search-ing for the platinum(II) complexes with ligandscontaining the thiourea derivatives focused on the

[3]. Krejzler J., Narbutt J., Foreman M.R.St.J., Hudson M.J.,Casensky B., Madic C.: Czech. J. Phys., 56, D459-D467(2006).

[4]. Geist A., Hill C., Modolo G., Foreman M.R.St.J.,Weigl M., Gompper K., Hudson M.J.: Solvent Extr. IonExch., 24, 463-483 (2006).

[5]. Drew M.G.B., Foreman M.R.St.J., Hill C., Hudson M.J.,Madic C.: Inorg. Chem. Commun., 8, 239-241 (2005).

[6]. Hudson M.J., Foreman M.R.St.J., Hill C., Huet N.,Madic C.: Solvent Extr. Ion Exch., 21, 637-652 (2003).

ESTIMATION OF CYTOSTATIC AND ANTIMICROBIAL ACTIVITYOF PLATINUM(II) COMPLEXES WITH THIOUREA DERIVATIVES

Elżbieta Anuszewska1/, Bożena Gruber1/, Hanna Kruszewska1/, Leon Fuks,Nina Sadlej-Sosnowska1/

1/ National Medicines Institute, Warszawa, Poland

Scheme. N-tetrahydrofurfurylthiourea (1) and N-2-methyl-tetrahydrothiophenethiourea (2).


Cytotoxic activity of the complexes was deter-mined with the use of MTT test. As shown in Table2 and Fig.2, all kinds of cells examined exhibit com-parable sensitivity to both platinum(II)-1 and plati-num(II)-2 complexes. The less sensitive to theplatinum(II) complexes appeared HeLa cells (an

immortal cell line derived from cervical cancer cellstaken from Henrietta Lacks, who died from hercancer in 1951), while the most sensitive were WS1cells – normal human fibroblasts.

The obtained data indicate that mammaliancells are about 10 times more sensitive than bacte-rial cells with reference to the platinum complexesstudied.

Stability of both complexes, with 1 and 2, in thestandard aqueous physiological solution was checkedby recording their UV-Vis spectra (200-800 nm,nmax=235 nm) vs. time. No changes in the spectrahave been detected within one week. The HPLCchromatograms of samples withdrawn occasionallyfrom the saline solutions of the complexes duringone week (isocratic elution using a CH3CN-H2Omixture, vol:vol=20:80; 230 nm) did not exhibitnoticeable changes either.

As a result of the presented work, we can con-clude that the biological activity of both plati-num(II)-1 and platinum(II)-2 complexes, deter-mined as their cytostatic IC50 and antimicrobialMIC values, is not very high. The same concernsthe results obtained already for the standard L1210murine leukemia cell line [10]. However, the foundcytotoxicity is significantly improved as comparedto that of platinum(II) complexes with the unsubsti-tuted thiourea molecules [5]. These results moti-

Fig.1. Activity of the investigated platinum(II) complexesagainst the bacterial strains.

Table 2. The IC50 values of the investigated platinum(II)complexes.

Fig.2. Activity of the investigated platinum(II) complexesagainst the tumor cells.

Table 1. MIC values of the investigated platinum(II) com-plexes.


vate us to continue the investigations, in particularon platinum(II) complexes with other thiourea de-rivatives, possibly useful in the chemotherapy.

References

[1]. Cvitkovic E., Spaulding J., Bethune V., Martin J.,Whitmore W.F.: Cancer, 39, 1357 (1977).

[2]. Burchenal J.H., Kalaher K., Dew K., Lokys L.: CancerTreat. Rep., 63, 1493 (1979).

[3]. Faraglia G., Fregona D., Sitran S., Giovagnini L.,Marzano C., Baccichetti F., Cesellato U., Graziani R.:J. Inorg. Biochem., 83, 31 (2001).

[4]. Canetta R., Rozencweig M., Wittes R.E., Shacter L.P.:In: Proceedings of the Fifth Nagaya InternationalSymposium on Cancer Treatment. Excerpta Medica,Tokyo 1990, pp. 318-323.

[5]. Fuks L., Sadlej-Sosnowska N., Samochocka K., Sta-rosta W.: J. Mol. Struct., 740, 229 (2005).

sorbate species, the latter is bound by differentmechanisms.

The biosorption equilibrium of heavy metals wasmodelled using adsorption-type isotherms. TheLangmuir [5] and Freundlich [6] models are usedas the most popular ones. The form of the Langmuirmodel is

(1)m ee

e

(b)(q )(C )q1 (b)(C )

=+

where: qe – the sorption capacity at equilibrium[mol g–1], qm – maximum sorption capacity [mol g–1],Ce – equilibrium concentration of metal ion [mol L–1],b – the Langmuir model constant [L/mol].The form of the Freundlich model is

qe = K(Ce)1/n (2)where K and n – the Freundlich model constants(dimensionless).

Seaweeds are accounted among the most popu-lar biosorbents because their macroscopic structuresoffer a convenient basis for production of sorbentparticles suitable for sorption process. Brown mar-ine algae tend particularly to sequester heavy metals[7,8], in particular cell wall material obtained fromSargassum biomass [9]. As a result, ion exchangeproperties of certain natural polysaccharides havebeen studied in detail, and it was found that bivalentmetal cations exchange with counter ions comingfrom the polysaccharides, e.g. alginic acid (Scheme)according to the following reaction [3]:

[6]. Fuks L.: Pt(II) chloride complexed by tetrahydrofur-furyl- or tetrahydrotiophenylthiourea: structural andbiological features. 3rd Cental European ConferenceChemistry towards Biology, Kraków-Przegorzały,Poland, 08-12.09.2006.

[7]. Hess S.M., Anderson J.G., Bierbach U.: Bioorg. Med.Chem. Lett., 15, 443 (2005).

[8]. Choudhury J.R., Bierbach U.: Nucleic Acids Res.,33, 5626 (2005).

[9]. Gruber B.M., Anuszewska E.L.: Toxicol. In Vitro,16, 663 (2002).

[10]. Fuks L., Kruszewski M., Sadlej-Sosnowska N.: Struc-tural studies and cytotoxicity assays of platinum(II)chloride complexed by (tetrahydrothiophene)thio-urea. In: INCT Annual Report 2005. Institute of Nuc-lear Chemistry and Technology, Warszawa 2006, pp.68-70.

Contamination of aquatic environment by variouspollutants (synthetics, organic, heavy metals, etc.)causes imbalance in natural functioning of the eco-system. Heavy metals cause particularly severedamage to the living systems at various levels. Mainsources of heavy metal contamination are: (i) urbanindustrial aerosols created by combustion of fuels,metal ore refining and other industrial process; (ii)liquid and solid wastes generated from animals andhumans; (iii) mining activities; and (iv) industrialand agricultural chemicals. The most importantfeature that distinguishes heavy metal ions fromother toxic pollutants is their non-biodegradability.The toxicity due to metal ion is owing to their abilityto bind with protein molecules and prevent repli-cation of DNA and subsequent cell division [1].To avoid health hazard, it is essential to removethese toxic heavy metals from water before theirintake by living organisms.

Search for new technologies involving the re-moval of toxic metals from wastewaters has directedattention towards biosorption, i.e. metal bindingby various biological materials. Biosorption can bedefined as the ability of biological materials to ac-cumulate heavy metals from aqueous solutionsthrough metabolically mediated or physicochemi-cal pathways of uptake [2]. Algae, bacteria and fungiand yeasts have proved to be potential biosorbentsof metal ions [3]. The major advantages of biosorp-tion over conventional treatment methods include:(i) low cost, (ii) high efficiency, (iii) minimizationof chemical and/or biological sludge, (iv) no addi-tional nutrient requirement; (v) easy regeneration ofbiosorbent, and (vi) possibility of metal recovery [4].

Biosorption process involves a solid phase(sorbent or biosorbent; biological material) and aliquid phase (solvent, normally water) containinga dissolved species to be sorbed (sorbate, metalions). Due to higher affinity of the sorbent for the

TRANSITION METAL SORPTION BY ALGINATE BIOSORBENTDorota Filipiuk1/, Leon Fuks, Marek Majdan2/

1/ Białystok Technical University, Poland2/ Maria Curie-Skłodowska University, Lublin, Poland

Scheme. Alginic acid carbohydrate chain.


thetic aqueous solutions containing a given metalion of known concentration. Then, the equilibriummetal content was determined spectrophotometri-cally using 4-(2-pyridylazo)resorcinol (PAR) as anindicator. The amounts of metal sorbed by the algi-

nate were calculated as the difference between theinitial and equilibrium concentrations in the aque-ous phase. The best fit parameters of equations (1)and (2) were obtained by regression analysis usingthe software package Microcal Origin for Windows(release 6.0). Table shows the model constants and

2NaAlg + Me2+ ↔ Me(Alg)2 + 2Na+ (3)In the presented paper, sorption data for the

selected divalent transition metal cations are re-ported, obtained from a batch equilibrium sorptionprocedure using calcium alginate pellets. The sor-

bent studied is comparable at low price to the orig-inal alginic acid, however its mechanical, chemi-cal and thermal resistance significantly exceedsthose of the acid.

Experiments were performed by shaking (6 h)the weighed amount of calcium alginate with syn-

*) Co=0.0005 mol/L.

Table. Isotherm model constants and correlation coefficients for biosorption of the selected divalent transition metalcations (concentrations expressed in mol L–1).

Fig.2. Freundlich adsorption isotherms for Cu(II) and Cd(II) ions.

Fig.1. Langmuir adsorption isotherms for Mn(II) and Ni(II) ions.


correlation coefficients for the isotherms, determinedfor the divalent transition metal cations studied.Figures 1 and 2 present the Langmuir and Freundlichisotherms determined for some of the metal ionsstudied.

The essential characteristics of the Langmuirisotherms can be expressed in terms of a dimension-less constant, called the separation factor or equi-librium parameter (RL) defined as:

RL = 1/(1+bCo) (4)where: b – the Langmuir constant mentioned above,Co – initial concentration of the metal cation. Ac-cording to McKay [10] the RL value indicates thetype of isotherm as follows: RL>1 – unfavourable,RL=1 – linear, 0<RL<1 – favourable and RL=0 –irreversible. The RL values found for the initialmetal concentration of 0.5 mmol L–1 are slightlysmaller than unity. The K and n parameters calcu-lated from the slopes of the Freundlich plots varywithin the ranges 0.0279÷1.6943 and 0.7107÷1.0266,respectively. The obtained RL values, being be-tween 0 and 1, indicate for the favourable descrip-tion of the process by the Langmuir model. Theexperimental values of n close to unity for all theinvestigated cations indicate for poor fitting of theprocess by the Freundlich theory, as discussed else-where [11].

The R2 values for the Langmuir isotherm higherthan respective values for Freundlich equation ob-

served for the majority of the metal ions, indicatethat a monolayer coverage on the surface of thecalcium alginate is formed in the process. Thismeans that the sorption proceeds on the functionalgroups/binding sites of the sorbent. The processshould be regarded as monolayer adsorption.

References

[1]. Kar R.N., Sahoo B.N., Sukla L.B.: Pollut. Res., 11,1-13 (1992).

[2]. Fourest E., Roux J.-C.: Appl. Microbiol. Biotechnol.,37, 399-403 (1992).

[3]. Volesky B.: Biosorption of heavy metals. CRC Press,Boca Raton, Florida 1990, 396 p.

[4]. Kratochvil D., Volesky B.: Water Res., 32, 2760-2768(1998).

[5]. Langmuir I.: J. Am. Chem. Soc., 40, 1361-1403 (1918).[6]. Freundlich H.: Z. Phys. Chem., 57 A, 385-470 (1907),

in German.[7]. Volesky B., Holan Z.R.: Biotechnol. Progr., 11,

235-250 (1995).[8]. Volesky B.: Hydromeallurgy, 71, 179-90 (2003).[9]. Fourest E., Volesky B.: Appl. Biochem. Biotechnol.,

67, 33-44 (1997).[10]. Mckay G., Blair H.S., Gardener J.R.: J. Appl. Polym.

Sci., 27, 3043-3057 (1982).[11]. Kadirvelu K., Namasivayam C.: Environ. Technol.,

21, 1091-1097 (2000).

with aqueous Rhodamine B, respectively [3], andthen quantitatively determined in selected samplesby atomic absorption analysis with flame atomiza-tion.

The ratio (R) of the isotope concentrations,[113In]/[115In] and [69Ga]/[71Ga], in the selectedfractions of the effluent was determined using aninductively coupled plasma mass spectrometer(ICP-MS) Perkin Elmer Elan 6100. The relative

In recent studies on the fractionation of galliumand indium by chemical methods we have discov-ered the gallium and indium isotope effects in thesystem: strongly acidic cation exchanger (Dowex50W-X8)/HCl [1,2].

The aim of the present work was to seek similarchemical isotope effects of the same elements in theanalogous system: strongly basic anion exchangerDowex 1-X8/HCl solution. The experimentalmethod was the same as that used in the earlierstudies. A long glass chromatographic column, 0.5cm in inner diameter, was filled with the Dowex1-X8 resin, 200-400 mesh up to the bed height of95 cm. The “merry-go-round” elution method wasused with the flow rate of the effluent (HCl at agiven concentration) of 0.11 ml/min. The concen-trations of the HCl were selected in such a way asto obtain moderate values of the distribution co-efficient of the metal ions, required for chromato-graphic experiment. At the HCl concentrationequal to 2.5 M for Ga3+ and 1.0 M for In3+, the Kdvalues were close to 4 (Fig.1). Two cycles of the elu-tion were done for gallium and 5 cycles for indium.During the last cycle the 1 ml fractions of the efflu-ent were collected. The contents of indium and gal-lium in the consecutive fractions were evaluatedby spot tests with alcoholic solution of alizarin and

GALLIUM AND INDIUM ISOTOPE EFFECTSIN THE DOWEX 1-X8/HCl SYSTEM

Irena Herdzik, , Witold Skwara, Ewa Bulska1/, Agnieszka Wysocka1/

1/ Faculty of Chemistry, Warsaw University, Poland

Fig.1. Kd of indium and gallium vs. HCl concentration inthe Dowex 1-X8/HCl system.

Wojciech Dembiński


mation, under the assumption that the shape ofthe eluted band resembles the normal distribution[5,6]. According to this theory, ε is equal to S/N0.5,where S is the slope of linear function of εi vs. theeluted fraction (Δn/n) at the X-axis scaled in stan-dardized differences (Z) of normal distribution(Fig.3), and N is the number of theoretical platespassed by the band.

This work was supported by the State Commit-tee for Scientific Research (KBN), under grant No.4 T09A 057 25.

References[1]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysoc-

ka A.: Indium isotope effect in the Dowex 50-X8/HClsystem – comparison with the isotope effect of gallium.In: INCT Annual Report 2005. Institute of NuclearChemistry and Technology, Warszawa 2006, pp. 77-78.

[2]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysoc-ka A.: Nukleonika, 51, 217-220 (2006).

[3]. Feigl F., Anger V.: Spot tests in inorganic analysis. 6thed. Elsevier, Amsterdam-London-New York 1972, pp.233-247.

[4]. Smith M.R., Martell A.E.: Critical stability constants.Vol. 4. Inorganic complexes. Plenum Press, New Yorkand London 1976, pp. 109-110.

[5]. Glueckauf E.: Trans. Faraday Soc., 51, 34-44 (1955).[6]. Glueckauf E.: Trans. Faraday Soc., 54, 1203-1208

(1958).

standard deviation of these measurements wasusually 0.05÷0.07%. Prior to the analysis, chlorideswere removed from the samples by evaporatingwith 4 M HNO3 to dryness and dissolving the resi-due in 0.1 M HNO3. The local separation factors,defined as qi =Ri/Rfeed, or the local separation gains,defined as εi=ln(qi), were calculated from thesedata.

Figure 2 shows the results of the separationexperiments, performed with 1.0 M HCl for indium,and in 2.5 M HCl for gallium. The opposite slopesof the S-shape curves demonstrate opposite signof the indium and gallium isotope effects. The resinphase was enriched with the light isotope of gal-lium and the solution with the heavy isotope. Thelight isotope of indium was accumulated in the sol-ution whereas the heavy isotope – in the resinphase. The value of the unit separation factor forgallium was found to be ε=+5.9x10–4, and for in-dium ε=-1.5x10–4. The opposite signs (using thesame convention) of the isotope effects in the sys-tems with the cation and anion exchanger reflectthe difference in the stability constants of the chlo-ride complexes of the metals, for Ga3+ – logβ1=0.01; while for In3+ – log β1=2.32, log β2=3.62and log β3=4.0 [4]. The unit separation factor wascalculated on the basis of the Glueckauf approxi-

Fig.2. Isotope separation gain of indium (in 1.0 M HCl)and gallium (in 2.5 M HCl) vs. eluted fraction of themetal.

Fig.3. Isotope separation gain of indium and gallium vs.eluted fraction. X-asis in Z units.

PROFICIENCY TESTING SCHEME PLANTS 6 – DETERMINATIONOF As, Cd, Cu, Hg, Pb, Se AND Zn

IN DRY MUSHROOM POWDER (Suillus bovinus)Halina Polkowska-Motrenko, Ewelina Chajduk, Jakub Dudek, Monika Sadowska-Bratek,

Michał Sypuła

Proficiency testing (PT) schemes are one of theelements of quality assurance and quality controlsystem in chemical measurements. PTs are one ofthe instruments of independent assessing the qual-ity of routine measurements. Participation in PTenables laboratories to demonstrate the reliabilityof the data they are producing. It is also one ofthe requirements of the international standard

ISO/IEC 17025:2005 [1] and can be used by ac-creditation bodies in accreditation decisions. TheInstitute of Nuclear Chemistry and Technology(INCT) has been involved in providing PT since2003. PT scheme PLANTS has been designed forthe purposes of laboratories from Poland andCentral and Eastern Europe determining trace el-ements in food of plant origin. PT PLANTS 6 –


Determination of As, Cd, Cu, Hg, Pb, Se and Znin dry mushroom powder (Suillus bovinus) hasbeen conducted in 2006. The adopted strategy ofthe PT scheme complies with the ISO/IEC Guide43-1:1997 [2], ISO 13528:2005 [3] and IUPAC har-monized protocol [4].Test materialPreparation of test material

Wild mushrooms (ca. 60 kg) were collected inthe forest in north-west Poland, cleaned from dust,soil and attached mosses. The end part of stalks wereremoved. Mushrooms (caps and stalks) were thencut into small pieces and air dried in a dryer accord-

ing to a procedure commonly used by food con-centrate producers (mainly 25oC, from time to time60oC). Dried mushrooms were milled in a centrifu-gal mill made of stainless steel and sieved by stain-less steel sieves. The fraction of particles with di-ameter ≤1 mm was collected. This fraction (ca. 5kg) was then homogenized by mixing and bottlingof 20 g test samples. Care was taken to avoid con-tamination. In order to ensure the long-term sta-bility of the test samples radiation sterilization wascarried out. All bottles with the test material wereirradiated with electron beam (energy 10 MeV, 9kW) from a linear accelerator LAE-13/9 (Depart-

Table 1. Results of As, Cd, Cu, Hg, Pb, Se and Zn determination provided by the reference laboratories.


ment of Radiation Chemistry and Technology,INCT). The sterilization dose was 30 kGy.Moisture determination

The procedure of moisture determination wasestablished on the basis of water desorption curvesdetermined at different temperatures. The refer-ence point has been chosen on a plateau that en-sures satisfactory reproducibility of the results. Ithas been recommended to dry subsamples of thematerial for 24 h at 50oC. In this case, the uncer-tainty associated with moisture content determi-nation was evaluated to be ≤1%.Homogeneity testing

Homogeneity testing was carried out accord-ing to the ISO 13528:2005 standard [3]. Contentsof the elements in question in 10 randomly selectedbottles were determined by the atomic absorptionspectrometry (AAS) method. Two samples of 250mg were taken from each bottle and analyzed. Meanvalue (Xmean), standard deviation of mean value(Sx), repeatability standard deviation (Sr) and be-tween samples standard deviation (Ss) were cal-culated using the following equations:

Xmean = ΣXaverage/gXaverage = (xt,1 + xt,2)/2

where: Xaverage – average result for t bottle, t – bottlenumber (t=1, 2, 3,…, g).

The material is considered to be homogeneousif:

Ss < 0.3σ̂where σ̂ is standard deviation for proficiency as-sessment.

On the basis of obtained results, it has beenfound that the material could be considered as ho-mogenous for the sample masses ≥250 mg for allthe determined elements.Assigning property values

Some of the test samples were selected ran-domly and analyzed by a group of reference labo-

ratories. The obtained results are summarized inTable 1. The assigned values and their uncertain-ties (Table 2) were calculated as the robust aver-

age of the results reported according to the proce-dure recommended by the ISO 13528:2005 stan-dard [3].Calculation of performance statistics

For the purpose of performance evaluation,the z-score and En-test score have been employed.En-test was used only when a participating labora-tory reported its own estimation of uncertainty.

The value of the z-score was calculated using theequation:

z = xlab

σ ^

– xref

where: xlab – result reported by participating labora-tory, xref – assigned value, σ̂ – standard deviationfor proficiency assessment calculated from Horwitz’sformula [5]:

σ̂ = 0.02 c0.8495

where c is concentration of the element in g g–1.The σ̂ values are equal to 0.065 mg kg–1 for As,

0.053 mg kg–1 for Cd, 1.05 mg kg–1 for Cu, 0.036mg kg–1 for Hg, 0.085 mg kg–1 for Pb, 0.209 mg kg–1

for Se and 5.25 mg kg–1 for Zn.The value |z|<3 has been set as an acceptance

level for this PT.

Table 2. Assigned values and their uncertainties.

* Expanded standard uncertainty (k=2).

Table 3. Number of PT participating laboratories determining individual elements, number of applied methods andnumber of accepted results.

2t ,1 t ,2Sr (x x ) /(2g)= −

2 2Ss Sx (Sr / 2)= −

2mean averageSx (X X ) /(g 1)= − −


The value of the En-test score are calculated fromthe following equation [11]:

lab refn 2 2

ref lab

x xEU U

−=

+where U is expanded standard uncertainty (k=2).

The value |En|≤1 has been set as an acceptancelevel for this PT.

Eighteen Polish laboratories participated in thePT. Seventeen laboratories provided the results.Number of PT participating laboratories determin-ing individual elements, number of applied methodsand number of accepted results are summarizedin Table 3.

As can be seen, the performance of the partici-pating laboratories can be recognized as satisfac-tory. Only 5 from 89 provided results are not ac-

cepted on the basis of z-score value. Some examplesof summary results are shown in Figs.1-4.

References[1]. ISO/IEC 17025:2005 – General requirements for the

competence of testing and calibration laboratories.ISO, Geneva 2005.

[2]. ISO/IEC Guide 43-1:1997 – Proficiency testing by inter-laboratory comparisons. Part 1: Development andoperation of proficiency testing schemes. ISO, Geneva1997.

[3]. ISO 13528:2005 – Statistical methods for use in profi-ciency testing by interlaboratory comparisons. ISO,Geneva 2005.

[4]. Thompson M., Ellison S.L.R., Wood R.: Pure Appl.Chem., 78, 1, 145-196 (2006).

[5]. Thompson M.: Analyst, 125, 385-386 (2000).

Fig.4. Results of laboratories participating in PT (z-score)for Zn determination.

Fig.3. Results of laboratories participating in PT (z-score)for Hg determination.

Fig.1. Results of laboratories participating in PT (z-score)for As determination.

Fig.2. Results of laboratories participating in PT (z-score)for Cd determination.

NEW POLISH CERTIFIED REFERENCE MATERIALSFOR INORGANIC TRACE ANALYSIS:

CORN FLOUR (INCT-CF-3) AND SOYA BEAN FLOUR (INCT-SBF-4)Halina Polkowska-Motrenko, Rajmund Dybczyński, Ewelina Chajduk, Bożena Danko,

Krzysztof Kulisa, Zbigniew Samczyński, Michał Sypuła, Zygmunt Szopa

Certified reference materials (CRMs) are an im-portant element of the metrological system. Inchemical measurements, CRMs are used as an in-ternal tool of quality assurance for checking accu-racy of results and for validation of measurementmethods [1-3]. As CRMs should be as similar tothe analyzed material as possible, the potential de-

mand for suitable CRMs in very big. The produc-tion and use of CRMs should meet requirementsof international guidelines [4-8]. The Institute ofNuclear Chemistry and Technology (INCT) hasissued two new materials of biological origin lately,namely: Corn Flour (INCT-CF-3) and Soya BeanFlour (INCT-SBF-4). The general strategy of prepa-


ration and certification of CRMs developed in theINCT [3] has been employed. The concentrationlevel of trace elements in these matrices are muchlower than in the biological type CRMs issued pre-viously by the INCT and differ strongly in fat con-tent what is important for the way of decompositionof the sample. So, INCT-CF-3 and INCT-SBF-4supplement the issued CRMs and should fulfill spe-cific laboratory needs.Origin, preparation and testingof the materialsCollection, grinding and sieving

Both raw materials were chosen from amongthe materials present on the Polish market. Cornflour was prepared from corn grown in Poland andsoya bean flour from soya grown in India. Corn flourwas produced by ViVi-Tak s.c. (Poland) accord-ing to Polish standard PN-A-74205:1997, thensieved through the 250 μm nylon sieves and storedin a polyethylene (PE) bag. Soya bean was milled,sieved through the 150 μm nylon sieves and storedin a PE bag. Approximately 50 kg of sieved cornflour and soya bean flour were collected.Homogenization and preliminary homogeneitytesting

In order to homogenize, the whole lot of each offlours (ca. 50 kg) was transferred to a 110 dm3 PEdrum, placed in a homogenizer and the materialwas mixed by the rotation for 20 hours. After thistime, a preliminary homogeneity testing was per-formed determining selected elements in the samplesrandomly selected from the drum by the X-ray fluo-rescence (XRF) method. It was found that thematerials did not show any significant inhomoge-neity. The materials were then distributed in 50 gportions (future CRM) into 150 cm3 polypropylene(PP) bottles with a screw-on cap and 10 g portions(intercomparison sample) into 60 cm3 poly(ethylenetetraphtalate) (PET) bottles, respectively.Determination of particle size

Examination by optical microscopy revealed thatMartin’s diameter (arithmetic mean of the maximumdistance between opposite sides of a particle anda distance in perpendicular direction) of over 98%of particles of INCT-CF-3 was below 25 μm andover 90% of particles of INCT-SBF-4 was below50 μm.Final homogeneity testing

Homogeneity have been studied by the deter-mination of selected element contents in 100 mgsamples using instrumental neutron activationanalysis (INAA). For INCT-CF-3, these were Br,Co, Fe, K, Mn, Na, Rb and Sc and Co, Fe, K, Scand Zn for INCT-SBF-4. The results (variances andmeans) for six samples randomly taken from dif-ferent containers and for six samples from a singlecontainer (also randomly chosen) were comparedby means of Fisher’s test (F-test) and t-Student’stest (t-test). No significant differences in variancesand means were found. Hence, the materials can beconsidered as homogeneous for the sample masses≥100 mg.Determination of total water content

Total water content in the candidate referencematerials was determined in the Institute for Ref-

erence Materials and Measurements – IRMM (Gell,Belgium) laboratory using the Karl-Fischer titrationmethod. It amounted to 11.09 g/100 g with relativeexpanded uncertainty of 11.3% in INCT-CF-3 and7.33 g/100 g with relative expanded uncertainty of10.9% in INCT-SBF-4.Radiation sterilization

All containers with the candidate CRMs weresterilized by irradiation with electron beam (en-ergy 10 MeV, 9 kW) from a linear acceleratorLAE-13/9 (Department of Radiation Chemistryand Technology, INCT). The sterilization dose was28 kGy.Stability testing

Long-term stability was checked by comparingthe results obtained for one bottle (randomlychosen) stored under controlled conditions: in anair-conditioned room at 20oC (normal storage).Samples of the CRM (ca. 100 mg) were taken fromthe bottle after 0, 20 and 32 months of storage andconcentration of six selected elements (Co, Fe, K,Rb, Sc and Zn) was determined by the INAAmethod. Short-term stability was examined by thedetermination of concentrations of the above men-tioned elements in the bottle stored in the CO2incubator (ASAB) at 37oC, 100% humidity and 5%CO2. Statistical evaluation of the obtained resultsusing t-Student’s test [9] indicates that there areno significant differences between the results ob-tained in both experimental conditions examinedand that no significant trends can be observed. Con-sequently, it can be stated that the material is stablein time. The test is being continued and stabilityof INCT-CF-3 and INCT-SBF-4 will be monitoredduring all storage.Determination of dry mass

In order to refer the results of analysis to thesame dry state of the material, a methods of waterdetermination on the basis of water desorptioncurves determined at few temperatures were estab-lished. The reference points have been chosen ona plateau that ensures satisfactory reproducibilityof the results. It has been recommended to drythe subsample of the materials for 24 h at 80oC.The standard uncertainty due to moisture contentdetermination was established on the basis of rep-licate measurement to be 0.51 and 0.45% forINCT-CF-3 and INCT-SBF-4, respectively.Characterization of the materials

The assignment of the certified values for ele-ment concentrations has been based on the resultsof the interlaboratory comparison organized in theyears 2004-2005. Ninety two laboratories from 19countries participated in the intercomparison. Thelaboratories were asked to analyze two candidateCRMs and a CRM of their own choice for a qual-ity assurance (QA) reason. Moreover, the partici-pating laboratories were asked to analyze the CRMsent together with the intercomparison samples,the identity of which was known only to the orga-nizer. The results of the analysis of that CRM werethen applied in the process of the certification. Twodata sets were created and evaluated: the first –“original” – consisted of all results reported by thelaboratories and the second – “alternative” – con-


sisted of the results provided by the laboratoriesfor elements certified in the CRMs when the con-fidence limits of the laboratory results overlappedwith the confidence limits of the CRM, i.e. whenthere is fulfilled the condition:

CRM lab CRM CRM lab labx x k u k u− ≤ ⋅ + ⋅ (1)where: xCRM – certified value, x–lab – laboratory mean,u – combined standard uncertainties, k – coveragefactors at a level of confidence of 95%.A method of data evaluation leading to assignmentof certified values was the same as that used previ-ously in our Laboratory [10]. This approach is be-ing based on outlier’s rejection procedure whichuses concurrently four statistical tests (Dixon,Grubbs, skewness and kurtosis) at the significance

level of 0.05, followed by calculation of the overallmeans of results remaining after outlier rejection,standard deviations, standard errors, confidenceintervals. The results of the evaluation of both datasets, i.e. original and alternative one were very simi-lar in the most cases.

For some elements, the results obtained by theradiochemical neutron activation analysis (RNAA)definitive method [11-18] were also employed inthe process of certification, as it is illustrated inFigs.1 and 2 and as it was done previously with therespect to the former CRMs issued by the INCT.The certified values for Al, Ba, Br, Ca, Co, Cs, Cu,K, La, Mg, Mn, Ni, P, Rb, S, Sr, Th and Zn were

Fig.2. Comparison of the certified values and their confi-dence limits and the result obtained by the definitivemethod for Mo in INCT-CF-3 on the background oforiginal range of results submitted by the partici-pants.

Fig.1. Comparison of central values and their confidencelimits for Co in INCT-SBF-4 obtained by variousapproaches to the background of original range ofresults submitted by participants.

Table 1. Certified values for Corn Flour (INCT-CF-3).


determined using the alternative database. In sucha way, these data are traceable to the existing CRM.On the other hand, the use of the CRM confirmsthe validity of the applied method of data evaluation[17]. The values for other elements were derived fromthe original database. The combined standard un-certainty of certified values uc consists of four un-certainty contributions, which are associated with

the result of the interlaboratory comparison uinterlab,the long-time stability ulstab, the short-time stabilityusstab and the moisture determination usm (expressedas standard uncertainties):

2 2 2 2interlab lstab sstab smu u u u u= + + + (2)

uinterlab is estimated as a relative standard deviationof the overall mean, ulstab – the standard uncertaintyestimated from the long-term stability studies, usstab– the standard uncertainty estimated from theshort-term stability studies, and usm – the standarduncertainty estimated from the moisture determi-nation study.The expanded uncertainty (U) is obtained by multi-plying uc by a coverage factor k=2 (correspondsto a level of confidence of approximately 95%).Certified values and their uncertainties (X ±U)established in the course of the present work forseveral elements in INCT-CF-3 and INCT-SBF-4are presented in Tables 1 and 2. Information valuesare listed in Table 3.

The relative frequency of using various analyti-cal techniques in this intercomparison is illustrated

Fig.3. Frequency of the use of analytical technique in thecertification campaign.

Table 2. Certified values for Soya Bean Flour (INCT-SBF-4).


in Fig.3. As can be seen, atomic absorption spectro-metry (AAS), neutron activation analysis (NAA),emission spectroscopy (OES) and mass spectro-metry (MS) were the methods most frequentlyused. The very significant share of results by NAA,much greater than could have been expected onthe basis of global contribution of this method toroutine analyses worldwide, is worth emphasizing.

The authors express their thanks to all labora-tories participating in this intercomparison for

to interferences caused by the matrices of suchsamples and by low concentration of the elementsto be determined. The mentioned difficulties maybe eliminated by the preliminary separation andpreconcentration of the contaminating elements.From among the methods usually used for this pur-pose, the solid-phase extraction is applied more andmore frequently because of its simplicity and manyadvantages in comparison with other methods[1-5].

Previously, we elaborated a dithizone sorbent andapplied it for the determination of noble metals inenvironmental samples [5], speciation of selenium

Table 3. Information values for Corn Flour (INCT-CF-3)and Soya Bean Flour (INCT-SBF-4).

The growing contamination of environment causesthat many toxic elements are able to form variousorgano-metallic compounds. In this form they canbe solubilized and enter soils, sediments, watersand plants, and, in consequence, they can enter thefood chain. This fact causes the necessity to checkthe contamination level of environment by heavymetals and what their physiological effect is. There-fore, the determination of these metals in soil,waters, plants and also in food products at very lowconcentration levels as μg g–1 and ng g–1 is required.However, the direct application of suitable analyti-cal instrumental methods is often restricted owing

good cooperation. This work was in part supportedby the State Committee for Scientific Research(KBN) grant No. 032290/C.PO6-6/2003.

References[1]. Stoeppler M., Wolf W.R., Jenks P.J.: Reference ma-

terials for chemical analysis. Certification, availabilityand proper usage. Wiley-VCH, Weinheim 2001.

[2]. Reference materials in analytical chemistry. A guidefor selection and use. Ed. A. Zschunke. Springer, Berlin2000.

[3]. Dybczyński R.: Food Addit. Contam., 19, 928 (2002).[4]. ISO/IEC Guide 35: Certification of reference materials

– general and statistical principles. ISO, Geneva 2006.[5]. ISO Guide 30: Terms and definitions used in con-

nection with reference materials. ISO, Geneva 1992.[6]. ISO/IEC Guide 34: Quality system guidelines for the

production of reference materials. ISO, Geneva 2000.[7]. ISO/IEC Guide 33: Uses of certified reference ma-

terials. ISO, Geneva 2000.[8]. ISO Guide 31: Contents of certificates of reference

materials. ISO, Geneva 2000.[9]. Linsinger T.P.J., Pauwels J. Lamberty A., Schimmel

H.G., van der Veen A.H.M., Siekmann L.: FreseniusJ. Anal. Chem., 370, 183 (2001).

[10]. Dybczyński R., Danko B., Kulisa K., Chajduk-Male-szewska E., Polkowska-Motrenko H., Samczyński Z.,Szopa Z.: Chem. Anal. (Warsaw), 49, 143 (2004).

[11]. Dybczyński R., Danko B, Polkowska-Motrenko H.:Fresenius J. Anal. Chem., 370, 130 (2001).

[12]. Samczyński Z., Dybczyński R.: Chem. Anal. (Warsaw),41, 873 (1996).

[13]. Polkowska-Motrenko H., Danko B., Dybczyński R.,Becker D.A.: J. Radioanal. Nucl. Chem., 207, 401(1996).

[14]. Danko B., Dybczyński R.: J. Radioanal. Nucl. Chem.,216 (1), 51 (1997).

[15]. Polkowska-Motrenko H., Danko B., Dybczyński R.:Anal. Bioanal. Chem., 379, 221 (2004).

[16]. Polkowska-Motrenko H., Danko B., Dybczyński R.:Chem. Anal. (Warsaw), 50, 155 (2005).

[17]. Polkowska-Motrenko H., Dybczyński R.: J. Radioanal.Nucl. Chem, 269, 339 (2006).

[18]. Dybczyński R., Danko B., Polkowska-Motrenko H.,Samczyński Z.: Talanta, 71, 529 (2007).

DETERMINATION OF CADMIUM, LEAD AND COPPERIN FOOD PRODUCTS AND ENVIRONMENTAL SAMPLES

BY ATOMIC ABSORPTION SPECTROMETRYAFTER SEPARATION BY SOLID PHASE EXTRACTION

Jadwiga Chwastowska, Witold Skwara, Elżbieta Sterlińska, Jakub Dudek, Leon Pszonicki


[6] and the determination of some heavy metals inhighly mineralized waters [7]. In the presented work,we demonstrate that this sorbent has a versatile

character and may be applied for the separation anddetermination by graphite furnace atomic absorp-tion spectrometry of most toxic elements in variousenvironmental materials and food products. This

fact enables the unification of analytical methodsand, thereby simplification of the work in the labo-ratories analyzing materials of various types.

The preliminary preparation of samples, theirmineralization and transformation into solution isa very important step of any analytical procedure.In the case of environmental and food samples con-taining mostly organic matter these operations

create often serious problems. On the one hand,some organic compounds are resistant to mineral-ization and require application of very strong con-

ditions, on the other hand, the toxic elements canform easy volatile organo-metallic compounds thatmay be easy lost. In the proposed method the samples

were dried, ground and mineralized in a micro-wave mineralizer. The mineralization conditionsare presented in Table 1. The obtained solutionswere evaporated to wet residues, dissolved in 0.2 M

hydrochloric acid, neutralized by sodium hydrox-ide to pH 4 and put into a column with the dithizonsorbent. The adsorbed elements were eluted by 2 Mnitric acid and determined by graphite tube atomicabsorption spectrometry.

The accuracy of the method was checked by thedetermination of cadmium, lead and copper in threevarious certified reference materials. The obtained

results are established in Table 2. All of them areinside the confidence intervals what proves that thetested method is accurate.

Table 3. Results of copper, cadmium and lead determination in selected food products and environmental materials(mean values for n=5).

* a – certified values.** b – determined values (mean values of 5 determinations).

Table 2. Results of analysis of certified materials.

Table 1. Conditions for sample mineralization and dilution (sample – 0.2-0.5 g, maximum volume of solution – 8 mL).


The presented method was applied for the analy-sis of some environmental materials (soil, street dustand grass) and various food products. The obtainedresults and their precision expressed as relativestandard deviations (RSD) are demonstrated inTable 3. The relative standard deviations vary in therange from 0.5 to 3% due to the type of sample andthe determined element and indicate that the pre-cision of the applied methods is satisfactory.

References[1]. Goswami A., Singh A.K.: Anal. Chim. Acta., 454, 229

(2002).[2]. Osman M.M., Kholeif S.A., Aboul Al.-Mauty N.A.:

Microchim. Acta, 143, 25 (2003).

the rms deviation of 0.0408(10) Å. Carboxylategroups deviate from the mean ring plane by 5.4(5)o

(C7O1O2) and 5.0(5)o (C8O3O4). Hydrogen bonds

The structure of bis(μ-pyridazine-3,6-dicar-boxylato-κ4N,O:N’,O’)-bis[diaquazinc(II)],Zn2(C6H2N2O4)2(H2O)4, is composed of isolatedcentrosymmetric dinuclear units built up of twoZn(II) ions bridged by two fully deprotonatedpyridazine-3,4-dicarboxylate ligand molecules.The Zn1 ion is cheleted by two N,O bondinggroups each donated by a different ligand mol-ecule: Zn1-O1 2.033(2) Å, Zn1-O3 2.045(2) Å,Zn1-N1 2.160(2) Å, Zn1-N2 2.172(2)Å and twowater oxygen atoms in axial positions (Zn1-O52.145(2)Å, Zn1-O6 2.121(2) Å) forming an octa-hedral enviroment. Figure 1 shows the molecule ofthe dimer with atom labelling scheme, Fig.2 – thepacking of dimers in the unit cell. The inversioncentres of the complex molecules coicide with the

inversion centres generated in the unit cell by thesymmetry elements of the space group Pbca. Zn(II)ions and the pyridazine rings are coplanar with

[3]. Pramanik S., Dhara S., Bhattacharyya S.S., Chatto-padhyay P.: Anal. Chim. Acta, 556, 430 (2006).

[4]. Burham N., Abel-Azeem S.M., El-Shahat M.F.: Anal.Chim. Acta, 579, 193 ( 2006).

[5]. Chwastowska J., Skwara W., Sterlińska E., PszonickiL.: Talanta, 64, 224 (2004).

[6]. Chwastowska J., Skwara W., Sterlińska E., Dudek J.,Pszonicki L.: Speciation analysis of selenium in mineralwaters by graphite furnace atomic absorption spectro-metry after separation on dithizone sorbent. Chem.Anal. (Warsaw), in press.

[7]. Chwastowska J., Skwara W., Sterlińska E., Dudek J.,Pszonicki L.: Determination of cadmium, lead, copperand bismuth in highly mineralized waters by solid phaseextraction and atomic absorption spectrometry. Chem.Anal. (Warsaw), in press.

Fig.2. The alignment of dimeric molecules in the unit cell.For clarity, only a half of the dimers is shown.

Fig.1. The asymmetric unit of the title compound with atomlabeling scheme. Displacement ellipsoids are drawnat the 50% probability level.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDSWITH HETEROCYCLIC CARBOXYLATE LIGANDS.

PART LIX. THE CRYSTAL AND MOLECULAR STRUCTUREOF A ZINC(II) COMPLEX WITH PYRIDAZINE-3,6-DICARBOXYLATE

AND WATER LIGANDSMichal Gryz1/, Wojciech Starosta, Janusz Leciejewicz

1/ Office for Registration of Medicinal Products, Medical Devices and Biocides, Warszawa, Poland


with lengths in the range from 2.743(3) to 2.816(3)Å operate between the coordinated water mol-ecules, and carboxylate oxygen atoms belonging toadjacent dimers. They are responsible for the co-hesion of the structure.

X-ray diffraction data collection was carried outon a KUMA KM4 four circle diffractometer at theInstitute of Nuclear Chemistry and Technology.Structure solution and refinement was performedusing SHELXL-97 program package.

References

[1]. Part LV. Premkumar T., Govindarajan S., Starosta W.,Leciejewicz J.: Diaquatetrakis(pyrazine-2-carboxy-lato-κ2O,N)-thorium(IV) trihydrate. Acta Crystallogr.,E62, m98-m100 (2006).

one, the Zn(II) ion is octahedrally coordinated bytwo, oriented in trans mode ligand molecules, eachvia its N,O bonding moiety and two water oxygenatoms. In the other, the Zn(II) ion is pentacoor-dinated by N,O bonding moieties of two ligandmolecules and one water oxygen atom (Fig.3). Six

Fig.3. The molecules of [Zn(C4H3N2O2)2(H2O)2][Zn(C4H3N2O2)2(H2O)]·3H2O with atom labelingscheme. Displacement ellipsoids are drawn at the50% probability level.

Fig.2. Packing diagram of Mg(C4H3N2O2)2(H2O)2.

Magnesium imidazolate: trans-diaquabis(imi-dazole-4-carboxylato-κ2N,O)-magnesium(II),Mg(C4H3N2O2)2(H2O)2, crystallizes in the mono-clinic system (space group P21/c). The structure iscomposed of monomeric molecules, each contain-ing a Mg(II) ion located at the inversion centreand chelated by two imidazole-4-carboxylate ligandmolecules via their N,O bonding moieties (Mg-N2.193(2) Å, Mg-O 2.070(2) Å) and two water oxy-gen atoms (Mg-O 2.063(2) Å). A fairly regularoctahedron with water oxygen atoms at the apical

positions is formed (Fig.1). The imidazole rings arecoplanar. The monomers are kept together by hy-drogen bonds in which the water molecules andprotonated nitrogen atoms act as donors (Fig.2).

Triclinic unit cell (space group P1) of zincimidazolate: [trans-diaquabis(imidazole-4-car-boxylato-κ2N,O)-zinc(II)][monoaquabis(imi-dazole-4-carboxylato-N,O)-zinc(II)] trihydrate,[Zn(C4H3N2O2)2(H2O)2][Zn(C4H3N2O2)2(H2O)]·3H2O,contains two monomeric complex molecules. In

[2]. Part LVI. Gryz M., Starosta W., Leciejewicz J.: trans-Di-aquabis(pyridazine-3-carboxylato-κ2O,N)-magnes-ium(II) dihydrate. Acta Crystallogr., E62, m123-m124(2006).

[3]. Part LVII. Starosta W., Leciejewicz J., Premkumar T.,Govindarajan S.: Crystal structures of two Ca(II) com-plexes with imidazole-4,5-dicarboxylate and waterligands. J. Coord. Chem., 59, 557-564 (2006).

[4]. Part LVIII. Starosta W., Leciejewicz J.: catena-Po-ly[[aquacalcium(II)]bis(μ-1H-imidazole-4-carboxy-lato)κ4N,O:O,O’; κ3O,O’:O’]. Acta Crystallogr., E62,m2648-m2650 (2006).

[5]. Part LIX. Gryz M., Starosta W., Leciejewicz J.:Bis(μ-pyridazine-3,6-dicarboxylato-κ4N,O:N’,O’)-bis[di-aquazinc(II)]. Acta Crystallogr., E62, m3470-m3472(2006).


PART LX. THE CRYSTAL AND MOLECULAR STRUCTURESOF MAGNESIUM(II) AND ZINC(II) COMPLEXES

WITH IMIDAZOLE-4-CARBOXYLATE AND WATER LIGANDSMichal Gryz1/, Wojciech Starosta, Janusz Leciejewicz


Fig.1. Mg(C4H3N2O2)2(H2O)2 molecule with atom labelingscheme. Displacement ellipsoids are drawn at the50% probability level.


labelling scheme, Fig.2 – the packing diagram of thestructure. The protonated carboxylic oxygen atoms,the coordinated water molecules, the solvationwater molecules and the protonated pyrazole ringnitrogen atoms participate in a network of hydro-

gen bonds responsible for the stability of the struc-ture. Their lengths are in the range from 2.509(2)to 2.916(2) Å.

Fig.2. The unit cell of Mn(C5H3N2O4)2·2H2O. Dashed linesindicate hydrogen bonds.

Fig.4. Packing diagram of [Zn(C4H3N2O2)2(H2O)2][Zn(C4H3N2O2)2(H2O)]·3H2O.

The structure of trans-diaquabis(1H-pyrazole-3,5--dicarboxylate-N,O)-manganese(II) dihydrate,Mn(C5H3N2O4)2·2H2O, is composed of monomericmolecules in which Mn(II) ions situated at theinversion centres are chelated, each by two singlydeprotonated pyrazole-3,5-dicarboxylate ligandmolecules and two water oxygen atoms in transarrangement. The coordination around the Mn(II)ion is slightly distorted octahedral. The chelationof the pyrazole-3,5-dicarboxylate ligand proceedsvia its N,O bonding moiety consisting of the hetero--ring nitrogen atom N2 and the oxygen atom O1of the nearest carboxylate group: Mn1-O1 2.183(2)Å, Mn1-N2 2.215(1) Å, Mn1-O5 2.156(2) Å. Theother carboxylate group remains protonated andparticipates only in a network of hydrogen bonds.The pyrazole ring is planar: rms 0.0005 Å. The pro-tonated carboxylic group C7O3O4 deviates fromit only by 1.9(1)o, the carboxylic group C6O1O2 –by 10.3(1)o. Figure 1 shows the molecule with atom

solvation water molecules in three symmetry in-dependent sites complete the content of the unitcell. The octahedron around the Zn(II) ion isslightly distorted with Zn-O, Zn-N and Zn-OH2bond distances of 2.152(2) Å, 2.041(3) Å and2.179(3) Å, respectively. The mean bond distancesin the pentacoordinated Zn(II) polyhedron are:2.101(2) Å (Zn-O), 2.040(2) Å (Zn-N) and 2.002(3)Å (Zn-OH2). An extended network of hydrogenbonds in which solvation water molecules, coordi-nated water molecules and protonated ring-nitro-gen atoms act as donors is responsible for the co-hesion of the structure. Hydrogen bond lengthsrange from 2.705(2) to 2.950(2) Å (Fig.4).



PART LXI. THE CRYSTAL AND MOLECULAR STRUCTUREOF A MANGANESE(II) COMPLEX

WITH PYRAZOLE-3,5-DICARBOXYLATE AND WATER LIGANDSThatan Premkumar1/, Subbian Govindarajan1/, Wojciech Starosta, Janusz Leciejewicz

1/ Department of Chemistry, Bharathiar University, Coimbatore, Tamilnadu, India

Fig.1. The molecule of Mn(C5H3N2O4)2·2H2O with atomlabeling scheme. Displacement ellipsoids are drawnat the 50% probability level.


carboxylate (2,3,5,6-PZTC) ligand molecules withtheir geometrical centres in the inversion centresat 0,1/2,1/2 (molecule 1) and 0,1/2,0 (molecule 2)

gen bonds are in the range from 2.6472(14) to2.7951(14) Å. Figure 2 shows the alignment of hy-drogen bridged almost flat molecular ribbons. Thepyridine ring of the title molecule is almost planar(rms 0.0129(1) Å). The dihedral angles between

the hetero-ring plane and the carboxylate and aminogroup planes are 5.6(1)o and 2.3(1)o, respectively.X-ray diffraction data collection was carried outon a KUMA KM4 four circle diffractometer usingan Oxford Cryogenic Cooler to maintain the tem-perature of the sample at 100 K. Structure solutionand refinement was performed using SHELXL-97program package. An analysis of inelastic neutronscattering spectra recorded at the Pulsed ReactorIBR-2 at Dubna (Russia) using a NERA-PR spec-trometer shows a good agreement with those cal-culated for a crystal.

Fig.2. The unit cell of 2-aminopyridine-3-carboxylic acid.Dashed lines indicate hydrogen bonds.

X-ray diffraction data collection was carried outon a KUMA KM4 four circle diffractometer at theInstitute of Nuclear Chemistry and Technology.


PART LXII. THE CRYSTAL STRUCTURE AND MOLECULAR DYNAMICSOF 2-AMINOPYRIDINE-3-CARBOXYLIC ACID

Andrzej Pawlukojć, Wojciech Starosta, Janusz Leciejewicz, Ireneusz Natkaniec1,2/,Dorota Nowak1,3/

1/ Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, Russia2/ The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland

3/ Faculty of Physics, Adam Mickiewicz University, Poznań, Poland

An interesting feature of the 2-aminopyridine-3-car-boxylic acid molecule is its zwitterionic structure inwhich the carboxylic proton is transferred not to theamino group but to the hetero-ring nitrogen atom.Figure 1 shows the molecule with atom labelling

scheme. This configuration produces intermolecu-lar hydrogen bonds in which the amino group andhetero-ring nitrogen atoms act as donors and thecarboxylate oxygen atoms in adjacent acid mol-ecules act as acceptors. The lengths of these hydro-

Structure solution and refinement was performedusing SHELXL-97 program package


PART LXIII. THE CRYSTAL AND MOLECULAR STRUCTUREOF A CALCIUM(II) COMPLEX

WITH PYRAZINE-2,3,5,6-TETRACARBOXYLATE AND WATER LIGANDSWojciech Starosta, Janusz Leciejewicz

Fig.1. The molecule of 2-aminopyridine-3-carboxylic acidwith atom labeling scheme. Displacement ellipsoidsare drawn at the 50% probability level.

Centrosymmetric, triclinic unit cell of Ca(II) containsfour (in two symmetry independent sites) Ca(II)ions, two fully deprotonated pyrazine-2,3,5,6-tetra-


and two water molecules coordinated to the metalions. All potential chelating sites of both ligandmolecules are engagged in bridging the metal ionsgiving rise to a three-dimensional molecular net-work.

N,O and NXIII, OXIII bonding moieties of theligand molecule 1 chelate the Ca1 and Ca1XIII ions,while the second oxygen atoms O12 and O12XIII arecoordinated to Ca1VII and Ca1VI ions, respectively.Belonging to the remaining carboxylate groupsoxygen atoms O13 and O13XIII are bonded to Ca2I

and Ca2IX ions respectively and the O14 and O14XII

oxygen atoms, each acting as bidentate are bondedto the Ca1VI and Ca1VIII ions (O14) and Ca1II andCa1VII ions (O14XIII). Thus, the ligand molecule 1bridges six Ca1 ions and two Ca2 ions. This bridg-ing pathway with the atom labelling in respect tothe inversion centre at 0,0,0 is shown in Fig.1.

Having its geometrical centre at the inversioncentre at 0,1/2,0, the ligand molecule 2 chelatesten Ca ions. Figure 2 illustrates the bridging path-way with atom labelling in respect to the inversion

centre at 0,0,0. The N,O bonding moieties com-posed of N21, O21 and N21IX, O21IX atoms coor-dinate the Ca2 and Ca2IX ions, respectively, whilethe second carboxylate oxygen atoms O22 andO22IX acting as bidentate are linked to Ca2IV, Ca1IV

and Ca2VI, Ca1VI ions, respectively. Oxygen atomsof the carboxylate groups which do not form theN,O bonding moieties act also as bidentate: O23chelates Ca2IV and Ca2II ions, while the O23IX atom– the Ca2VI and Ca2XIV ions. The O24 and O24IX

atoms are bonded to Ca1IV and Ca1XIV ions, respec-tively. In this way, the ligand molecule 2 bridgessix Ca2 and four Ca1 ions.

The bridging pathways via ligand molecules 1and 2 are interconnected by carboxylate oxygenatoms O13 and O13IX donated by the ligand mol-ecule 1 to the coordination (Fig.3).

In the third bridging pathway, the coordinatedwater oxygen atom O10 joins two adjacent Ca1 andCa2 ions. Since the Ca1-O10-Ca2 angle is 94.81(8)o,a catenated zig-zag motif is observed. The watermolecule O10 acting as a donor provides also anadditional pathway via very weak hydrogen bondsto carboxylate O14VIII and O12VII atoms.


Symmetry code in respect to the inversion cen-tre at 0,0,0: I x, y, z-1; II x, y-1, z; III -x+1, -y+2, -z+1;IV -x+1, -y+1, -z+2; V -x+1, -y+2, -z+2; VI x-1, y, z;VII -x+1, -y+1, -z+1; VIII -x, -y+2, -z+1; IX -x, -y+2,-z+1; X x+1, y, z; XI x, y, z+1; XII x, y+1, z; XIII -x,-y+1, -z+1; XIV -x, -y+2, -z+2.

Fig.1. The bridging mode of ligand molecule 1.

Fig.3. The packing of molecules in the unit cell ofCa2(2,3,5,6-PZTC)(H2O)2.

Fig.2. The bridging mode of ligand molecule 2.




PART LXIV. THE CRYSTAL AND MOLECULAR STRUCTUREOF A ZINC(II) COMPLEX WITH PYRAZOLE-4-CARBOXYLATE

AND WATER LIGANDSMichal Gryz1/, Wojciech Starosta, Janusz Leciejewicz


The monoclinic structure (space group C2/c) oftrans-tetraquabis(pyrazole-4-carboxylato-N)-zinc(II)trihydrate, Zn(C4H3N2O2)2·3H2O, contains mono-meric molecules in which the central metal ion lo-cated at the inversion centre is chelated by twopyrazole-4-carboxylate ligands via their hetero-ringnitrogen atoms and by four water oxygen atoms.The coordination around the Zn(II) ion is octa-hedral with Zn-N bond distance of 2.078(2) Å andmean Zn-O bond length of 2.125(3) Å (Fig.1).Deprotonated carboxylate groups of the ligand

molecules are not active in coordination but par-ticipate in a network of hydrogen bonds responsiblefor the cohesion of the crystal (Fig.2).

Fig.2. The unit cell of Zn(C4H3N2O2)2·3H2O. Dashed linesindicate hydrogen bonds.Fig.1. The molecule of Zn(C4H3N2O2)2·3H2O with atom

labeling scheme. Displacement ellipsoids are drawnat the 50% probability level.

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IRON CHELATORS INHIBIT DNIC FORMATIONTO THE SAME EXTENT, INDEPENDENTLY OF PERMEABILITYKamil Brzóska, Hanna Lewandowska, Sylwia Męczyńska, Barbara Sochanowicz,

Jarosław Sadło, Marcin Kruszewski

Dinitrosyl iron complexes (DNIC) are a group ofphysiologically important transducers of nitric ox-ide (NO) [1,2]. The low molecular-weight DNIChave been shown to modulate redox properties ofthe cellular interior through the inhibition of glu-tathione-dependent enzymes. Previously, we haveshown [3] that depletion of lysosomal LIP (labileiron pool) by either chelation with deferoxamine(DFO) or lysis inhibition (by treatment with 10 mMNH4Cl) in K562, human myelogenous leukemiacells leads to a considerable decrease (down to 50%,depending on the incubation time) of DNIC form-ing in the cells treated with 70 μM nitric oxide do-nor (DEANO).

We further investigated the nature of the cel-lular LIP involved in formation of DNIC in K562cells. The cells were treated with a nitric oxide do-nor in the presence of a permeable (salicylaldehydeisonicotinoyl hydrazone – SIH) or a nonpermeable(DFO) iron chelator. SIH is a highly lipophilic mol-ecule that readily enters cells and firmly chelatesthe intracellular pool of redox active iron. Thus, itwas plausible to suppose that it would chelate bothcytosolic and compartmented LIP, including lyso-somal LIP. The nonpermeable iron chelator, DFO,is a hydrophilic molecule that is taken up predomi-

nantly via endocytosis and localizes almost exclu-sively within the lysosomal compartment, where itseems to remain. Hence, we expected that the ef-fect exerted by DFO would depend on the controlof reactivity of the intralysosomal iron pool.

DNIC formation was recorded using EPR (elec-tron paramagnetic resonance). The EPR spectrawere recorded on Bruker ESP 300 at 77 K, micro-wave power – 1 mW, microwave frequency – 9.31

GHz, modulation amplitude – 3.027 G and timeconstant – 41 ms. In order to estimate the values ofg coefficients computer simulation was performedon SimFonia 1.25 software (Bruker AnalytischeMesstechnik, DE).

The results presented in Figs.1-3 show that DFOinhibits DNIC formation to the similar extent as

SIH, indicating that both chelators affect similarpool of labile iron. Taken together, our present andprevious results support the view that lysosomaliron considerably contributes to the total LIP inthe cell.

Fig.1. Dose dependent induction of DNIC specific EPR sig-nal in K562 cells incubated for 6 h with different con-centrations of SIH or DFO then treated with 100 μMNO for 15 min at 37oC. Solid bars – mean ±SD, n=3.Asterix denotes statistically significant difference vs.samples treated with 100 μM NO alone (a positivecontrol), p<0.05. Open bars – per cent of initial value(cells treated with 100 μM NO alone).

Fig.2. Inhibition of EPR signal induction in K562 cells incu-bated with 100 μM SIH for 0, 1, 3 and 6 h, and thentreated with 100 μM NO for 15 min at 37oC. Solidbars – mean ±SD, n=3. Asterix denotes statisticallysignificant difference vs. samples treated with 100 μMNO alone (a positive control), p<0.05. Open bars –per cent of initial value (cells treated with 100 μMNO alone).

Fig.3. Inhibition of EPR signal induction in K562 cells incu-bated with 1000 μM DFO for 1, 3 and 6 h, and thentreated with 100 μM NO for 15 min at 37oC. Solidbars – mean ±SD, n=3. Asterix denotes statisticallysignificant difference vs. samples treated with 100 μMNO alone (a positive control), p<0.05. Open bars –per cent of initial value (cells treated with 100 μMNO alone).

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The work was supported by the Polish Ministryof Education and Science statutory grant for theINCT.

References[1]. Vanin A., Kleschyov A.: In: Nitric oxide in transplant

rejection and anti-tumor defence. Eds. S. Lukiewicz,

of DNA damage was evaluated by the alkaline cometassay [2]. To investigate the influence of ghrelin oncells’ ability to repair DNA damage, BMNC wereirradiated with 2 Gy of X-radiation and disappear-ance of DNA breaks was monitored 0.5, 1 and 2 hafter irradiation.

We found that ghrelin had a marked effect onthe level of X-ray induced DNA damage: there wasa significant increase in the initial level of DNAstrand breaks in cells from ghrelin treated animalsas compared with untreated controls (Fig.1). How-ever, no effect of ghrelin was observed on the cel-lular capacity to rejoin DNA strand breaks (Fig.2).

This is the first observation of the participationof ghrelin in the cellular response to X-irradiation.It points to the role of ghrelin in enhancing thegenotoxicity of oxidative stress-inducing factorsgenerated during inflammation.

The work was supported by the Polish Minis-try of Education and Science, project numberPBZ-KBN-093/P06/2003.

References[1]. Gil-Campos M., Aguilera C.M., Canete R., Gil A.: Br.

J. Nutr., 96, 201-226 (2006).[2]. Wojewodzka M., Kruszewski M., Iwanenko T., Collins

A.R., Szumiel I.: Mutat. Res., 416, 21-35 (1998).

Ghrelin, a recently described endogenous ligandfor the growth hormone secretagogue receptor(GHS-R), is a 28 amino acid peptide encoded byGHRL gene and is derived from a 117 amino acidprecursor peptide. It is produced by stomach cellsand is a potent regulator of food intake, energy ex-penditure, adiposity, and growth hormone secre-tion (reviewed in [1]). Ghrelin reduces peripheralenergy expenditure and enhances appetite by ac-tivating neurons that express Agouti-related pep-tide and neuropeptide Y. GHS-R and ghrelin areexpressed in human T lymphocytes and monocytes,where ghrelin inhibits the expression of proinflam-matory cytokines. Other functional roles of ghrelinat the cellular level remain poorly defined.

We investigated the effect of ghrelin addition tofood on the susceptibility of peripheral blood mono-nuclear cells (BMNC) to DNA damage generatedby X-irradiation. Ghrelin was applied intragastric-ally to newborn piglets for 7 days at a dose of 15μg/kg body mass. After treatment, blood was col-lected by heart puncture and BMNC were isolatedby density gradient centrifugation on Histopaque1137, resuspended in RPMI1640 medium supple-mented with 20% of foetal calf serum. Isolated cellswere exposed to X-radiation (dose range – 0-3 Gy,200 kV, 5 mA, dose rate – 1.2 Gy/min). The extent

J.L. Zweier. Kluwer Academic Publishing, Boston 1999,pp. 49-82.

[2]. Ueno T., Yoshimura T.: Jpn. J. Pharmacol., 82, 95-101(2000).

[3]. Męczyńska S., Lewandowska H., Kruszewski M.: ActaBiochim. Polon., 55, Suppl. 1, 192 (2006).

GHRELIN, A LIGAND FOR THE GROWTH HORMONESECRETAGOGUE RECEPTOR, INCREASES DNA BREAKAGEIN X-IRRADIATED PIGLET BLOOD MONONUCLEAR CELLSMarcin Kruszewski, Teresa Iwaneńko, Jarosław Woliński1/, Maria Wojewódzka

1/ The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences,Jabłonna, Poland

Fig.1. The effect of ghrelin treatment on the initial X-ray-in-duced DNA breaks in piglet BMNC evaluated by thealkaline comet assay.

Fig.2. Lack of effect of ghrelin treatment on the capacity ofpiglet BMNC to repair DNA damage induced by 2 Gyof X-radiation.

RADIOBIOLOGY 101

The recently described endogenous ligand for thegrowth hormone secretagogue receptor, ghrelin,was found to inhibit hydrogen peroxide-inducedcytokine release in human umbilical vein endothe-lial cells [1]. This suggested that the peptide blocksredox-mediated cellular signalling. Moreover, ghrelininhibited basal and TNF-alpha-induced activationof nuclear factor-kappaB [1], a process initiated byDNA damage [2]. However, the effect of ghrelin onDNA damage induction has not been studied untilnow.

We investigated the effect of ghrelin additionto food on the susceptibility of piglet peripheralblood mononuclear cells (BMNC) to DNA dam-age generated by hydrogen peroxide. Ghrelin wasapplied intragastrically to newborn piglets for 7 daysat two doses (7.5 and 15 μg/kg body mass). Aftertreatment, blood was collected by heart punctureand BMNC were isolated by density gradient cen-trifugation on Histopaque 1137, resuspended inRPMI1640 medium supplemented with 20% offoetal calf serum. Isolated cells were exposed to hy-drogen peroxide (0-250 μM) in phosphate bufferedsaline for 15 min at 4oC. The extent of DNA dam-age was evaluated by the alkaline comet assay [3].

We found that ghrelin had a marked effect onthe level of hydrogen peroxide-induced DNA dam-age: there was a significant increase in the initiallevel of DNA strand breaks in cells from ghrelintreated animals as compared with untreated con-

trols (Fig.1). This effect did not depend on ghrelindose (Fig.2), supporting the relation of the observedenhancement of DNA damage to cellular signal-ling.

Together with the preceding report on the ef-fect of ghrelin on the initial DNA breaks in X-ir-radiated cells, this observation points to the roleof ghrelin in enhancing the genotoxicity of oxida-tive stress-inducing factors generated during in-flammation. Overproduction of ghrelin may leadto excessive DNA damage and consequent cyto-toxicity, especially under inflammatory conditions,where DNA damaging agents, such as reactiveoxygen or nitrogen species, are produced. Thus,the discovered effect of ghrelin may have somerelevance to the pathophysiology of obesity-linkeddiseases.


References[1]. Li W.G., Gavrila D., Liu X., Wang L., Gunnlaugsson S.,

Stoll L.L., McCormick M.L., Sigmund C.D., Tang C.,Weintraub N.L.: Circulation, 109, 2221-2226 (2004).

[2]. Wu Z.H., Shi Y., Tibbetts R.S., Miyamoto S.: Science,311, 1141-1146 (2006).

[3]. Wojewódzka M., Kruszewski M., Iwaneńko T., CollinsA.R., Szumiel I.: Mutat. Res., 416, 21-35 (1998).

Fig.1. The effect of ghrelin treatment on the initial hydro-gen peroxide-induced DNA breaks in piglet BMNCevaluated by the alkaline comet assay.

GHRELIN INCREASESHYDROGEN PEROXIDE-INDUCED DNA BREAKAGE

IN PIGLET BLOOD MONONUCLEAR CELLSTeresa Bartłomiejczyk, Teresa Iwaneńko, Maria Wojewódzka, Jarosław Woliński1/,

Roman Zabielski2/, Marcin Kruszewski1/ The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences,

Jabłonna, Poland2/ Warsaw Agricultural University, Poland

Fig.2. Lack of effect of ghrelin dose on the initial hydro-gen peroxide-induced DNA breaks in piglet BMNCevaluated by the alkaline comet assay.

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Leptin, an adipose tissue cytokine is known to re-duce food intake and to increase energy expendi-ture. Previous studies in rats indicated that gastricleptin is involved in cytoprotection in the rat pan-creas and gastric mucosa. This protection dependsupon vagal activity and sensory nerves and involveshyperemia probably mediated by nitric oxide andmimicking the gastroprotective effect of cholecys-tokinin (CCK) [1]. On the other hand, long form ofleptin receptor (Ob-Rb) is expressed on the peri-pheral blood mononuclear cells (BMNC) and theexistence of a reciprocal regulatory network is an-ticipated, by which leptin may control immune cellactivation and inflammation (reviewed in [2,3]).Leptin up-regulates growth hormone secretagoguereceptor (GHS-R) expression on human T lym-phocytes, modulates the activation of peripheralBMNC and it is known to have a proinflammatoryaction.

We examined the influence of leptin on the sus-ceptibility of human cells to ionizing radiation orhydrogen peroxide. Human peripheral BMNCwere isolated from whole blood by density gradi-

ent centrifugation on Histopaque 1137, resus-pended in RPMI1640 medium supplemented with20% of foetal calf serum, stimulated with phyto-hemagglutinin (PHA) and pretreated with leptin

(20 μg/ml) for 20 h. After pretreatment, cells wereX-irradiated (dose range – 0-8 Gy) in an ANDREXX-ray machine (Holger Andreasen, Denmark; 200kV, 5 mA, dose rate – 1.2 Gy/min) or exposed toH2O2 (0-250 μM) in phosphate buffered saline for15 min at 4oC. The extent of DNA damage wasevaluated by the alkaline comet assay [3].

Leptin had no effect on BMNC proliferationafter PHA stimulation. Pretreatment with leptin hadno effect on the level of X-radiation- and H2O2-in-duced DNA breakage (Figs.1 and 2).

The results described here and in the preced-ing two reports indicate that leptin has different ef-fects on cellular susceptibility to DNA damagingagents in vivo and in vitro.


References[1]. Brzozowski T., Konturek P.C., Pajdo R., Kwiecien S.,

Ptak A., Sliwowski Z., Drozdowicz D., Pawlik M.,Konturek S.J., Hahn E.G.: J. Physiol. Pharmacol., 52,583-602 (2001).

[2]. Popovic V., Duntas L.H.: Horm. Metab. Res., 37,533-537 (2005).

[3]. Broberger C.: J. Intern. Med., 258, 301-327 (2005).

THE EFFECT OF LEPTIN ON DNA BREAKAGEINDUCED BY GENOTOXIC AGENTS

IN HUMAN PERIPHERAL BLOOD MONONUCLEAR CELLSMarcin Kruszewski, Teresa Iwaneńko, Maria Wojewódzka, Jarosław Woliński1/,

Roman Zabielski2/

1/ The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences,Jabłonna, Poland

2/ Warsaw Agricultural University, Poland

Fig.2. The effect of leptin treatment on the initial hydro-gen peroxide-induced DNA breaks in human BMNCevaluated by the alkaline comet assay.

Fig.1. Lack of effect of leptin treatment on the initial X-ray--induced DNA breaks in human BMNC evaluatedby the alkaline comet assay.

RADIOBIOLOGY 103

frequently used, sometimes combined with centricrings, and the cytokinesis blocked micronucleus(CBMN) assay has also been developed. Numerousstudies, performed both on animals and humans,have demonstrated a close correspondence betweenaberrations or micronuclei induced in peripheralblood lymphocytes under in vitro and in vivo condi-tions. This allows one to estimate a radiation doseabsorbed during an accident by reference to an invitro calibration curve. This curve is generated byirradiating blood samples, collected from controldonors, with several doses of radiation. Followingculturing of lymphocytes, microscopic slides are

The aim of biological dosimetry is the calculationof the dose and the range of uncertainty to whichan accident victim was exposed. This process re-quires the use of the maximum likelihood methodfor the proper fitting of an in vitro calibration curve,a procedure which is not implemented in popular,commercially available statistical computer pro-grams.

The most specific and sensitive technique of bio-logical dosimetry relies on estimating the frequencyof unstable chromosomal damage in peripheralblood lymphocytes of the exposed person [1,2]. Thedicentric chromosome aberration assay is the most

Fig. A screenshot of the main menu of the program.

CABAS – A FREELY AVAILABLE PC PROGRAMFOR FITTING CALIBRATION CURVES

IN CHROMOSOME ABERRATION DOSIMETRYJoanna Deperas1/, Marta Szłuińska2/, Marta Deperas-Kaminska3,4/, Alan Edwards2/,David Lloyd2/, Carita Lindholm5/, Horst Romm6/, Laurence Roy7/, Raymond Moss8/,

Josselin Morand8/, Andrzej Wójcik1,4,8/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Health Protection Agency, Centre for Radiation, Chemical and Environmental Hazards, Chilton,

Didcot, United Kingdom3/ Joint Institute for Nuclear Research, Dubna, Russia

4/ Świętokrzyska Academy, Kielce, Poland5/ Radiation and Nuclear Safety Authority (STUK), Helsinki, Finland

6/ Bundesamt für Strahlenschutz, Neuherberg, Germany7/ Institut de Radioprotection et de Sûreté Nucléaire, Fontenay-aux-Roses Cedex, France

8/ Institute for Energy – JRC European Commission, Petten, the Netherlands

RADIOBIOLOGY104

prepared and the frequencies of dicentrics andrings are estimated in first division metaphases ormicronuclei in binucleate cells. The points of thedose-response relationship are fitted to an equa-tion which is linear-quadratic for low LET (linearenergy transfer) radiation and linear for high LETradiation.

The correct fitting procedure is not trivial be-cause it requires an appropriate weighting of datapoints. Several laboratories have produced theirown curve fitting programs for internal use but theseare frequently not user-friendly and not availableto outside users. Therefore, a PC-based freely avail-able program called CABAS, for fitting dose-re-sponse curves to chromosomal aberration or micro-nucleus data and for calculating the dose and con-fidence limit (CL) has been developed and tested.The program consists of (i) the main curve-fittingand dose estimating module, (ii) a module for cal-culating the dose in cases of partial body exposure,(iii) a module for estimating the minimum numberof cells necessary to detect a given dose of radia-

Whereas temperature of pre-irradiation incu-bation as well as that during exposure exerted adistinct effect on the frequency of radiation-inducedmicronuclei in human peripheral blood lympho-cytes, the presence of DMSO completely abolishedthis effect: the dose-effect curves for all three tem-peratures were identical.

In the interaction of ionizing radiation withDNA one discerns direct and indirect effect, thelatter produced in the water layer surrounding theDNA molecule. Since DMSO is a scavenger of theOH• radical which is produced in the process ofwater radiolysis, the presented results indicatethat temperature conditions affect the indirectlyinduced damage. At this stage of our research,we cannot explain which mechanisms are respon-sible for the effect of temperature on the level ofradiation-induced cytogenetic damage, althoughwe presume that chromatin conformation mayplay a role. It is plausible to assume that acces-sibility of DNA to the radical attack depends onthe steric relations of the chromatin componentsand specifically, on the extent of protection byproteins. Temperature dependent structural tran-sitions in the protein-DNA complex (e.g. [4]), aswell as temperature dependence of binding ofspecific nuclear proteins to DNA (e.g. [5,6]) havebeen described but not systematically exploredfrom the point of view of chromatin radiosensi-tivity.


The impact of temperature on the frequency ofradiation-induced chromosome aberrations in thehuman lymphocytes was first described by Bajerskaand Liniecki [1]. We have previously described [2]experiments carried out to analyze the impact ofblood temperature at irradiation in vitro on thelevel of radiation-induced micronuclei. We foundthat temperature of pre-irradiation incubation aswell as that during exposure exerted an effect onthe frequency of radiation-induced micronuclei inhuman peripheral blood lymphocytes. The highestfrequency of micronuclei was observed for bloodsamples incubated at 37oC before and during irra-diation in vitro with doses of 2 and 2.7 Gy, inter-mediate – at 20oC and the lowest one – at 0oC.

Blood samples were drawn from two healthymale donors aged 24 and 45 years and irradiatedat 0, 20 and 37oC with X-rays 200 kVp, 5 mA, 3 mmCu filter. The doses were: 0, 1 and 2 Gy for thefirst donor, and 0, 1.35 and 2.7 Gy for the seconddonor. For 20 min before irradiation as well as dur-ing irradiation, the blood samples were incubatedat 0, 20 or 37oC. dimethylsulphoxide (DMSO) wasadded 5 min before irradiation at the concentra-tion of 0.5 mol/dm3. After irradiation, the sampleswere centrifuged in order to discard supernatantscontaining DMSO; cells were then transferred into4.5 ml RPMI 1640 medium supplemented with 25%calf serum, 2.5% phytohaemagglutinin (PHA),antibiotic solution and incubated for 72 h at 37oCand 5% CO2. Lymphocyte preparations for micro-nuclei analysis were prepared according to thestandard method of Fenech [3].

tion, and (iv) a module for calculating the dose inthe case of a fractionated or protracted exposure(Fig.).

The program can be downloaded as freewarefrom http://www.pu.kielce.pl/ibiol/cabas or obtainedfrom any of the present authors. The use of the pro-gram is straightforward and it can be expected thatits use will improve the precision of dose estimatesby biological dosimetry in cases of radiation acci-dents. Furthermore, it should facilitate setting upinter-laboratory dose effect curves.


References[1]. Cytogenetic analysis for radiation dose assessment. A

manual. IAEA, Vienna 2001.[2]. Voisin P., Barquinero J.F., Blakely B., Lindholm C.,

Lloyd D., Luccioni C., Miller S., Palitti F., PrasannaP.G., Stephan G., Thierens H., Turai I., Wilkinson D.,Wojcik A.: Cell. Mol. Biol., 48, 501-504 (2002).

THE TEMPERATURE EFFECTON THE FREQUENCY OF RADIATION-INDUCED MICRONUCLEI

IN HUMAN PERIPHERAL BLOOD LYMPHOCYTESIS ABOLISHED BY DMSO

Kinga Brzozowska, Andrzej Wójcik

RADIOBIOLOGY 105

tions including the complex ones were transformedinto primary breaks. The break frequencies werescaled to the whole genomic frequencies. The re-sults are presented in Fig.1. For all donors, the low-est frequency of breaks was observed in chromo-some 2 and the highest in chromosome 14 in lym-phocytes of donor 3, chromosome 8 of donor 2,and at the same level in chromosomes 8 and 14 ofdonor 1 (Fig.1A). The found break frequency isbelow the expected values for chromosome 2 andabove the expected values for chromosomes 8 and14. Only for chromosome 14 of donor 2 the ratiois close to unity (Fig.1B).

The lowest frequencies of exchanges werescored in chromosome 2 and the inter-donor vari-

ability was low. Chromosomes 8 and 14 were in-volved in exchanges more frequently than expectedon the basis of DNA content. In contrast, the in-volvement of chromosome 2 was less frequent thanexpected.

This is the first study investigating the individualradiosensitivity of chromosomes of human periph-eral blood lymphocytes to heavy ions. Generally,the sensitivity of chromosome 2 was lower, and that

References

[1]. Bajerska A., Liniecki J.: Int. J. Radiat. Biol., 16, 483-493(1969).

[2]. Brzozowska K., Wójcik A.: The effect of temperatureon the frequency of radiation-induced micronuclei inhuman peripheral blood lymphocytes. In: INCT AnnualReport 2005. Institute of Nuclear Chemistry and Tech-nology, Warszawa 2006, pp.102-103.

For a wide variety of biological effects, radiationsof high linear energy transfer (LET) have beenknown to have greater biological effectiveness perunit dose than those of low LET [1]. Little is knownabout the extent of individual variability in theradiosensitivity of human cells to high LET radia-tion. In all published studies dealing with individualradiosensitivity, the studied cells (lymphocytes orfibroblasts) were only exposed to low LET radia-tion. The purpose of this study was to investigateby FISH the distribution of radiation-inducedchromosomal aberrations in chromosomes 2, 8 and14 in lymphocytes of 3 donors.

Irradiation of blood from 3 healthy donors wasperformed at the Nuclotron accelerator at the Joint

Institute for Nuclear Research (Dubna, Russia).Whole blood samples were irradiated with 1.1, 2.3and 3.5 Gy of 12C-ions. At the position of the samplethe beam energy was 480 MeV/n and LET=10.6keV/μm. Chromosomes 2, 8 and 14 were paintedin different colors and aberrations scored with thehelp of an image-analysis system, as described in [2].

In order to assess the overall radiosensitivity ofthe painted chromosomes, chromosomal aberra-

[3]. Fenech M.: Mutat. Res., 285, 35-44 (1993).[4]. Peters W.B., Edmondson S.P., Shriver J.W.: J. Mol.

Biol., 343, 339-360 (2004).[5]. Santilli G., Schwab R., Watson R., Ebert C., Aronow

B.J., Sala A.: J. Biol. Chem., 280, 15628-15634 (2005).[6]. Ferreira M.E., Hermann S., Prochasson P., Workman

J.L., Berndt K.D., Wright A.P.: J. Biol. Chem., 280,21779-21784 (2005).

VARIABLE RADIOSENSITIVITY OF CHROMOSOMES 2, 8 AND 14IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES

EXPOSED TO 480 MeV/n 12C-IONSMarta Deperas-Kaminska1,2/, Gennady N. Timoshenko1/, Eugene A. Krasavin1/, Andrzej Wójcik2,3/

1/ Joint Institute for Nuclear Research, Dubna, Russia2/ Świetokrzyska Academy, Kielce, Poland

3/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland

Fig.1. Primary breaks observed in the painted chromosomes of 3 donors. Breaks calculated from aberrations observedafter exposed to 3.5 Gy of 480 MeV/n 12C-ions were summed up and scaled to the whole genomic frequency. Theabsolute numbers are shown in Fig.1A and the ratios of found to expected are shown in Fig.1B. Error bars representstandard deviations from the mean; also, values are shown for the three painted chromosomes of all donors.

RADIOBIOLOGY106

of chromosomes 8 and 14 – higher than expected.These data suggest that the sensitivity of humanchromosome to heavy ions is individually variable.The results are in line with those of a recent studyon the sensitivity of chromosomes 2, 8 and 14 togamma rays [2].

down the DSB rejoining in M059 K and has noeffect in M059 J cells. This suggested a direct linkbetween EGFR kinase activity and DNA-PK-de-pendent DSB rejoining and was consistent with ob-servation of other authors [3]. Now, we have examin-ed survival of both cell lines after X-irradiationcombined with tyrphostin treatment. The doserange for each cell line was chosen so that the sur-vival level was comparable (between 90 and 1%).The survival data were expressed as the ratio ofsurvival after combined treatment to that afterX-irradiation alone. Ratio equal to unity means astrictly additive effect, that is, independent effectof each of the agents tested. A less than additiveeffect (protection) or more than additive effect (sen-sitisation) indicate an interaction of both agents.As shown in Fig., in M059 K cells there is a morethan additive effect of combined (X+T) treatment,i.e. radiosensitisation; this effect is absent in M059Jcells (close to additive effect at doses up to 1 Gyand protective effect at higher doses).

In conclusion, tyrphostin AG 1478 slowes downthe DSB rejoining in M059 K and has no effect inM059 J cells. This effect corresponds with a decreasein survival in M059 K but not in M059 J cells sub-jected to combined (T+X) treatment and suggestsa direct relation between EGFR kinase activity,DNA-PK-dependent DSB rejoining and survival.


References[1]. Amorino G.P., Hamilton V.M., Valerie K., Dent P.,

Lammering G., Schmidt-Ulrich R.K.: Mol. Biol. Cell,13, 2233-2244 (2002).

[2]. Harari P.M., Huang S.M.: Semin. Radiat. Oncol., 11,281-289 (2001).

[3]. Dittmann K., Mayer C., Fehrenbacher B., Schaller M.,Raju U., Milas L., Chen D.J., Kehlbach R., RodemannH.P.: J. Biol. Chem., 280, 31182-31189 (2005).

[4]. Anderson C.W., Dunn J.J., Freimuth P.I., GallowayA.M., Allalunis-Turner M.J.: Radiat. Res., 156, 2-9(2001).

[5]. Grądzka I., Buraczewska I., Sochanowicz B., SzumielI.: Eur. J. Biochem., 271 (Suppl. 1, Pt1), 1-12 (2004).

The epidermal growth factor (EGF) receptor(EGFR) is a mediator of both proliferative and sur-vival signals in mammalian cells (reviewed in [1]).Nuclear translocation of EGFR was observed afterX-irradiation and was found to be important forregulation of DNA repair processes [2,3]. We inves-tigated the effect of EGFR inhibition on variousaspects of the cellular response to X-irradiationin two related human glioma cell lines M059 K andM059 J, the latter highly sensitive to X-radiationdue to the lack of a catalytic subunit (DNA-PKcs)of DNA-dependent protein kinase (DNA-PK) [4].Tyrphostin AG 1478 was used as a specific inhibi-tor to block EGFR tyrosine kinase activity.

We have previously found that double strandbreak (DSB) rejoining after X-irradiation is fasterin M059 K than in M059 J cells [5] because of a de-fect in a nonhomologous DNA end-joining (NHEJ)in the latter cell line [4]. Tyrphostin AG 1478 slowed

References[1]. Goodhead D.T.: J. Radiat. Res., 40 (Suppl.), 1-13

(1999).[2]. Sommer S., Buraczewska I., Wojewodzka M., Bouzyk

E., Szumiel I., Wojcik A.: Int. J. Radiat. Biol., 81,741-749 (2005).

EFFICIENT DOUBLE STRAND BREAK REJOINING AND SURVIVALIN X-IRRADIATED HUMAN GLIOMA M059 CELLS ARE DEPENDENT

ON EGF RECEPTOR KINASE ACTIVITYIwona Grądzka, Barbara Sochanowicz, Irena Szumiel

Fig. Survival ratio after combined (X+T) treatment to thatafter X-irradiation alone (see text for explanations).

RADIOBIOLOGY 107

With the use of an anti-γH2AX antibody witha fluorescent tag, a pattern of γH2AX foci can berevealed a few minutes after irradiation. The fociare markers of DSB and allow to directly count theDSB number per nucleus (review in [3]). As shownin Figs.1 and 2, in xsr6 cells GPI 19015 treatmentcauses a faster disappearance of foci than in theinhibitor-untreated cells. In CHO-K1 cells thereis no effect of the inhibitor, in agreement with theweak effect on DSB rejoining estimated with thecomet assay. As stated previously, the possible rea-son of this effect may lay in the impaired DNA-PK(DNA-dependent protein kinase) dependent non-homologous end-joining (D-NHEJ) in xrs6 cells:DSB repair in these cells has to rely on the ho-mologous recombination repair or DNA-PK in-

In the preceding reports, we described the effectof sirtuin inhibitor, GPI 19015 treatment on therepair of DNA double strand breaks (DSB) andsurvival in CHO-K1 and xrs6 cells [1]. In CHO-K1cells a relatively weak effect was noted (using theneutral comet assay) at the 15 min repair interval.In contrast, in the DSB repair (nonhomologousend-joining – NHEJ) defective mutant cell line, xrs6,the increase in the rate of DSB repair was more pro-nounced, especially in G1 phase of the cell cycle.The cells were treated with sirtuin inhibitor 200 μMGPI 19015 at 37oC for 1 h and X-irradiated with 10Gy without medium change. Applying the same ex-perimental schedule, we determined the number ofγH2AX foci in both cell lines, using the foci methodas described in [2].

Fig.1. Photographs of histone γH2AX foci in control cells and cells irradiated with 1 Gy X-irradiation. Time-dependentdecrease of the histone γH2AX foci number in untreated and inhibitor-treated CHO-K1 and xrs6 cells also ispresented in Fig.2.

DECREASED PERSISTENCE OF γγγγγH2AX FOCIIN X-IRRADIATED xrs6 CELLS TREATED WITH SIRTUIN INHIBITOR

Maria Wojewódzka, Marcin Kruszewski, Irena Szumiel

Control Irradiation 1 Gy Irradiation 1 Gy 0 h 4 h

CHO-K1

CHO-K1+GPI

xrs6

xrs6+GPI

RADIOBIOLOGY108

dependent (backup) nonhomologous end-joining(B-NHEJ) [4,5]. It can be expected that sirtuin in-hibition increases histone acetylation and thus,facilitates the access of repair enzymes to the dam-aged DNA sites.

Supported by the Polish Ministry of Educationand Science statutory grant for the INCT.

References

[1]. Wojewódzka M., Kruszewski M., Szumiel I.: Backupnonhomologous end-joining is the target of sirtuin

inhibitor. In: INCT Annual Report 2005. Institute ofNuclear Chemistry and Technology, Warszawa 2006,pp. 107-108.

[2]. Cowell I.G., Durkacz B.W., Tilby M.J.: Biochem.Pharmacol., 71, 13-20 (2005).

[3]. Pilch D.R., Sedelnikova O.A., Redon C., Celeste A.,Nussenzweig A., Bonner W.M.: Biochem. Cell Biol.,81, 123-129 (2003).

[4]. Wang H., Perrault A.R., Takeda Y., Qin W., Wang M.,Iliakis G.: Nucleic Acids Res., 31, 5377-5388 (2003).

[5]. Wang H., Rosidi B., Perrault R., Wang M., Zhang L.,Windhofer F., Iliakis G.: Cancer Res., 65, 4020-4030(2005).

Fig.2. Time-dependent decrease of the histone γH2AX foci number in untreated and inhibitor-treated CHO-K1 cells(A) and xrs6 cells (B). The foci numbers are expressed as a percentage of mean initial foci number in irradiatedcells. Number of foci in controls was subtracted. Foci in 100 cells were scored for each time interval.

L5178Y-S (LY-S) subline is the longest knownmammalian radiation sensitive cell line. Althoughit is clear that the reason for radiation sensitivityof LY-S cells is an impaired DNA DSB (doublestrand break) repair, the molecular defect is un-known. LY-S cells show both phenotypic featuresthat are characteristic of cells with a defective NHEJ(nonhomologous end-joining): a pronounced G1phase radiosensitivity and a slown down DSB re-pair. Nevertheless, the NHEJ defect in LY-S cellsis not due to DNA-PK (DNA-dependent proteinkinase), Xrcc4 or ligase IV mutation. Another poss-ible defect concerning autophosphorylation in theso-called ABCDE cluster of serine and threonineresidues in the central part of the catalytic subunithas also been eliminated as a reason for impairedrepair of DSB (reviewed in [1]).

A recent paper [2] pointed to a role of 53BP1protein in the NHEJ system. 53BP1 (p53 bindingprotein) is a BRCT domain-containing protein thatis rapidly recruited to DSB after X-irradiation. Itsfunction probably consists in acting as a scaffoldprotein and contributing to ligase IV and Artemisfunctioning, as shown in Fig.1. Its absence in chickenDT40 cells was phenotypically manifested as a NHEJdefect [2] and exactly matched the phenotype ofLY-S cells; hence, there was a possibility that LY-S

cells are deprived of this protein. Therefore, weexamined the total cell extracts from both closelyrelated LY sublines, LY-R (repair competent) and

TWO p53 BINDING PROTEINSARE PRESENT IN LY-R (REPAIR COMPETENT)

AND LY-S (REPAIR DEFICIENT) CELLSIN DIFFERENT PROPORTIONS

Barbara Sochanowicz, Irena Szumiel

Fig.1. Model of NHEJ pathways according to [2]: (A) thecore NHEJ pathway, (B) ATM/Artemis – dependentpathway, (C) 53BP1 – dependent pathway. The 53BP1protein contributes to both B and C pathway. Lig IV– ligase IV.

RADIOBIOLOGY 109

LY-S (repair deficient), for 53BP1 protein, usinga specific antibody (rabbit polyclonal to 53BP1,ab36823, Abcam) and Western blotting method.K562 cells served as a positive control.

As shown in Fig.2, we detected one proteinband with the anti-53BP1 antibody in K562 cells

and two bands in LY-R and LY-S cells. In LY cellsthe two detected proteins seem to sum up to thesame amount. Nevertheless, the band correspond-ing to 53BP1 of similar molecular weight as thatin K562 cells is less abundant in LY-S cells than inLY-R cells.

There are no data on 53BP1 isoforms in theliterature. The antibody was obtained with the useof a peptide representing a portion of human 53BP1encoded in part by exons 11 and 12 as immunogen.It reacts with both the human and murine protein.Notwithstanding the possible significance of thepresence of two detected proteins expressed invarious proportions in LY sublines, it can be statedthat there is no analogy between this observationand that concerning DT40 cells with a DSB repairdefect due to lack of 53BP1. Thus, absence of 53BP1protein is not a reason of defective DSB repair inLY-S cells.

References[1]. Szumiel I.: Int. Radiat. Biol., 81 (5), 353-365 (2005).[2]. Iwabuchi K., Hashimoto M., Matsui T., Kurihara T.,

Shimizu H., Adachi N., Ishiai M., Yamamoto K.,Tauchi H., Takata M., Koyama H., Date T.: GenesCells, 11(8), 935-948 (2006).

Fig.2. Western blot showing one band detected with theanti-53BP1 antibody in K562 cells and two bands inLY-R and LY-S cells. Note that in LY cells the twodetected proteins seem to sum up to the sameamount but the ratio of band 1 to 2 differs.

PREMATURE CHROMOSOME CONDENSATIONIN BIOLOGICAL DOSIMETRY

AFTER HIGH DOSE GAMMA IRRADIATIONSylwester Sommer, Iwona Buraczewska, Andrzej Wójcik

Biological dosimetry is necessary in the case ofradiation accidents or accidental exposures to ion-izing radiation, especially in the case of lack or fail-ure of physical measurements of the dose [1].Analysis of Giemsa-stained dicentrics in humanperipheral blood lymphocytes is regarded by theInternational Atomic Energy Agency as the mostaccurate and reliable assay of biological dosimetry[1]. In the case of high radiation doses, problemscan occur with obtaining a sufficient number ofmitotic cells for analysis [1,2]. The use of drug-in-duced PCC (premature chromatin condensation)was proposed to overcome this problem [2,3].Therefore, we decided to determine the frequencyof aberrations induced by high doses of radiationin painted chromosomes 2, 8 and 14, both accu-mulated in mitotic cells and after PCC induction.

Human lymphocytes of 6 healthy donors, irra-diated with 0, 3, 5, 7 and 10 Gy of γ 60Co were cul-tured in whole blood cultures for 48 h. Twenty fourhours after set-up of cultures, colcemid was addedto the final concentration of 1 μg/ml to arrest cellsin the first mitosis after irradiation. Two hours be-fore the end of cultivation, calyculin A (50 nM) wasapplied to induce PCC. Lymphocytes were fixedaccording to the standard procedure. FISH stain-ing was performed on 3 pairs of chromosomes: 2,8, 14, using directly labeled probes from Oncor,according to the manufacturer’s protocol. At least150 cells for each dose were analyzed for every do-

nor, to the total number of 10 020 cells. Excess frag-ments or entities with color junctions, involving 3painted pairs of chromosomes, were regarded asaberrations.

Figure presents the dose-effect curve for totalaberrations in chromosomes 2, 8 and 14, scored inlymphocytes of 6 patients. There was a clear dose– dependence and no saturation of aberration yields

Fig. Dose response curves for total aberration yields de-termined with the PCC method combined with FISHstaining after in vitro irradiation of peripheral bloodlymphocytes from 6 donors with 0, 3, 5, 7 and 10 Gy ofgamma rays.

LY-R LY-S LY-R LY-S K562 60 μg 30 μg 30 μg

RADIOBIOLOGY110

up to the dose of 10 Gy. In spite of relatively lowvalues of the mitotic index (except controls) – lowerthan 1% – it was possible – due to PCC – to analyzemore than 150 spreads from each slide; this wouldnot be possible if only cells arrested in metaphaseby colcemid block were analyzed. Simultaneoususage of PCC and whole chromosome FISH al-lowed to score not only excess fragments but alsothe exchange type of aberrations, usually not rec-ognizable in PCC-spreads, because of their poorquality.

We could not see any differences between in-dividual radiosensitivity of donors – there wereonly slight differences between curves. Such resultconfirms our previous report where we also foundno difference between donors with respect to ra-diation sensitivity [4].

Our experimental scheme allows to analyze ex-clusively aberrations in cells in G2/M phase andmitosis of the first cycle after irradiation; this isimportant, since there is a loss of damaged (aber-rant) cells during cell division. Also important is

the possibility of analyzing heavily damaged cellswhich would be arrested before entering mitosise.g. in the G2 phase checkpoint. We conclude thatafter establishing suitable calibration curves, simul-taneous use of PCC and chromosome paintingcould be a very useful tool for biological dosimetryin the case of high doses of radiation.

The work was supported by the Polish Ministryof Education and Science – grant No. 6 P05A 11920and statutory grant for the INCT.

References

[1]. Cytogenetic analysis for radiation dose assessment. Amanual. IAEA, Vienna 2001. Technical Reports SeriesNo. 405.

[2]. Gotoh E., Durante M.: J. Cell. Physiol., 209, 297-304(2006).

[3]. Kanda R., Minamihisamatsu M., Hayata I.: Int. J.Radiat. Biol., 78, 857-862 (2002).

[4]. Sommer S., Buraczewska I., Wojewódzka M., Boużyk E.,Szumiel I., Wójcik A.: Int. J. Radiat. Biol., 81, 741-749(2005).

NUCLEAR TECHNOLOGIES

AND

METHODS


PROCESS ENGINEERING

METHOD FOR COLLECTION OF NITRATE FROM WATER SAMPLESAND DETERMINATION OF NITROGEN AND OXYGEN ISOTOPE

COMPOSITIONMałgorzata Derda, Stela Maria Cuna1/, Ryszard Wierzchnicki

1/ National Institute for Research and Development of Isotopic and Molecular Technologies,Cluj-Napoca, Romania

Problem associated with anthropogenic nitrogencontributions to the biosphere and hydrosphere areincreasingly being recognized. Nitrate contamina-tion, often related to agricultural activities, is oneof the major problems in surface and groundwatersystem.

Nitrogen availability is one of the main controlson productivity and is an important factor regulat-ing biodiversity. At present, nitrogen input fromhuman sources, chiefly synthetic fertilizers andburning of fossil fuels, approximately equals theinput from natural nitrogen fixation. The increasednitrogen input from anthropogenic sources causeseutrophication of lakes, streams, and coastal water-ways, acidification of environments, and degrada-tion of drinking water quality [1].

Nitrogen in terrestrial and aquatic ecosystemcycles among oxidized, reduced, organic and in-organic species, of which the nitrate is relativelyabundant and mobile. Nitrogen and oxygen isotoperatios of nitrates provide a powerful tool to investi-gate nitrate sources and cycling mechanisms. Theanalysis of nitrates for both δ15N and δ18O allowsimproved discrimination among potential sourcesand reaction mechanisms [2,3].

Our objectives were to develop methods for con-centrating dissolved nitrates and to prepare themfor nitrogen and oxygen isotope analysis. We havedeveloped ion exchange methods because thesemethods offer a number of important advantagesover other methods: i) nitrates can be concentratedfrom dilute waters, ii) columns can be loaded inthe field, iii) many samples may be processed atone time. The main disadvantage of this methodis time required for collection and preparation ofsamples.

The technical procedure of the method include:quantitative extraction of nitrates from watersamples, preparation of other nitrogen and oxygenbearing species for 15N and 18O analysis, and con-version of the nitrate fraction to suitable gases fornitrogen and oxygen isotopic analysis.

Samples were prepared by an anion exchangeresin method as shown in Fig. [4]. The nitrate frac-tion was collected by passing the water samplethrough pre-filled, disposable, anion exchange resincolumns. Nitrate fraction was then eluted from the

column with 15 ml of 3 M HCl. The nitrate-bear-ing acid eluent was neutralized with Ag2O and fil-tered to remove the AgCl precipitate. The samplecontaining AgNO3 was split into aliquots in theratio 1:2 for δ15N and δ18O analysis.

One portion for δ15N analysis was drying at55-65oC to evaporate water and to obtain AgNO3as a solid phase [5]. After drying, the AgNO3 wasredissolved by adding 2 ml of deionized water. Theresulting precipitate was pipetted into 3 silver cap-sules such that each capsule contained 6-10 μmolof NO3. The capsules were drying and after add-ing sucrose, δ15N was measured using an EA-IRMS(elemental analyzer-isotope ratio mass specto-meter) in continuous flow. Nitrogen isotope values(δ15N) are reported in per mill (‰), relative to theatmospheric air.

The portion for δ18O determination was driedand then CO2 was produced by off-line pyrolysiswith graphite in a vacuum line. The δ18O analysiswas carried out using the dual inlet system Deltaplus IRMS. The δ18O values were reported relativeto the standard VSMOW.

The anion exchange resin techniques offer anefficient and reliable means of collecting, transport-ing, and storing, water samples for nitrogen andoxygen isotope analysis for the nitrate. Multiplesamples may be sorbed on columns in field condi-tions using a common and relatively inexpensive

Fig. Schematic representation of the procedure for collec-tion, elution and processing of δ15N and δ18O analysis.

PROCESS ENGINEERING114

THE KINETICS OF TRANS-DICHLOROETHYLENE DECOMPOSITIONIN AIR UNDER ELECTRON-BEAM IRRADIATION

Yongxia Sun, Andrzej G. Chmielewski, Sylwester Bułka, Zbigniew Zimek, Henrietta Nichipor1/

1/ Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus,Minsk, Belarus

In our previous work [1,2], we have experimentallystudied 1,1-dichloroethylene – 1,1-DCE (H2C=CCl2)and trans-dichloroethylene – trans-DCE (trans--HClC=CHCl) decomposition in an air mixtureunder electron-beam (EB) irradiation. It was foundthat the decomposition efficiency of 1,1-DCE in airunder EB irradiation is higher than trans-DCE inthe same range of initial concentration. The degra-dation organic by-product of 1,1-DCE was identi-fied as chloroacetyl chloride (CH2ClCOCl) bymeans of gas chromatography with a flame ioniz-ing detector (GC-FID) analysis, while no organic

compounds were observed as by-products fortrans-DCE degradation in air under EB irradia-tion using the same analytical method. 1,1-DCEand trans-DCE are geometric isomers. Whethertheir decomposition mechanism in the air mixtureunder EB irradiation is the same or not is not clearto us. In this work, we made a computer simula-tion of trans-DCE degradation in the air mixtureunder EB irradiation, the decomposition mechan-ism was proposed and compared with 1,1-DCE.

The computer simulation of trans-DCE degra-dation in air under EB irradiation was carried out

equipment. The laboratory preparation of samplesfor δ15N analysis requires little technician time persample (about 30 min) and most of the total timerequired for sample preparation is spent for dry-ing and combustion steps.

The preparation of a sample for δ18O analysesis more time-consuming (about 2 h) because of thenecessity of eliminating non-nitrate, oxygen-bear-ing anions and finally extraction of CO2.

The presented method will be used for moni-toring water systems and investigation of anthro-pogenic impact on the condition of Polish rivers.

References

[1]. Vitousek P.M., Aber J.D., Howarth R.W., Likens G.E.,Matson P.A., Schindler D.W., Schlesinger W.H., TilmanD.G.: Ecol. Appl., 7, 3, 737-750 (1997).

[2]. Amberger A., Schmidt H.L.: Geochim. Cosmochim.Acta, 51, 2699-2705 (1987).

[3]. Boettcher J., Strebel O., Voerkelius S., Schmidt H.L.:J. Hydrol., 114, 413-424 (1990).

[4]. Silva S.R., Kendall C., Wilkison D.H., Ziegler A.C., ChangC.C.Y., Avanzino R.J.: J. Hydrol., 228, 22-36 (2000).

[5]. Fukada T., Hiscock K.M., Dennis P.F., Grischek T.:Water Res., 37, 3070-3078 (2003).

Fig.1. Scheme of reaction pathways of trans-DCE decomposition and by-products formation.


by using the computer code “Kinetic” [3] and GEARmethod, 320 reactions involving 78 species wereconsidered, five main groups of reactions were in-cluded, the rate constants of reactions were mostlytaken from the literatures [4,5]. The rate of Wj of jtype species generated from matrix with k typemolecules was calculated according to equation:

Wj = Σ Gjk I ρk/ρwhere: Gjk – value of j type species from k typematrix, I – dose rate, ρk – gas phase density of thematrix, ρ – overall density of the gas phase.

When fast electrons from electron beams areabsorbed in the carrier gas, they cause ionizationand excitation process of the nitrogen, oxygen andH2O molecules in the carrier gas. Primary speciesand secondary electrons are formed. These primaryspecies and thermalized secondary electrons causetrans-DCE degradation by complex chemical reac-tions, a scheme of reaction pathways of trans-DCEdecomposition and organic products formation ispresented in Fig.1. Based on our calculation re-sults, similar to 1,1-DCE degradation in air underEB irradiation, Cl– dissociated thermalized second-ary electron attachment, Cl addition reaction withtrans-DCE followed by peroxyl radical reactionsis a main reaction pathway for trans-DCE degra-dation. Calculated and experimental results oftrans-DCE degradation in the air mixture vs. doseunder EB irradiation are presented in Fig.2. Thekey reactions which cause trans-DCE or 1,1-DCEdecomposition and products formation in air underEB irradiation can be generally written as follows:

e + C2H2Cl2 = Cl– + C2H2Cl· k1=1.0×10–9

Cl– + A+ = Cl + A(A+ is any positive ion in the gas phase)

C2H2Cl2 + Cl = C2H2Cl3 (k3)O2 + C2H2Cl3· = C2H2Cl3(O2)·

2C2H2Cl3(O2)· = C2H2Cl3(O)· + O2C2H2Cl3(O)· = CH2ClCOCl + Cl (for 1,1-DCE)or C2H2Cl3(O)· = HCOCl + CHCl2 (for trans-DCE)

The rate constant of Cl addition reaction to1,1-DCE (k3a=1.4×10–10 cm3·molecule–1·s–1) ishigher than to trans-DCE (k3b=9.58×10–11 cm3·mol-ecule–1·s–1), this is the main reason why the decom-position efficiency of 1,1-DCE in air under EB ir-radiation is higher than that of trans-DCE.

Mechanism of trans-DCE degradation in the airmixture under EB irradiation is similar to 1,1-DCE,Cl– dissociated thermalized secondary electronattachment, Cl addition reaction with trans-DCEfollowed by peroxyl radical reactions is the mainreaction pathway for trans-DCE degradation.HCOCl which was not and cannot be detected byGC-FID analysis was predicted as a main productof trans-DCE degradation based on modellingsimulation results. OH radical presence increasesdecomposition efficiency of trans-DCE less than10%.

References[1]. Sun Y. et al.: Radiat. Phys. Chem., 61, 353-360 (2001).[2]. Sun Y. et al.: Radiat. Phys. Chem., 68, 843-850 (2003).[3]. Bugaenko W.L. et al.: Program for modeling of chemical

kinetics. Institute of Theoretical and ExperimentalPhysics, Moscow 1980. Report ITEP No. 50.

[4]. Albritton D.L.: At. Data Nucl. Data, 22, 1-101 (1978).[5]. http://kinetics.nist.gov/kinetics/index.jsp.

Fig.2. Concentration of trans-DCE vs. dose under EB ir-radiation (solid lines – experimental results [2],dashed lines – calculation results).

ELECTRON BEAM OF VOCs TREATMENT EMMITTEDFROM OIL COMBUSTION PROCESS

Anna Ostapczuk, Janusz Licki1/, Andrzej G. Chmielewski1/ Institute of Atomic Energy, Świerk, Poland

Electron beam (EB) processing has been alreadyapplied on industrial scale for the treatment of fluegas from coal combustion: full-scale EB installa-tions have been put into operation in Poland [1]and China [2] for the removal of acidic pollutantslike SO2 and NOx. The technology has been investi-gated for volatile organic compounds (VOCs) re-moval from flue gases since the late ’80ies and re-cent research in a pilot plant scale has shown thepossibility to decompose/detoxify of dioxins stream

in waste-incineration [3] and polycyclic aromatichydrocarbons (PAHs) in coal combustion flue gases[4]. It has been observed that the investigated groupsof compound change their distribution profile tohomologues, which are characterized by lowertoxicity factor and, as the consequence, the overalltoxicity of flue gas decreased [3-5]. The change ofconcentration and distribution profile observed influe gas treated by EB irradiation can be causedby three processes: (i) destruction in the oxidation


processes [6,7], adsorption on the aerosol surfaceand (iii) new compound formation in radical pro-cess [8]. The experimental work done in the pilotplant on real flue gas has been concentrated onthe EB influence on the homologues belonging toone group of compounds. VOCs have been inves-tigated as a single model compound irradiated ina gaseous mixture and as a main decompositionpathway OH radicals – initiated oxidation is pro-posed [9-10]. The process is analogical to atmo-spheric chemistry, and VOCs are mineralized andtransformed into other organic compounds.

Laboratory scale experiments on EB treatmenthave been performed to investigate the change ofthe composition of organic fraction of flue gasemitted from oil combustion process. The flue gas(v=5 m3/h) passing the irradiation chamber hasbeen irradiated by EB from an ILU-6 acceleratorthrough a titanium window with a dose rangingfrom 3.5 to 8.8 kGy. The concentration of organiccompounds in flue gas at the inlet and outlet ofthe irradiation chamber have been compared withthe aim to find how EB irradiation influences thecomposition of organic fraction of flue gas. Thequalitative and quantitative analysis of the concen-trated extracts was performed by gas chromato-graphy-mass spectrometry (GC-MS) by a ShimadzuGC-17A gas chromatograph connected with aquadropole mass spectrometer Shimadzu QP5050.Analyzed mixtures were separated on a non-polarcolumn HP5-MS (Hewlett Packard, 30 m×0.25 mmID×0.25 mm film thickness).

The composition of the organic fraction of oilcombustion flue gas has been determined qualita-tively and quantitavely in several experimental se-

ries with the purpose to establish the key groupsof emitted compounds. The categories of the de-tected organic compounds and their concentrationlevel are listed in Table.

The composition of the organic fraction of fluegas has changed after irradiation: the concentra-tion of PAHs and aromatic compounds (BTX)decreased after irradiation. The average removalefficiency for a dose of 5.3 kGy of these compoundswas 60 and 84%, respectively. Decomposition ra-tio of the investigated compounds increased withdose absorbed. The initial concentration of the in-

dividual compounds like PAHs has been loweredeven by two orders of magnitude.

Simultaneously, an increase of oxygen-contain-ing aromatic compounds (OAH) like phenol, ben-zaldehydes, benzoid acids and others has beenobserved. OAH is a dominating group of VOCspresent in flue gas, in contast to the compositionof flue gas before EB treatment (Fig.). The higherconcentration of oxidized compounds and increase

of CO content in irradiated flue gas is effected byoxidative decomposition of aromatic compounds.

The work has been partially co-finansed by theInternational Atomic Energy Agency (IAEA re-search contract No. POL 13136) and the Ministryof Science and Higher Education (agreement No.7/IAEA/2006/0).

References[1]. Tymiński, B.; Pawelec, A.: Economic evaluation of

electron beam flue gas treatment. In: Radiation treat-ment of gaseous and liquid effluents for contaminant

Fig. Distribution of PAH, BTX and OAH in the organicfraction of flue gas at the inlet and the outlet of irra-diation chamber; dose D=5.3 kGy, initial VOC con-centration ci=72.5 μg/m3.

Table. Organic compounds and their concentration level detected in oil combustion gas.


removal. Proceedings of a technical meeting held inSofia, Bulgaria, 07-10.09.2005. IAEA, Vienna 2005,pp. 25-34, IAEA-TECDOC-1473.

[2]. Mao B.: Process of flue gas desulphuration with elec-tron beam irradiation in China. In: Radiation treat-ment of gaseous and liquid effluents for contaminantremoval. Proceedings of a technical meeting held inSofia, Bulgaria, 07-10.09.2005. IAEA, Vienna 2005,pp. 45-51, IAEA-TECDOC-1473.

[3]. Hirota K., Hakoda T., Taguchi M., Takigami M., KimH.-H., Kojima T.: Environ. Sci. Technol., 37, 3164(2003).

[4]. Chmielewski A.G., Ostapczuk A., Zimek Z., Licki J.,Kubica K.: Radiat. Phys. Chem., 63, 653-655 (2002).

[5]. Chmielewski A.G., Ostapczuk A., Licki J.: Polycyclicaromatic hydrocarbons removal from flue gas by elec-tron beam treatment – pilot plant tests. In: Radiation

ELECTRON BEAM TREATMENT OF FLUE GASFROM FUEL OIL COMBUSTION

Andrzej G. Chmielewski, Andrzej Pawelec, Bogdan Tymiński, Zbigniew Zimek, Janusz Licki1/,Ahmed A. Basfar2/

1/ Institute of Atomic Energy, Świerk, Poland2/ King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia

of the parametric tests indicate that, with the ex-ception of dose, SO2 and NOx removals depend onthe different process conditions. By controlling theseconditions it is possible to obtain maximum removalefficiencies. NOx removal is mostly energy-consum-ing, while SO2 removal is sensitive to temperature,humidity and ammonia stoichiometry. The properselection of the process conditions (gas humidity– 10-15 vol.%, ammonia stoichiometry – 0.90-0.95and gas temperature – 60-700C) guarantees high SO2removal efficiency at low energy consumption. Adose of 6-9 kGy is sufficient to achieve over 90%SO2 and 70% NOx simultaneous removal from fluegas under optimum operating conditions. HigherNOx removal efficiencies require higher energyconsumption. No impact of oxygen concentration,in the analyzed range, on the process efficiency wasobserved. The optimal parameters were very simi-lar for all three grades of oil. This means that theelectron beam flue gas treatment technology maybe applied for any grade of oil.

The by-product is almost a pure mixture ofammonium sulphate and ammonium nitrate, thatmakes it a valuable fertilizer. The combination ofthese two compounds provides a suitable qualitymaterial for direct soil application or as a blend-ing component in the standard manufacture ofcommercial fertilizer (NPK type).

The obtained results correspond with thosepreviously obtained for the experiments conductedwith coal combustion flue gases. The above resultsprove the possibility of electron beam flue gastreatment technology to be applied for the purifi-cation of flue gases from different fuel combus-tion process.

During operation of the plant installed at the Po-morzany Electric Power Station, the electron beamflue gas treatment technology has proved its us-ability for industrial applications. The technologyallows for simultaneous removal of both sulphurdioxide (SO2) and nitrogen oxides (NOx) with highefficiency. Beside of this the process is wastelessand economically competitive to the conventionalemission control methods. One of the importantadvantages is the possibility of application of thismethod for cleaning of flue gas from various, notonly coal combustion based, technological pro-cesses. Research on the purification of flue gasfrom the fuels different than coal was undertakenin the Institute of Nuclear Chemistry and Tech-nology.

The process of treatment of flue gas from fueloil combustion was studied. Three types of oil con-taining various amounts of sulphur (oil I – 2.81%,oil II – 2.9% and oil III – 3.1%) were taken for labo-ratory experiments. The composition of the fluegas depends on burning conditions and oil itself.Generally, the basic flue gas parameters were asfollows:- volume flow rate – 5 Nm3/h,- SO2 concentration – 800-1850 ppmv,- NOx concentration – 80-190 ppmv,- gas temperature at process vessel – 60-120oC.

The influence of such factors as irradiation dose,gas temperature at the inlet to process vessel, am-monia stoichiometry, gas humidity and oxygen con-centration on the process efficiency was studied.

High SO2 and NOx removal efficiency up to 99%for SO2 and 90% for NOx (respectively, 98% and85% in optimal conditions) was achieved. Results

treatment of gaseous and liquid effluents for con-taminant removal. Proceedings of a technical meetingheld in Sofia, Bulgaria, 07-10.09.2005. IAEA, Vienna2005, pp. 63-68, IAEA-TECDOC-1473.

[6]. Biermann H.W., Mac Leod H., Atkinson R., WinerA.M., Pitts J.N.: Environ. Sci. Technol., 19, 1115(1985).

[7]. Atkinson R., Arey J., Zielinska B., Aschmann S.M.:Int. J. Chem. Kinet., 22, 1071 (1990).

[8]. Gerasimov G.Ya.: High Energ. Chem., 39, 60 (2005).[9]. Prager L., Mark G., Mätzing H., Paur H.-R., Schubert

J., Frimmel F.H., Hesse S., Schuchmann H.-P.,Schuchmann M.N., Sonntag C.V.: Environ. Sci.Technol., 37, 379-385 (2003).

[10]. Hirota K., Mätzing H., Paur H.-R., Woletz K.:Radiat. Phys. Chem., 45, 649-655 (1995).


The second best choice would be calorimetryof flue gas for the determination of average dose.However, there are uncertainties using this method;mainly how adiabatic is the system. The main sourceof uncertainty arises from the contribution of thewalls of the reaction vessel to the temperature riseof the flue gas since it is unavoidable that radia-tion (electrons) will deposit part of its energy inthe walls. However, by judiciously matching thesize of the reaction vessel to the beam energy, thisuncertainty can be minimized.

The third method, measurement with soliddosimeters, is still less reliable. One can measuredose using several dosimeters and calculate somekind of average dose for the entire reaction vessel.There are two difficulties in this method. First, tobe very accurate, dose should be measured at avery large number of locations. Second, this is themeasurement of dose rate, and not dose to gas. Oneneeds then to assume that the residence time of thegas is the same through each part of the vessel;that will be true if it were a plug (segregated) flow.On the other hand, it would be irrelevant if thegas flow were turbulent. But that is hardly the case.

The only method to measure non-uniformity ofdose absorbed in gas is to measure the dose rate atvarious locations in the vessel with fixed dosimeters,such as cellulose tri-acetate (CTA). This informa-tion then can be used to calculate dose absorbedby different portion of gas as it travels through thevessel. However, as mentioned above, one thenassumes that there is a plug (segregated) flow. Onthe other hand, if the flow were completely turbu-lent, the dose would be uniform to all the gas. Yetanother method is to carry out a detailed MonteCarlo simulation of the system. The reliability ofthe results of such a calculation of course dependson the quality of the input data. Thus, we have toknow the type of flow of the gas through the vessel:plug or turbulent and extent of each. And it isalways prudent then to validate the results withmeasurements.

References

[1]. Chmielewski A.G., Zimek Z.: Nuclear technology forcleaning coal emissions. In: The environmental chal-lenges of nuclear disarmament. Eds. T.E. Baca, T. Flor-kowski. Kluwer Academic Publishers, The Netherlands2000, pp. 139-148.

[2]. Chmielewski A.G., Ostapczuk, Namba H., TokunagaO., Hashimoto S., Tanaka T., Ogura Y., Doi Y., AokiS., Izutsu M.: Radiat. Phys. Chem., 46, 1103-1106(1995).

The most widely applied systems for coal firedboilers are wet flue gas desulphurization (FGD) us-ing lime or limestone as reagent and selective cata-lytic reduction for NOx reduction. Therefore, it isstill important to develop new treatment methodsthat do not have these problems. The electron beamtreatment of flue gas is one of the new technologies.Its success in significantly reducing SO2 and NOxhas already been demonstrated in many pilot plantsand a few full commercial plants.

There are several advantages in employing ion-izing radiation (electrons) for this purpose, includ-ing [1]:- several polluting gases are removed simulta-

neously with high efficiency;- dry system without any wastewater treatment;- simple system with easy operation;- compact plant, thus easy for retrofitting in an

existing power station;- high energy efficiency, and by-product can be

used as fertilizer.This process requires beam power of 300 kW

or more, and electron energy in the range of 0.8 to1 MeV. Accelerators suitable to fulfill such require-ments are based on high-power, high-voltage trans-formers according to the present state-of-the-artaccelerator technology. Industrial linac technology,which was developed for military applications, isbeing demonstrated now as an appropriate tech-nical and cost-effective competitive alternative [2].The electron beam technology is relatively flexibleand adaptable to local conditions. The process canbe easily adapted for different removal efficiencylevels and adjusted for use with different fuels.Also, retrofitting of existing facilities to reduce NOxand SO2 concentrations to meet low-space require-ments is an attractive option.

Dose and dose distribution in the reactionvessel of a flue gas treatment facility very stronglyinfluence the removal efficiency of NOx, and to asmaller degree of SO2. Thus, it is essential thatthese two parameters are measured and optimizedfor better economy of the process.

The recent dosimetry related work carried outby the authors at the Institute of Nuclear Chemis-try and Technology (INCT) lead to conclusion thatthe best method for measuring average dose to thegas is through a dosimetry system that relies onthe reaction in the gas phase. Such measurementswill truly represent the dose absorbed by the fluegas. Thus, it is a matter of selecting a most suit-able system whose G value is known fairly accu-rately and the product(s) is easily measurable.

DOSIMETRY FOR COMBUSTION FLUE GAS TREATMENTWITH ELECTRON BEAMKishor Mehta1/, Sylwester Bułka

1/ Vienna, Austria


Recycling of polyolefine wastes by thermal degra-dation into liquid hydrocarbons is being intensivlystudied. Several plants producing a wide hydro-carbon fraction, similar to heavy crude petrol oilfrom polyolefine wastes, exist in Poland. Previousinvestigations showed that it is possible, withoutadditional energy consumption, to receive morevaluable gasoline and light oil fractions from thesame plastic wastes. Lately, we concentrated onchecking of quality of wastes on final products.There were made five experiments with the use ofdifferent wastes. Experiments were made in a largelaboratory installation shown in Fig. Products werewithdrawn from five levels at the distillation col-umn and were analyzed in the same way as reportedin paper [1,2]. The main results are presented inTable. In the first three experiments the wastes wereprepared in our laboratory from relatively cleanmaterials. The next two experiments were madewith wastes from a company selecting the wastes.The wastes were in the form of flakes of unknowncomposition. From Table, it follows that the distil-lates from these wastes (experiments Nos.4 and 5)contain more heavy fraction and its temperatureof freezing point is higher. In one case, not shownin Table, the wastes contained a component witha high melting temperature which caused pluggingthe melter. To avoid this design of the melter wasimproved. After improvement, the temperature in

the melter significantly increased and there wasno more problems with plugging of the melter.

The distillates from the distillation column con-tain some heavy oil which makes worse the prop-erties of the gasoline and light oil fraction. For theseparation of gasoline and light oil fractions withhigher purity, the distillates were purified in a batchand continuous distillation process. In the continu-ous distillation process, the temperature in theboiler was 360oC and the gasoline fraction collectedat temperatures 230 to 170oC and the light oil frac-tion – at temperatures 200 to 270oC. During distil-lation of the fractions containing more light hydro-

carbons, these temperatures were lower. In thebatch distillation it was easy to separate fractionswith a demanded range of boiling points. Both

methods of distillation give more pure and stableproducts [2].

References

[1]. Tymiński B., Zwoliński K., Jurczyk R., Darkowski A.:Investigation of catalysts for cracking of polyethylenewastes into liquid hydrocarbons. In: INCT AnnualReport 2005. Institute of Nuclear Chemistry and Tech-nology, Warszawa 2006, pp. 113-114.

[2]. Tymiński B., Zwoliński K., Jurczyk R.: Prace NaukoweInstytutu Inżynierii Ochrony Środowiska PolitechnikiWrocławskiej, 81, Seria konferencje 12, 263-268 (2006),in Polish.

CATALYTIC CRACKING OF POLYOLEFINE WASTESIN A LARGE LABORATORY INSTALLATIONBogdan Tymiński, Krzysztof Zwoliński, Renata Jurczyk

Fig. Scheme of a large laboratory installation for catalyticcracking of polyolefine wastes.

Table. Main results of decomposition of plastic wastes (PP – polypropylene, PE – polyethylene).


Raw biogas contains about 55-65% methane (CH4),30-45% carbon dioxide (CO2), traces of hydrogensulphide (H2S) and fractions of water vapour. En-richment of methane in biogas from anaerobic di-gestion in fermentation tanks or landfills to obtainfuel of higher calorific value can be achieved by re-moving carbon dioxide and other gaseous impuri-ties like hydrogen sulphide. Elimination of carbondioxide from the flue gas helps in increasing its calo-

rific value as well as in eliminating the greenhousegas, CO2. Carbon dioxide thus generated can beutilized as an effective refrigerant.

Current technologies to purify off-gas and in-crease its caloric value have been primarily limitedto physicochemical methods such as chemical sepa-ration, membrane separation, cryogenic separationas well as adsorption. Chemical methods are basedon absorption under elevated pressure (in water,30% solution of potassium carbonate (K2CO3),solution of monoethyloamine, etc.). Other methodsare based on adsorption in which a vital role playsa suitable adsorbent material [1].

Laboratory experiments with the use of gas sepa-ration membranes from polyimide showed a greatpotential for membrane permeation as a separa-tion method of gaseous components of biogas [2,3].At common concentration of methane, a singlestage unit seems sufficient to achieve 94% enrich-ment, and multistage systems are not required. Forlower methane concentrations (<60%), the stan-dard gas GZ-50 can be produced by a multistage

separation. The high permeability of the polyimidemembranes to water vapour and hydrogen sulphide,common impurities of gas produced in biomassfermentation process, makes them useful for biogasprocessing without special pretreatment.

Preliminary economic evaluations proved thatthe application of membranes is reasonable. Table1 performs the production abilities of the absorp-tion method carried in a Benfield type apparatus.At the same flow rate of biogas, the absorptionmethod produces 40% more of methane thanmembrane permeation. The productivity of themembrane system is reduced by methane losses

Table 1. The comparison of the capabilities of absorption and membrane methods.

ECONOMICAL COMPARISON OF ABSORPTIONAND MEMBRANE METHODS APPLIED

FOR THE ENRICHMENT OF METHANE IN BIOGASMarian Harasimowicz1/, Grażyna Zakrzewska-Trznadel1/, Weronika Ziółkowska2/,

Andrzej G. Chmielewski1,2/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Faculty of Chemical and Process Engineering, Warsaw University of Technology, Poland

Table 2. A comparison of energy and reagents consumption in two methods: absorption and membrane separation.


that are equal ca. to 84 000 Nm3 per year. However,the expenses related to methane losses are compen-sated by the lower costs of materials consumption.The chemical method is more energy-consuming,uses more reagents like potassium carbonate, acti-vator (DEA) and corrosion inhibitor (KVO3). Inthis method, in some parts of installation wasteheat can be utilized, that reduces the total energyconsumption.

In Table 2, the consumption of energy and re-agents is presented. The energy consumption forabsorption is reduced by waste energy utilized insome parts of installation.

The investment costs of both methods are listedin Table 3. The tentative cost evaluation showed

that the membrane method is more economicalthan the absorption method. Both capital and op-erational costs are lower for the membrane pro-cess than for chemical absorption. Additionally,

the membrane installation is simple, compact anddoes not need complex control equipment likechemical methods. Despite of high costs of themembrane modules for gas separation, the totalcapital costs of the membrane installation arelower than for the Benfield installation.

Comparison of the operational costs is alsofavourable for membrane permeation. Eventhough the membrane method consumes muchenergy for gas compression, it does not use theexpensive reagents, which are necessary for chemi-cal process.

The work proved that the absorption methodcan be superseded by membrane separation. Thanksto the development of material science that pro-duces modern high selective materials and newachievements in process engineering, separationof gaseous components of biogas are reliable. Bothselectivity and efficiency of membranes are suffi-cient to produce gas of appropriate parameters ofstandard gas GZ-50.

References[1]. Sarkar S.C., Bose A.: Energ. Convers. Manage., 38,

Suppl. 1, 105-110 (1997).[2]. Harasimowicz M., Orluk P., Zakrzewska-Trznadel G.,

Chmielewski A.G.: Application of polyimide mem-brane from biogas purification and enrichment. In:Proceedings of the 5th European Meeting on ChemicalIndustry and Environment, EMChIE 2006, Vienna,Austria, 03-05.05.2006, pp. 617-622.

[3]. Harasimowicz M., Ziółkowska W., Zakrzewska-Trzna-del G., Chmielewski A.G.: Economical comparison ofabsorption and membrane methods applied for enrich-ment of methane biogas. In: Proceedings of the XXIARS SEPARATORIA, Toruń, Poland, 03-06.07.2006,pp. 52-54.

Table 3. Economy of two processes: absorption and mem-brane separation for methane enrichment – a com-parison.

Pressure-driven membrane filtration is an import-ant process for separation of colloids and particu-late matter from liquid suspensions in many fieldsof engineering and applied science. There are manyexamples of application of pressure-driven mem-brane processes in nuclear technology. Such pro-cesses like reverse osmosis, ultrafiltration or micro-filtration can be used for liquid radioactive wasteprocessing, cleaning reactor waters, boric acid re-covery and separation of isotopes. The pressure--driven membrane filtration process can operateat either cross-flow or dead-end flow mode. In caseof dead-end filtration the resistance increases withformation of the cake on the membrane surface,while in cross-flow process the deposition continuesuntil the cake adhesion is balanced by shearingforces of the liquid passing over the membrane. It

is important to keep appropriate hydrodynamicconditions in the apparatus that avoid continuousbuilding-up of the cake layer which results in in-crease of the resistance and reduction of the per-meate flux. The term of concentration polarizationdescribes the tendency of the solute to accumu-late in the membrane-liquid interface. It is import-ant to suppress the concentration polarization byadjusting the flux on the level that avoid the bound-ary level development or by promoting the turbu-lence by all available means. For understanding ofpermeate flux decline mechanisms and predictingof the permeate flow rate, the development ofmathematical models and tools for simulations andoptimization are of great importance.

The hybrid membrane process for removal ofcobalt ions, the main components of the liquid

STUDY OF BOUNDARY-LAYER PHENOMENAIN MEMBRANE PROCESSES

Grażyna Zakrzewska-Trznadel, Agnieszka Miśkiewicz, Marian Harasimowicz, Ewa Dłuska1/,Stanisław Wroński1/, Agnieszka Jaworska1/, Cornel Cojocaru2/

1/ Faculty of Chemical and Process Engineering, Warsaw University of Technology, Poland2/ ”Gh.Asachi” Technical University of Iaºi, Romania


radioactive wastes produced in Poland, was run inthe ultrafiltration unit equipped with a membranecontactor with a central rotor. Helical Couette-Taylor flow was expected to promote the turbu-lence and vortices in the apparatus that resultedin good transport parameters. Before filtration,

cobalt ions were complexed by soluble chelatingpolymers like polyacrylic acid derivatives oradsorbed on activated carbon seeds dispersed inthe solution. In both cases the improvement of fil-tration conditions and increase of permeate fluxthrough the membrane were observed when dy-namic conditions were applied (Figs.1-2). There

was evidence that by promoting the turbulence theresistance of boundary layer and the resistance ofthe deposit accumulated on the membrane surfacewere reduced. Permeate flux, Jv, can be expressedas a function of total membrane-cake resistanceby the equation:

(1)

where: ΔP – transmembrane pressure, μ – viscosityof the liquid.Membrane resistance, Rm, was estimated fromwater permeability and cake layer resistance Rδ –from the total resistance determined in experi-ments. On the other hand, permeate flux can bedescribed by the relationship analogical to theequation of the filtration through the sediments:

μ δΔ

=vP KJ

(2)

where: K – cake permeability, δ – thickness of thecake layer.From comparison of eqations (1) and (2), the thick-ness of the residual deposit layer can be estimated.The cake thickness determined for different pro-cess conditions, assuming K=10–17 m2, was in a0.035-0.186 mm range for dynamic conditions.The thickness showed a marked influence of rota-tion: the δ values decreased with increasing rota-tion frequency in the helical-flow membrane appa-ratus. The influence of rotation on the separationefficiency was not observed. In experimentalconditions at rotation frequency W=1000-1500rpm and for ion to polymer concentration ratioCCo2+/Cpolymer=1/4, the retention factors higher than90% were achieved.

The models for simulation and optimizationof cross-flow filtration developed from theory ofconcentration polarization and response surfacemethodology (RSM) were elaborated. The regress-ion analysis in order to find empirical models forfitting the experimental data of flux decline wasemployed. The models were determined by mini-mization of the residual variance S2

res:

(3)

The experimental data of the kinetics of flux de-cline were fitted well by polynomial equation oftype:

1 2 30 1 2 3 4 5( ) −= + + + + +J t a a t a t a t a t a t (4)

Two responses derived from kinetic curves of fluxdecline were used: the average permeate flux cal-culated by integration of J(t) function from t1=1min up to tn=180 min as follows:

1

1 ( )< >= ∫nt

n t

J J t dtt (5)

where J(t) means the regression functions deter-mined by regression analysis, and the cumulativeflux decline defined as

( ) ( )( )

1

2 1=

⎛ ⎞−= ⎜ ⎟⎜ ⎟

⎝ ⎠∑

ni

FDi

J t J tS

J t (6)

Fig.3. Permeate flux vs. time for optimal conditions:ΔP*=0.19 bar, QR

*=54 L/m2h and W*=2480 rpm.

Fig.2. Permeate flux vs. time. Cobalt removal in hybrid pro-cess: complexation by polyacrylic acid (PAA)-ultra-filtation.

Fig.1. Permeate flux vs. time. Cobalt removal in hybrid pro-cess: sorption on activated carbon (AC)-ultrafiltra-tion.

( )vm

PJR RδμΔ

=+

( )22 experres

1

1 ( ) min2

n

j jj

S J t Jn =

= − →− ∑


The cumulative flux decline defined by equation(6) gives information about all experimental pointsin flux decline curve for the time interval studied,i.e. 1 min≤t≤180 min. By means of the multiplelinear regression method, the empirical models ofcross-flow filtration, which gave the informationabout the influence of hydrodynamic parametersupon J and SFD were developed. The cumulativeflux decline and average permeate flux were usedas the objective functions in optimization by theLagrange multiplier method using MathCAD soft-ware. The calculated optimal values in terms of ac-tual operating variables were ΔP*=0.19 bar, QR

*=54L/m2h and W*=2480 rpm. For these operation con-

ditions, the check out experiment was carried outto determine the permeate flux vs. time (Fig.3). Theinitial flux decline was observed in the time interval1 min≤t≤60 min; after that a slight increase of fluxwas recognized for t>60 min. This means that inoptimal operating conditions the vortices createdby Taylor flow led to self-cleaning effect of themembrane surface for t>60 min. For all experi-ments concerning the polymer-assisted cross-flowultrafiltration process carried out in the helicalmembrane module, the average value of the rejec-tion coefficient was 91.54% with a standard devia-tion of 4.06%.

Isotope ratio mass spectrometry (IRMS) methodsplay a very important role in food authenticity andorigin control. The measurements of bioelements(hydrogen, nitrogen, carbon, oxygen, and sulfur)composition provide a very sensitive tool to foodcontrol. The isotopic methods of origin and authen-ticity control were recently implemented in Euro-pean Union for wine, juice, and honey.

The aim of our study is to explore the relation-ship between isotopic composition of milk and itsorigin (regional, seasonal). The stable isotope com-position of food is strictly connected with environ-mental conditions (climate, geographical positionand included pollutants).

The bases for this study are isotopic effects (bio-logical, physical and chemical) which are respon-sible for different isotopic composition in nature:soil, air and water. The effect of differentiation ofisotope composition is connected with differentcomposition of cow diet (maize, grass etc.) anddifferent composition of drinking water for cows[1-3]. Seasonal and regional variations of cow dietcomposition cause seasonal and regional variationsof isotopic composition of milk and finally dairyproducts (Table).

In the frame of the project, many samples ofmilk and dairy products from main regions of milkproduction were gained. The collected sampleswere measured by the use of IRMS DELTAplus(Finnigan, Germany), connected with peripheralunits as: GasBench, H/Device and ElementarAnalizer (ThermoFinnigan).

Correlation between the stable isotope compo-sition 18O/16O, 13C/12C, 15N/14N and δD in milk com-ponents was analyzed. The variability of the pa-rameters related to environmental factors like:geology, climate and anthropogenic factors wasstudied (Fig.).

Finally, on the basis of the collected results amap of isotopic parameters distribution will bedrawn. The information about the relation be-tween the isotopic compositions and the regionaland seasonal factors will be an important research

result of this project. In the future, on the database of authentic value of stable isotope composi-tion, the method for origin control of milk anddairy products will be proposed.

The study was supported by the Polish Minis-try of Science and Higher Education in the frameof project No. 2P06T03928.

A STUDY OF STABLE ISOTOPE COMPOSITION IN MILKRyszard Wierzchnicki, Małgorzata Derda

Fig. Factors determining the water isotopic compositionof dairy products – a schematic way from the farm tothe consumer.

Table. Chemical components of milk and their important isotopic composition.


References

[1]. Rossmann A., Haberhauer G., Hölzl S., Horn P., Pichl-mayer F., Voerkelius S.: Eur. Food Res. Technol., 211,32-40 (2000).

[2]. Knobe N., Vogl J., Pritzkow W., Panne U., Fry H.,Lochotzke H.M., Preiss-Weigert A.: Anal. Bioanal.Chem., 386, 104-108 (2006).

[3]. Renou J.P., Deponge Ch., Gachon P., Bonnefoy J.C.,Coulon J.B., Garel J.P., Verite R., Ritz P.: Food Chem.,85, 63-66 (2004).

samples of water with 3H concentration in an in-terval of 0-20 TU.

In test VI participated 86 laboratories and 6samples of water with 3H concentration in an in-terval of 0-25 TU and with one unknown samplewith a concentration of about 500 TU were mea-sured.

The results of tests are presented in Tables 1and 2.

The real concentration, Cr, is defined as themean value – the result of averaging all data ob-tained by the test participants whose result Ci ful-filled the condition |Ci – Cr|<2δ.The measured concentration is the result obtainedin the INCT laboratory with an error of ±0.5 TU.

The results of the test realized by the IAEA in2005, for the moment, were not published.

The data obtained in the INCT laboratory in-dicate sufficient agreement with the interlaboratoryresults especially with those for higher 3H concen-tration.

Successive observation and measurements of 3Hcontents in water samples has been realized inPoland in a few laboratories starting since 1967. Themeasurement of this kind is being performed inthe Institute of Nuclear Chemistry and Technology(INCT) since 1999 and is connected with the ob-servations of 3H concentration changes in surface

and underground waters in the surrounding of thecoal mine “Bełchatów”. About 240 3H measure-ments are realized each year.The results of these measurements are used for thediagnosis of environmental processes occurring inthe open lignite mine area.

The International Atomic Energy Agency(IAEA) organizes from time to time (every 5 years)

interlaboratory tests for checking the correctnessof data obtained in the laboratories which are reg-istered in the IAEA – laboratories net.

The INCT laboratory participated in the testsorganized in 1994 (test V), 2000 (test VI) and 2005.

In test V participated 91 laboratories from nu-merous countries which measured the same 4

INTERLABORATORY TESTS FOR 3H MEASUREMENTSIN WATER SAMPLES

Wojciech Sołtyk, Jolanta Walendziak, Jacek Palige

Table 1. Results of test V.

Table 2. Results of test VI.

MODELLING FOR GROUNDWATER FLOWIN THE OPENCAST BEŁCHATÓW AREA

Robert Zimnicki

The groundwater flow modelling is one of the mostimportant steps in characterizing transport andproperties of contaminants in industrial area likecoal-mine. The majority of processes based on natu-ral raw material exploitation causes a significiantenvironment destruction. The majority of problemsconcerning water quality like salinity or organic pol-lutant contents, water interchange and their resi-

dence time in ground could be forecasted by com-puter simulation of flow processes.

Modelling for the Bełchatów opencast areastarted in 2006. Simulation was done using Modflowsoftware based on the application of the finite ele-ment method for the solution of appropriate 3Dflow equation system for porous media. The Darcylaw was applied for filtration velocity description.


At the beginning, data concerning porosity of thematerials, boundary conditions for a certain part ofopencast, like salt dome, outer dump, first drivingarea, were collected. The applied model consist ofsix layer describing three principal geological plies(Mesozoic, Quaternary and Cenozoic). The schemeof exploitation area is presented in Fig., where theprincipal mine objects are indicated.

The Bełchatów model consist of 680x360x6 cells,in reality, the dimensions are 34 000 m length and18 000 m width. Step size between bend is 50 m.The porosity for sand is equal to 45%, granite –0.7% and total as 10% were sets. The transmissi-

vity for all area 5 m2/day were preset. Rain param-eter is equal to 0.0016 m/day.

Actually the model is being verified. The sensi-tivities of applied procedures on boundary condi-tions changing is tested [1].

References

[1]. Zimnicki R., Owczarczyk A., Chmielewski A.G.: Obser-wacja zmian hydrochemicznych wód podziemnych w re-jonie powstającej odkrywki węgla brunatnego. In: Ma-teriały z IV Ogólnopolskiej Konferencji Naukowo-Tech-nicznej “Postęp w inżynierii środowiska”, Bystre nearBaligród, Poland, 21-23.09.2006, pp. 521-529 (in Polish).

Fig. Scheme of exploitation area.

TRACER AND CFD INVESTIGATIONSOF SEDIMENTATION PROCESSES IN RECTANGULAR SETTLER

Jacek Palige, Andrzej Dobrowolski, Sylwia Ptaszek, Andrzej G. Chmielewski

Wastewater treatment process is realized in dif-ferent apparatus such as equalizers, aeration tanks,settlers and final sedimentation basins. The treat-ment efficiency strongly depends on the work of asecondary settler.

Many researches concerning the sludge sedi-mentation process were carried out [1-3]. Actually,few methods are used for investigations of settlers.The tracer method is used for the determinationof residence time distribution (RTD) function and

Fig.1. Scheme of a secondary settler and experimental results of spatial sludge ceoncentration distribution: A – in pro-files at 8, 24 and 37 m from the wastewater input as a function of depth; B – 1 and 2 m below the water table in theaxis of the settler.


computational fluid dynamics (CFD) [4-6] for ob-taining the water flow structure inside a settlertank.

In this work, the results of tracer investigationsand CFD simulations for an industrial rectangularsettler with immersed input (width 10 cm in allsettler width) are presented. Volume of unit underinvestigation was V=1050 m3 (length L=41.5 m,height H=3÷4 m), flow rate of wastewater q=160m3/h, output of sewage in the settler was realizedby overflow. For this inflow structure, the sedimentconcentrations have been measured 1 and 2 mbelow the water table in the axis of the settler andin profiles at 8, 24, 37 m from the wastewater in-put as a function of depth. The scheme of the set-tler and the distribution of sediment inside thesettler are presented in Fig.1.

The velocity of sludge sedimentation was de-termined in laboratory tests. The value of this vel-

ocity was 3 cm/min. Using the CFD codes, the sedi-mentation process of monodisperse sludge withinput concentration 2 kg/m3 and flow rate of fluid0.041 m3/s was simulated. Numerical 3D simulationsof the sedimentation process with numerical codeof FLUENT software application were carried outusing the Euler-granular scheme and standard k-εmodel of flow turbulence for a mixture of waterand sludge.The characteristic backflow, up to 30 m in settler(Fig.2) for this construction of inflow, was observednear the surface and bottom of the tank.Numerical sludge concentration distribution as afunction of depth in the axis of the settler are pre-sented in Fig.3.A satisfactory agreement of numerical and experi-mental curves of concentration sludge distributionwas observed in profiles 1 and 2. In profile 3, alarge decrease of sludge concentration obtainedin numerical simulation is connected with the factthat, for example, the sludge drift in the bottomand scrapper movement in real settler tank is nottaken into account.

References[1]. White D.A., Verdone N.: Chem. Eng. Sci., 55, 2213-2222

(2000).[2]. Berres S., Buger R., Tory E.M.: Chem. Eng. J., 111,

105-117 (2005).[3]. Burger R., Karlsen K.H., Towers J.D.: Chem. Eng. J.,

111, 119-134 (2005).[4]. Krebs P., Armbruster M., Rodi W.: Gaz, Woda Tech.

Sanit., 11 (2000), in Polish.[5]. Palige J., Dobrowolski A., Owczarczyk A., Chmielew-

ski A.G., Ptaszek S.: Inż. Ap. Chem., 42, 72-75 (2003),in Polish.

[6]. Palige J., Owczarczyk A., Ptaszek S.: Inż. Ap. Chem.,44, 24-26 (2005), in Polish.Fig.3. Profiles of sludge concentration in the axis of the set-

tler as a function of depth (8, 24, 37 m from the waste-water input).

Fig.2. Distribution of axial velocity component in planes orthogonal to the settler axis at distances: 6, 15, 25, 30 and 38 mfrom the wastewater input.

NATIVE AND TRANSPLANTED Pleurozium schreberi (Brid.) Mitt.AS BIOINDICATOR OF NITROGEN DEPOSITIONIN A HEAVY INDUSTRY AREA OF UPPER SILESIA

Grzegorz Kosior1/, Aleksandra Samecka-Cymerman1/, Andrzej G. Chmielewski,Ryszard Wierzchnicki, Małgorzata Derda, Alexander J. Kempers2/

1/ Department of Ecology and Nature Protection, Wrocław University, Poland2/ Department of Environmental Sciences, Radboud University of Nijmegen, the Netherlands

During the period of 90 days, an assay was carriedout with the moss Pleurozium schreberi trans-planted from an uncontaminated control site to

the most polluted industrial region of Poland in theUpper Silesia (Poland). Within the same period alsosamples of native Pleurozium schreberi growing in


the industrial region were collected together withthe same species from an unpolluted control site.Concentrations of total nitrogen in soil, nitrate andammonia in rainfall, nitrogen in mosses as well aslead and zinc as pollution markers in mosses weremeasured. The natural abundance of 15N was de-termined in transplanted, native and control Pleu-rozium schreberi. The examined soils from the pol-luted sites were contaminated with high levels ofnitrogen and also the concentrations of lead andzinc in mosses seriously exceeded the levels of theseelements in plants from the control sites. The in-put of atmospheric ammonium nitrogen by deposi-tion significantly exceeded that of the nitrate nitro-gen at all sites. Established correlations confirmeda general suitability of the examined moss speciesfor at least a rough estimation of the nitrogen in-put. The transplanted Pleurozium schreberi was a

better nitrogen accumulator in the less pollutedparts of the area showing a relation between theδ15N signature and the tissue nitrogen concentra-tion to the ratio NH4

+ N/NO3–N after 45 days of ex-

posure. The same species transplanted into themore polluted sites of the industrial area did notreach the level of nitrogen of native species within90 days of exposure and showed a relation to at-mospheric nitrogen deposition only after 90 daysof exposure. Therefore, it may be concluded thatthe transplanted moss needs at least 90 days in itsnew environment to give indications for pollutingnitrogen compared to the indications obtainedfrom the native mosses. Therefore, the transplantswere worse indicators of nitrogen deposition inheavy polluted areas compared to those in lesspolluted areas.

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS128

MATERIAL ENGINEERING, STRUCTURAL STUDIES,DIAGNOSTICS

Connection between the content of trace elementsin lead white and the place, time and technology of

its production can be determined on the way of ex-tensive studies carried out on sample paintings rep-

IDENTIFICATION OF LEAD WHITEOF THE 15th CENTURY GDAŃSK PANEL PAINTINGS

BY MEANS OF INSTRUMENTAL NEUTRON ACTIVATION ANALYSISEwa Pańczyk, Justyna Olszewska-Świetlik1/, Lech Waliś

1/ Faculty of Fine Arts, Nicolaus Copernicus University, Toruń, Poland

Table. Description of the analyzed samples.


resenting different periods in history and variouscountries [1-5]. More sensitive detection methodscurrently applied in neutron activation analysis(NAA), and first of all, high-resolution gammaspectrometry allow to increase the number of de-tectable elements and to more accurately deter-mine their concentrations in the lead white [2]. Amore complete distribution pattern of trace ele-ments permits also to take into account the ele-ments that were not present in original paints in agiven period of history. This is particularly impor-tant for elimination of the impurities accidentallyintroduced into paint during creation of a paint-ing. The objective of the work are systematic stud-ies on the lead white in Polish painting. The pre-sented results of analyses constitute merely a partof broader studies on lead white produced in 15thand 16th centuries. The following work containsthe results of researches of the chosen set of panelpaintings of Gdańsk from the second half of the15th century. A set of 16 pieces of panel painting,most of which were taken from the important shrineof Gdańsk – the Church of the Blessed Virgin Mary– were the object of the research. Additionally, thestudy of the retable from the Parish Church atWróblewo, an altar from the St. Peter and St. Paulchurch at Hel and Grudziądz Polyptych from theCastle of the Teutonic Knights at Grudziądz weretaken. The workshop of these three panel paint-ings is closely connected to Gdańsk painting tradi-tion. Only a part of works of art remained until ourtimes [6]. Those that were preserved, in most casesconstitute only a part of retables (panels of poly-ptychs, predellas).

All the samples were taken from paintings sub-jected to a routine maintenance work after reveal-

ing their structure and state of preservation of theoriginal layers, After removal of protective coat-ing with a scalpel under a microscope, a sample ofthe white was taken directly to a quartz ampoule.The sampling spots were selected so that they hadnot shown admixtures of other pigments as indi-cated by UV luminescence tests. Detailed descrip-tion of the paintings is presented in Table. 1-6samples from each object, with a mass from 0.1 to1 mg were collected.

The analysis of lead white samples was carriedout using the instrumental neutron activationanalysis (INAA) method without chemical sepa-ration, using standards of analyzed elements. Thesamples were packed together with standards ofsuch elements as Na, K, Sc, Cr, Mn, Fe, Co, Ni,Cu, Zn, Ga ,Ge, As, Se, Br, Rb, Sr, Zr, Mo, Ru,Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu,Tb, Dy, Ho, Er, Yb, Lu, Hf, Ta, W, Ir, Au, Hg, Thand 238U. Also attached were the standards of goldand scandium evaporated onto a piece of alu-minium foil. They played the role of the thermalneutron flux monitor.

Irradiation of the samples was carried out in theMARIA reactor at Świerk, in a channel with 8*1013

n/cm2s thermal neutron flux. The irradiation timewas 24 h with subsequent 8-hour cooling. Then,the irradiated samples were unpacked and washedin 1:1 hydrochloric acid solution and rinsed in al-cohol to remove surface contaminations.

Measurements of activity of samples and stan-dards prepared in such a way were carried out us-ing an HP germanium detector with an active vol-ume of 80 cm3 and an energy resolving power of1.95 keV for the 1333 keV peak from 60Co. Thedetector cooperates with a S100 Canberra analyzer,

Fig. Dendrogram of 56 lead white samples taking from 19 panel paintings (number of features is 28) – standardizedvariables.


controlled by IBM/PS-2. The analysis of complexgamma radiation spectra was carried out usingmicro-SAMPO and Gene 2000 programs. Themeasurements were repeated six times within threemonths after irradiation. The measurement timevaried between 300 and 10 000 s. Thirty two ele-ments were identified and determined in the ana-lyzed samples.

Ultimately, 28 elements were selected formultiparameter statistical analysis aimed at iden-tifying the degree of similarity of analyzed paint-ings.

The clustering analysis using STATISTICA(StatSoft) program was carried out to identify thesimilarity degree of analyzed objects. The cluster-ing analysis was carried out for standardized vari-ables.

The results of clustering analysis for all thetested 19 panel paintings (56 samples of lead white)are presented in Fig., which clearly shows divisioninto four groups. Based on to date quantitativeanalysis of the trace elements in lead white col-lected from paintings from the 15th-19th century,it can be concluded that lead white from the stud-ied panel paintings shows a lower content of cop-

per and manganese and a higher content of sliverand antimony than lead white from regions southto Alps and is more similar to lead white appliedin Northern Europe [4,5,7]. The results of the con-ducted analyses revealed features characteristic ofpainting technique of Gdańsk of the second halfof 15th century.

References

[1]. Perlman I., Asaro F., Michel H.V.: Annu. Rev. Nucl.Sci., 22 (1972).

[2]. Sayre E.V.: Advan. Activ. Anal., 2 (1972).[3]. Fleming S.J.: Authenticity in art. London 1975.[4]. Houtman J.P., Turkstra J.: Neutron activation analysis

and its possible application for age determination ofpaintings. In: Proceedings of the Conference on Radio-chemical Methods of Analysis, Salzburg, Austria 1964.IAEA, Vienna 1965, vol.1.

[5]. Lux F., Braunstein L.: Z. Anal. Chem., 221 (1966), inGerman.

[6]. Olszewska-Świetlik J.: Technologia i technika gdań-skiego malarstwa tablicowego drugiej połowy XV wie-ku. Toruń 2005, in Polish.

[7]. Pańczyk E., Ligęza M., Waliś L.: Nukleonika, 37, 29(1992).

For the last twenty centuries, lead white hasbeen one of the most frequently used pigment. Itspurity is directly related with the development ofmethods of production and purification of lead.Owing to this fact, it is possible to distinguish thegroups of the artists by whom the painting has beencreated by determining trace elements present inthe lead white used. In addition, it is possible toidentify repainted fragments and conservationsteps made which is of great importance to art his-torians. The variation seen in trace element com-positions according to region and time, properauthentication would require compiling a libraryof analyses of carefully documented paintings tocompare statistically the painting in question. Suchwork can confidently contribute to the reassign-ment of dates and the placement of objects in theircorrect historical context [1-4].

The lead white of commerce that has been usedin painting is the basic carbonate 2PbCO3·Pb(OH)2.Lead carbonate hydroxide is chemically equivalentto the naturally occurring hydrocerrusite, however,the mineral equivalent is extremely rare and con-sequently rarely used as a pigment source. Duringthe Roman period, lead white was well-known his-torically as a synthetic pigment that is made frommetallic lead and vinegar. Lead white was com-monly adulterated with other white pigments, par-ticularly chalk, baryte and kaolinite to cut cost [4].

The goal of the described work is the compari-son of trace element patterns and particle mor-phology of contemporary lead white pigments andBologna chalk which was used very often as an

The analysis of pigments on artworks is of majorsignificance in art conservation as it leads to detailedcharacterization of materials and is thus importantfor dating and authentication, as well as for poss-ible conservation or restoration of artwork. Pigmentanalysis can be a challenging problem due to thecomplexity of materials analyzed because one mayhave to identify several different pigments used inmulticomponent mixtures and in different paintlayers. The problem becomes even more demand-ing for artworks in which sampling is either ex-tremely limited or even forbidden. Several analyti-cal techniques for identification of pigments havebeen in use for many years such as scanning elec-tron microscopy (SEM), energy-dispersive X-ray(EDX), X-ray diffraction (XRD), X-ray fluor-escence (XRF), Fourier-transform infrared spec-troscopy (FT-IR), UV-visible absorption, particle--induced X-ray emission (PIXE), proton-inducedgamma-ray emission (PIGE), Rutherford back-scattering spectroscopy (RBS), instrumental neu-tron activation analysis (INAA) and prompt gammaactivation analysis (PGAA) [1-3].

Natural and synthetic pigments are subject tovarious geological, mining and manufacturing pro-cesses, which are unique to each manufacturer.Understanding of the manufacturing process ofcommon pigments allows the forensic scientist tounderstand how trace elements may become in-corporated into the final product, and validity ofthe concept of using their association pattern inthe paint as a provenance establishment tech-niques.

ELEMENTAL COMPOSITION AND PARTICLE MORPHOLOGYOF LEAD WHITE PIGMENTS

Bożena Sartowska, Ewa Pańczyk, Lech Waliś


admixture to lead white specially in grounding ofpaints, with lead white pigment taken from thepanel painting of Crucifixion Triptych (Gać Śląska,dating on 1440/1450) which belongs to the so-calledSilesian Painting School. We used two methods:INAA for determination of trace elements and SEMfor revealed morphology of investigated pigments.

The activation analysis is one of the moderninstrumental analytical methods. Since 1950 it hasbeen an important technique used to analyze trace

elements at a level of ppb or even better in a widerange of materials. In the 1950’s there was no tech-nique that could compete with this method. Atpresent, though there are other methods with com-parable sensitivity, neutron activation analysis(NAA) still offers new capabilities thanks to thedevelopment of electronics and availability of in-creasingly technologically advanced instruments.This results in enhanced precision, accuracy andrepeatability [1,3].

Table. Composition of lead white and chalk samples [ppm].


The analysis of lead white samples was carriedout using the INAA method without chemicalseparation, using standards of analyzed elements.The samples were packed together with standards[3]. Also attached were the standards of gold andscandium evaporated onto a piece of aluminiumfoil. They played the role of the thermal neutronflux monitor.

Irradiation of the samples was carried out inthe MARIA reactor at Świerk, in a channel with8x1013 n/cm2s thermal neutron flux. The irradiationtime was 24 h with subsequent 8-hour cooling. Mea-surements of radioactivity of samples and standardswere carried out using an HP germanium detectorwith an active volume of 80 cm3 and an energy re-solving power of 1.95 keV for the 1333 keV peakfrom 60Co. The detector cooperates with a S100Canberra analyzer, controlled by IBM/PS-2. Theanalysis of complex gamma radiation spectra wascarried out using micro-SAMPO and Gene 2000programs. The measurements were repeated sixtimes within three months after irradiation. Themeasurement time varied between 300 and 10 000s. Thirty two elements were identified and deter-mined in the analyzed samples. The results of thisanalysis are presented in Table.

It follows from the comparison of the data setsobtained for the investigated samples that the oilcolour from Grumbacher N.Y. firm characterizeda very high concentration of zinc which is an ad-

mixture in this contemporary paint. In original,lead white taken from the Crucifixion Triptych con-tained a higher concentration of copper and lowerof silver than in contemporary pigments.

The same four different kinds of pigments wereinvestigated by means of SEM: powder of CaCO3– calcite, powder of 2PbCO3·Pb(OH)2 – lead whitepure pigment (Poland), oil colour form GrumbacherN.Y. and original lead white pigment taken fromthe panel painting of the Crucifixion Triptych withlinseed oil binder.

Powders of pigments and small pieces of paintswere fixed at the microscopic tables using the con-ductive glue (Quick Drying Silver Paint, Agar Scien-tific Ltd.). The surfaces of the samples were coatedwith a thin layer of metal to reduce the chargingwhich takes place during SEM observations [5].They were covered with a thin layer (less than 10nm) of gold using a vacuum evaporator JEE-4X(JEOL, Japan). Observations were carried out us-ing scanning electron microscope DSM 942 (Zeiss,Germany).

Powder of CaCO3 consists of agglomerates ofneedle-shape grains (Fig.1A). Needles-grains withdifferent sizes are in the shape according to thetheoretical calcite orthorhombic crystal system [6].

Powder of lead white consists of agglomeratesof hexahedron plate-shape grains (Fig.1B). Thesizes of these plates are: the diagonal – about 2.4μm and the thickness – about 0.3 μm. The shape

Fig.2. Oil colour (Grumbacher N.Y.): A – surface, B – brittle fracture.

A

Fig.1. Pigments: A – calcite CaCO3, B – lead white 2PbCO3·Pb(OH)2.

B

B

A


oil paint from Gać Śląska shows a spherical shapeof the pigment particles dispersed in used oil.

In this work, it was demonstrated that a com-bined method approach, performed directly on theartwork and small samples, is able to identify thematerials that were used to manufacture artefacts.The consequence of these findings, in relation todating and authenticating the investigated artefact,are consistent with the art historical observations.

According to our experience, the NAA andSEM methods are a powerful tool to identify andcharacterize the pigments.

References[1]. Houtman J.P., Turkstra J.: Neutron activation analysis

and its possible application for age determination ofpaintings. In: Proceedings of the Conference onRadiochemical Methods of Analysis, Salzburg 1964.IAEA, Vienna 1965, vol.1.

[2]. Lux F., Braunstein L.: Z. Anal. Chem., 221 (1966), inGerman.

[3]. Pańczyk E., Ligęza M., Waliś L.: Nukleonika, 37, 29 (1992).[4]. Eastugh N., Walsh E., Chaplin T., Siddall R.: Pigment

compendium. Elsevier 2004.[5]. Goldstein I.J.: Electron microscopy and X-ray micro-

analysis. A text for biologist, material scientists andgeologists. Plenum Press, New York 1992, 820 p.

[6]. Poradnik fizykochemiczny. Praca zbiorowa. WNT,Warszawa 1974, 1985 p. (in Polish).

[7]. Spychaj T., Spychaj S.: Farby i kleje wodorozcieńczalne.WNT, Warszawa 1996, 323 p. (in Polish).

of the observed plates are in good agreement withthe theoretical hexagonal crystallographic latticeof 2PbCO3·Pb(OH)2 [6].

The Grumbacher N.Y. oil colour was in the driedform as a bulk material. Pieces of this paint havethe smooth surface without cracks and inclusions.Visible grains are fixed in the matrix. Diameter ofthe single grain is less than 1.1 mm (Fig.2A). Sur-face of brittle fracture shows a lot of cracks andvoids, free pieces of material could be distinguished.Much smaller particles (about 0.3 μm) fixed in thematrix are visible at the fracture (Fig.2B).

The sample of lead white from the CrucifixionTriptych was in the form of some small particles ofdried paint. Their surfaces are rough with voidsand inclusions (Fig.3A). The interesting objects –groups of the spherical particles are also observed.The spheres are in different sizes: from less than0.3 μm in diameter (Fig.3B) to rather big – 17.6μm in diameter (Fig.3C). This shape is the resultof the pigment formation: the particles of solidphase of 2PbCO3·Pb(OH)2 are dispersed in theliquid phase of used oil [7].

Scanning electron microscopy is a useful toolfor investigations of the morphology of pigmentsand paints. The investigated pigments consist ofsmall particles with the shape in accordance withthe theoretical shape of crystallized CaCO3 and2PbCO3·Pb(OH)2. The investigated paints showthe pigment particles fixed in the oil matrix. The

Fig.3. Lead white from the panel painting Crucifixion Triptych with linseed oil binder: A – bulk sample, B – dispersedparticles x20 000, C – dispersed particles x5000.

A B

C


Analyses by wavelength dispersive spectrometryin the EPMA system were carried out usingCameca SX-100 at the Electron Microprobe Labo-ratory, Faculty of Geology, Warsaw University.Standards were oxides and minerals. Corning B,C, D, and NIST 610, 612, among others, were usedas secondary standards.

The obtained results have confirmed that bluefluorescence of baroque central European vesselglass is connected to the presence of lead in glass.There is no border PbO concentration that causethe phenomenon. The PbO concentration evenbelow 0.2% can cause the bright blue fluorescence.On the other hand, in this range slightly below0.5% of PbO, a few examined glasses did not showthe fluorescence at all. These vessels are attributedto unknown Polish and/or Russian factories runby the end of the 18th century.

The presence or absence of blue fluorescencedoes not seem to depend on the concentration ofMn and Fe, thought the relative ratios of Pb, Mnand Fe influence the changes of glass fluorescenceunder UV-C in the case of such small lead con-centrations.

When the PbO content is higher (over 0.5%),glass shows this fluorescence independently of thekind of glass matrix composition. There is one ex-ception found and it concerns a few vessels attrib-uted to Zechlin (or Potsdam), Brandenburgia(Fig.1). It should be underlined that not all glassesfrom this glass centre behave in this way; other

examples also containing lead show the blue fluor-escence. We do not know the reason of it.

Three groups of leaded central European glass,which show blue fluorescence under UV-C radia-

About 1200 colourless glass vessels originatedmainly from central European areas and dated to17th and 18th centuries were analyzed by the useof energy dispersive X-ray fluorescence (EDXRF)analysis and examined under UV-C radiation.These observations were carried out to distinguishthe items that show blue fluorescence, which isassociated with the presence of lead in glass. Thecolour of fluorescence was determined with thenaked eye. Also, small samples were taken fromthe 88 examined objects. They were analyzed bythe use of electron probe microanalysis (EPMA).

The project constitutes a continuation of ourprevious paper [1].

A band with the dominant line of 253.7 nm(usually denoted as UV-C) was applied. Commer-cially available sources of the UV-C radiation wereused (two low pressure TUV 15 V mercury lamps,manufactured by Philips). They were installed in aspecial chamber for safe observation of the phe-nomenon. The total radiation intensity in thechamber amounted to 8.257x10–4 W/cm2 (for thewavelength range of 200-398 nm), with a singledominant peak of 2.503x10–4 W/cm2 for a wave-length of 254 nm.

Energy dispersive X-ray fluorescence was usedin a surface manner. The 109Cd and 241Am radio-isotope annular sources were applied to excite theelements in the glass. X-ray spectra were measuredusing Si(Li) and a planar HPGe detectors. The livetime of the measurements was 600 s. The analyzed

area of glass amounted to approximately 2 cm2.No quantitative chemical analysis was carried outby the use of EDXRF. Only PbO contents were es-timated.

ULTRAVIOLET BLUE FLUORESCENCEOF CENTRAL EUROPEAN BAROQUE GLASS (FURTHER RESULTS)

Jerzy Kunicki-Goldfinger, Joachim Kierzek, Piotr Dzierżanowski1/

1/ Faculty of Geology, Warsaw University, Poland

Fig.1. Triangular diagrams for the variables Pb, Mn, and Fe. The variables have been transformed in such a way that thesum of their values is constant for each case.


Tab

le. C

hem

ical

com

posi

tion

of 2

1 gl

asse

s an

alyz

ed b

y th

e us

e of

EP

MA

[wt%

].

< –

bel

ow d

etec

tion

lim

it.

For

all

sam

ples

: P2O

5<0.

4.


We know relatively little about glass productionin the second half of the 17th century, when vari-

ous technologies and manufacturing processes thatwould later become commonplace were still being

tion, have been distinguished (tentatively markedA, B, and C) (Fig.2). “A” is white (chalk) glass with

highest PbO concentration reaching c. 2%. “B” iscrystal glass. The PbO content did not exceed 6%.“C” is also crystal glass, but with the PbO contentover 6%. These groups differ from one anotherin the chemical composition as a consequence ofthe application of determined recipes and raw ma-terials.

Chemical composition of 21 glasses with thehighest PbO concentration analyzed by the use ofEPMA (in wt%) are presented in Table. The itemshave been sorted according to their lead contentand the presence of blue colour of their fluorescenceis indicated. The PbO level in the remaining 67glasses, also examined by the use of EPMA, re-mains below 0.04% and they did not show bluefluorescence. It can be seen that the glasses withPbO content over about 0.2-0.3% show this distinctblue fluorescence. Though, there are two excep-tions and both vessels were produced in Zechlin.

According to our previously published results,we can now divide leaded crystal central Europeanglass from the 18th century into two groups, B andC. The further conclusion is that all glasses thatbelong to group C showed blue fluorescence.Among the glasses from group B, we have found afew exceptions.

We have also found a few examples with verylow lead content (or with its concentration belowthe detection limit) that exhibit weak pale-bluefluorescence. This phenomenon is caused probablyby the presence of other kind of fluorescent centrein glass than lead.

Spectroscopy seems to be undoubtedly neededfor further studies on this phenomenon.

The project has been carried out at the Instituteof Nuclear Chemistry and Technology in Warsawwithin the frameworks of a few separated projectssince 1998.

The following museums made the vessels avail-able for examination: the National Museums(Gdańsk, Cracow, Poznań, Warsaw, Wrocław), theRoyal Castle in Warsaw, the Wawel State Art Col-lection, the Czartoryski Museum and the Jagiellon-ian University Museum (Cracow), the District Mu-seums (Jelenia Góra, Rzeszów, Tarnów), the Łań-cut Castle Museum, Museum in Nieborów andArkadia, the Museum-Palace in Wilanów, the His-torical Museum of Warsaw and private collectors.

References[1]. Kunicki-Goldfinger J.J., Kierzek J.: Glass Technol.,

43C, 111-113 (2002).

Fig.2. The scatter plots for PbO [wt%] and, respectivelyRb, Y and Zr. Rb, Y and Zr contents are expressedin arbitrary units. Three groups of leaded glass havebeen distinguished.

LATE 17th CENTURY GLASS VESSELS FROM EILAND– TECHNOLOGICAL APPROACH

Jerzy Kunicki-Goldfinger, Martin Mádl1/, Piotr Dzierżanowski2/

1/ National Museum & Institute of Art History, Academy of Sciences of Czech Republic, Prague,Czech Republic

2/ Faculty of Geology, Warsaw University, Poland


developed and tested. In the catalogs of Europeanglass collections, we find only a few objects that canbe reliably dated between the 1650s and the 1690s,with the exception of enameled glass that derivesfrom the Renaissance tradition.

This article draws attention to several luxuryobjects that are intriguing because of their crizzledglass and forming and finishing techniques. We havemanaged to date these objects with considerableprecision. At the same time, we have attempted tosituate them in the broader context of Europeanglass production, and specifically to link them withthe important Hessian glassmaker Georg Gunde-lach and his heretofore little-known work in Bohe-mia.

Our primary method for the identification ofobjects has been art-historical analysis, augmentedby chemical analysis of the selected samples. Threeobjects attracted our special attention. One of themis a goblet of Matthias Helfried von Plönstein dec-orated with a prelate’s coat of arms in the glass col-lection of the Prague City Museum (inv. no. 137 969).The next object that deserves our attention is a gob-let of Christoph Lodron and Catharina von Spaurbearing the coat of arms of the Lodrons in the col-lection of the Museum of Applied Arts in Prague(inv. no. 4 462). Another vessel that can be linkedwith the Thun court and perhaps also with the glass-works in Eiland is a small jug of Marie Adelheid,Countess Thun with the motif of the Virgin andChild in the collection of the Department of CzechHistory of the National Museum in Prague (inv. no.H2 – 6 579).

The main goal of this part of our study was toidentify the technology used in the manufacture ofthe three glass vessels. We assumed that this wouldcontribute important complementary informationto the study of the provenance and dating of theobjects.

Two preliminary assumptions have been madein writing this section. First, we use the term “glass”to mean only the material, not the object, and wecharacterize this “glass” exclusively in terms of itschemical composition. Second, when interpretingthe chemical composition, we consider only thelikely intention of the glassmaker, assuming thatthis composition reflects, at least to some extent,the recipe used. This method of analysis differsfrom an assessment of the optical quality of theglass that is made with the naked eye, since thelatter involves an examination of the final prod-uct, which does not always reflect the glassmaker’sintention. In some instances, glass that was intendedto be of particularly fine quality emerged from themanufacturing process as an inferior material, andthe reverse also happened.

We use the terms “crystal glass”, “white glass”(also referred to as “chalk glass”), and “ordinaryglass” in referring to the chemical composition ofthe glass. These terms correspond to the three typesof glass compositions developed by the Venetians:cristallo, vitrum blanchum, and vetro commune [1].These three basic formulas for colorless glass wereused during the period under discussion, and theyare known from documentary sources. Their char-

acteristics and distinct properties have been dis-cussed elsewhere [2].

We took small samples of glass from the threevessels and analyzed them by wavelength-disper-sive spectrometry with electron-probe microanaly-sis (EPMA). The samples for analysis were col-lected with a diamond point. They came from thepontil mark of the goblet of Matthias Helfried vonPlönstein; from the bowl of the jug of Marie Adel-heid, Countess Thun; and from the stem of the gob-let with the coat of arms of the Lodron family. Thesamples were mounted in blocks of epoxy resin,polished to 0.25 μm, and coated with a layer ofcarbon. The analyses were carried out using aCameca SX-100 equipped with three simulta-neously working spectrometers (PET, LIF, TAPcrystals, and PC2 for boron) at the Electron Micro-probe Laboratory (Faculty of Geology, WarsawUniversity). The measurement conditions were asfollows: (i) for main constituents – 15 kV, 6 nA, 20μm beam diameter, counting time 20 s for eachelement; (ii) for minor and trace constituents (withfixed concentration of main constituents) – 20 kV,100 nA, 80 μm beam diameter, counting time 20-60s; and (iii) for boron (with fixed concentration ofmain and minor constituents) – 5 kV, 100 nA, 20μm beam diameter, counting time 20 s. The stan-dards were oxides and minerals. Corning referenceglass D, CRM-glasses 4001 and 4002 (Glass Insti-tute, Hradec Králové, Czech Republic), and NISTCRM-glasses 610 and 612 were used as secondarystandards.

The results are presented in Table (Nos.1, 2,and 11). For comparison, we include the results ofchemical analyses of luxury glasses manufacturedin central Europe from the late 17th through the18th centuries. Because there are almost no pub-lished chemical analyses of central European luxurybaroque glasses from the late 17th century, we haverelied mainly on examples from the first half ofthe 18th century and on two vessels from about1700 that were specially examined for our study.They are shown in Table as Nos.3 and 4. Bothglasses are crizzled. The analyses were also car-ried out using EPMA, under the same conditions.

The presence of certain chemical componentsand their concentrations in all of the glasses inTable provide clues to their provenance and dat-ing. The near absence of MgO and P2O5, as well asthe presence of As2O3, suggests that the glass wasmelted from batches containing potash (and/orsaltpeter) as a flux, arsenic, and other ingredients.Saltpeter and arsenic began to be used in the pro-duction of certain types of colorless vessel glass incentral Europe probably not earlier than in thesecond half of the 17th century.

The glasses in Table are grouped into three setsaccording to composition. The first set consists ofsix examples of central European crystal glass dat-ing from the late 17th century and about 1700. Itincludes the goblet of Matthias Helfried von Plön-stein and the goblet with the coat of arms of theLodron family. These examples are distinguishedby their uniquely low concentration of CaO, whichis significantly below one weight percent (<1%),


All

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, 8, a

nd 1

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d bu

t not

qua

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< –

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lim

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: P2O

5<0.

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O3<

0.4,

Rb 2

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0.07

, ZrO

2<0.

01, Y

2O3<

0.03

, ZnO

<0.

03.

Col

umn

3: N

M –

Nat

iona

l Mus

eum

, MA

A –

Mus

eum

of A

pplie

d A

rts,

MP

– M

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m P

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Tab

le. C

hem

ical

com

posi

tion

of l

uxur

y ve

ssel

gla

ss fr

om c

entr

al E

urop

e, la

te 1

7th

and

18th

cen

turi

es [w

t%].


and five of these vessels have relatively high levelsof B2O3. The EPMA system used for the analysesallowed us to quantify boron oxide only when itsconcentration exceeded about 0.7-1%, dependingon the glass matrix. Because of this, in certain cases,boron could be found but not quantified.

The low CaO content suggests that calciumcould have been introduced to the glass as con-tamination or as a minor constituent of certain rawmaterials (possibly potash or wine stone). If thistype of crystal glass was made without adding cal-cium as a raw material, it may be considered a suc-cessor to Venetian cristallo. Another possible ex-planation is that chalk was added as an ingredientin very small quantities. Chalk appears in lists ofraw materials used during this period, but we donot know if it was used in the production of thisparticular type of glass. The higher concentrationof B2O3 seems to be a characteristic only of crystalglass, and documentary sources from the periodconfirm that borax was used in the production ofcrystal glass. Five of these six early examples of crys-

tal glass are known to have been manufactured inBohemian and German centers. The vessel fromAltmünden is dated to about 1710, and it differsfrom the other glasses in this set in its possible lackof B2O3 and its high PbO content. It may thus beseen as a later variation of this early crystal glassformula. It appears that lead compounds wereintroduced as separate raw materials in centralEuropean colorless vessel glass formulas not ear-lier than about 1700 [3].

The second set contains four objects from thefirst half of the 18th century. They were made inDresden, Zechlin, Naliboki, and an unidentifiedGerman glasshouse. The composition of this latercrystal glass is distinguished by a higher CaO con-tent (which does not go much above 5% in any ofthe discussed examples). The other characteristicfeatures of the chemical composition of this glassare its significant PbO content and the lack of, ormarkedly lower concentration of, B2O3.

The four examples of white glass in the thirdset, which date from the late 17th century to theend of the 18th century, originated in Bohemia,Germany, and Poland. Their composition is char-acterized by a lack of B2O3 and a significantlyhigher CaO concentration (ranging from 7.5 to9.5%).

White glass and crystal glass may generally bedistinguished by calculating variables from thealkaline and alkaline earth oxide concentrations,as shown in Fig.1. This plot clearly shows thatbaroque crystal glass and white glass followed the

tradition of Venetian cristallo and vitrum blanchum,respectively.

In Figure 1, we can also observe the division ofbaroque crystal glass into the earliest formulation,which is characterized by a virtual lack of CaO (agroup of points in the lower right corner of the plot),and later formulations. The same division can beseen even more distinctly in Fig.2, which is a plotof As2O3 and CaO concentrations. Based on thisplot, we can tentatively conclude that levels of these

Fig.1. Venetian soda-ash glass (vitrum blanchum and cristallo) and the late 17th and 18th century central Europeanpotassium glass (white glass and crystal) shown in a scatter plot for the variables calculated from the alkaline andalkaline earth oxide concentrations. The three vessels that are considered to be Eiland products are indicated byarrows [2,4].


oxides gradually increased in crystal glass from thetime its manufacture in this part of Europe beganin the late 17th century.

We conclude that the goblet of Matthias Hel-fried von Plönstein and that with the coat of armsof the Lodron family are made of crystal glass fromthe earliest known phase of its development incentral Europe, while the jug of Marie Adelheid,Countess Thun is an example of white glass. Bothof the goblets are crizzled, and it is well known thatcrystal glass is particularly susceptible to crizzling[5,6].

The glasses from which these two goblets weremade have very similar chemical compositions, andthey may therefore be considered as products of thesame glasshouse and made during the same period.In this article, these glasses are tentatively attributedto the Eiland glassworks. However, we can neitherexclude nor confirm the same attribution for thejug of Marie Adelheid, Countess Thun. Moreover,the chemical composition of this glass affords noclues to its dating.

Because of the lack of published chemical analy-ses of Bohemian luxury vessel glasses from the late17th century, as well as any known object that canbe securely attributed to the Eiland glasshouse, allconclusions concerning the dating and attributionof the three vessels discussed in this article mustremain a working hypothesis.

It is very encouraging that the art-historical andtechnological studies we conducted produced suchsimilar results. On some points, our findings werecomplementary, enabling us to offer bolder hypoth-eses. However, a consistently wide margin of un-certainty has to be taken into account, as is usualfor this type of research.

Two of the objects discussed in this article – thegoblet of Matthias Helfried von Plönstein and theLodron goblet – show many similarities in typol-

ogy, stylistic features, iconography, and the tech-nology used in their manufacture. Both vessels areexceptional in their decorative features and thequality of their glass. Their chemical compositionrepresents an early phase in the development ofcrystal glass in central Europe. Based on histori-cal research, we can date the goblets quite securelyabout 1675, while chemical analysis confirms thatthey were probably produced in the late 17th cen-tury. We can be fairly sure that the goblets weremade with the same technology, in the same fac-tory, and by the same glassmaker. The Eiland glass-works and Georg Gundelach are the strongest can-didates, although the lack of comparative materialmakes this attribution uncertain.

As for the jug of Marie Adelheid, CountessThun, we can say only that it was made of whiteglass after 1688. This dating, unlike that of thegoblets, is based solely on stylistic analysis and his-torical research. The jug differs from the two gob-lets both technologically and stylistically.

We cannot rule out the same attribution for allthree vessels. However, we did not find any clearevidence indicating that the jug was manufacturedin the same glasshouse as the goblets. This remainsan open question [7].

References[1]. Moretti C., Toninato T.: Rivista della Stazione Speri-

mentale del Vetro, 1, 31-40 (1987), in Italian.[2]. Kunicki-Goldfinger J., Kierzek J., Dzierżanowski P.,

Kasprzak A.J.: Central European crystal glass of thefirst half of the eighteenth century. In: Annales du 16e

Congres de l’Association Internationale pour l’Histoiredu Verre (London 2003). AIHV, Nottingham 2005, pp.258-262.

[3]. Kunicki-Goldfinger J., Kierzek J., Kasprzak A.J.,Dzierżanowski P., Małożewska-Bućko B.: Lead inCentral European 18th-century colorless vessel glass.In: Archäometrie und Denkmalpflege – Kurzberichte

Fig.2. Crystal and white glass from various central European glasshouses (late 17th and 18th centuries). The three vesselsthat are considered to be Eiland products are marked as black squares. Scatter plot for As2O3 and CaO concentrations.


Silica biocides insoluble in water obtained by coat-ing a carrier (TiO2, dolomite etc.) with an ammo-nium salt (QAC – quaternary N-alkylammoniumcompound) and water glass (WG) stabilized bysulphuric acid have been described previously [1-3].

Many scientific papers on the synthesis of silicamaterials with the application of acid or basichydrolysis of alcoholic solution of tetraethoxysilan(Si(OEt)4) have been published [4,5]. Nanosol, whichcan be connected with other materials creatingnanogel, can be obtained by this procedure.

On the basis of the earlier developed technol-ogies, we have elaborated a method for the syn-thesis of water soluble silica materials containingquaternary alkylammonium salts (s-SiO2-QAC).

Example: 20 ml of 50% aqueous solution ofbenzalkonium chloride (Aldrich) was dissolved in20 ml of Si(OEt)4 (Aldrich), then 100 ml of isopro-panol was added and the mixture was stirred. Next,10 ml of 0.04% HCl or 0.02% H2SO4 was addedand the mixture stayed at room temperature untilthe next day. Properties of the hydrolyzate indicatecomplete hydrolysis of Si(OEt)4 and binding ofsilica with QAC. The hydrolyzate is bound quan-titatively with carrier C (e.g. TiO2, dolomite) andthe product indicates properties characteristic of

insoluble in water materials C(SiO2-QAC): bindsacid dyes effectively, binds Ag+ from water andzero-valent silver atoms obtained due to UV irra-diation.s-SiO2-QAC can be also incorporated into fabricsand similar materials.

Investigations of biocidal properties of solublematerials s-SiO2-QAC and their binding with dif-ferent carriers as well as structural investigationare being continued.

References[1]. Łukasiewicz A., Krajewski K.J., Gajewska J., Chmiele-

wska D.: Właściwości biocydowe nowych materiałówdla budownictwa modyfikowanych IV-rzędową soląN-alkiloamoniową związaną z krzemionką. In: Czwarto-rzędowe sole amoniowe. Wydawnictwo Instytutu Tech-nologii Drewna, Poznań 2005, pp. 432-437 (in Polish).

[2]. Łukasiewicz A., Chmielewska D., Waliś L., KrajewskiK.: Ekologia, 29, 3, 36-37 (2005), in Polish.

[3]. Chmielewska D.K, Łukasiewicz A., Michalik J., Sar-towska B.: Nukleonika, 51, Suppl. 1, 69-72 (2006).

[4]. Mahltig B., Haufe H., Bottcher H.: J. Mater. Chem.,41, 15, 4385-4398 (2005).

[5]. Haufe H., Thron A., Fiedler D., Mahltig B., BottcherH.: Surf. Coat. Int. B: Coat. Trans., 88, 1, 55-60 (2005).

WATER SOLUBLE SILICA BIOCIDESCONTAINING QUATERNARY AMMONIUM SALTS

Andrzej Łukasiewicz, Dagmara K. Chmielewska, Lech Waliś

2003 (Berlin). Etnologischen Museum StaatlicheMuseen zu Berlin, Berlin 2003, pp. 56-58.

[4]. Verità M.: Rivista della Stazione Sperimentale delVetro, 15, 1, 17-29 (1985), in Italian.

[5]. Kunicki-Goldfinger J., Kierzek J., Małożewska-BućkoB., Kasprzak A.: Glass Technol., 43C, 364-368 (2002).

[6]. Kunicki-Goldfinger J.: Preventive conservationstrategy for glass collections: identification of glassessusceptible to crizzling. In: Proceedings of the 5th EC

Conference “Cultural Heritage Research: A Pan-Euro-pean Challenge”, Cracow, Poland, 16-18.05.2002. Ed.R. Kozłowski. Institute of Catalysis and SurfaceChemistry, Polish Academy of Sciences and EuropeanCommunities, Cracow 2003, pp. 301-304.

[7]. Mádl M., Kunicki-Goldfinger J.: J. Glass Stud., 48,255-277 (2006), (the full text of the article, which com-prises both historical and technological approaches).

THE ROLE OF CARBON, CHROMIUM AND NITROGENIN AUSTENITIZATION OF UNALLOYED AND ALLOYED STEELS

BY INTENSE PLASMA PULSESJerzy Piekoszewski1,2/, Ludwik Dąbrowski3/, Bożena Sartowska1/, Lech Waliś1/,

Michał Kopcewicz4/, Justyna Kalinowska4/, Marek Barlak2/, Jacek Stanisławski2/,Zbigniew Werner2/, Adam Barcz5/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland

3/ Institute of Atomic Energy, Świerk, Poland4/ Institute of Electronic Materials Technology, Warszawa, Poland

5/ Institute of Physics, Polish Academy of Sciences, Warszawa, Poland

In our previous works it was shown that normaland so-called expanded austenite phases (γN , γC)can be formed not only in the stainless steel butalso in carbon steels and even in the pure α-iron ifthey are treated with high intensity nitrogen plasmapulses [1,2]. The purpose of the present work was

to study how the alloying elements such as carbon,chromium and nitrogen influence the efficiency ofaustenitization of steels treated by argon and ni-trogen plasma pulses [3]. The steel samples con-tained initially 2.5-4.2 at.% C, 0.12-14 at.% Cr andabout 1 at.% N after the nitrogen plasma treatment


THERMAL STABILITY OF THE PHASES FORMEDIN THE NEAR SURFACE LAYERS OF CARBON STEEL

BY NITROGEN PULSED PLASMA TREATMENTBożena Sartowska1/, Jerzy Piekoszewski1,2/, Lech Waliś1/, Jacek Stanisławski2/, Lech Nowicki2/,

Renata Ratajczak2/, Michał Kopcewicz3/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland

3/ Institute of Electronic Materials, Warszawa, Poland

The intense pulsed plasma beams were used forcarbon steel surface modification. The energy den-sity of the pulse was high enough to melt the nearsurface region of the substrate and nitrogen was in-troduced into the liquid alloy. The nitrogen expandedaustenite – γN (austenite in which iron atoms haveone or more nitrogen atoms in the nearest neigh-bourhood) was found in the near-surface region ofcarbon steel and significant increase of hardnessand tribological properties were observed [1]. Theformation of nitrogen expanded austenite does notfollow the equilibrium phase Fe-N diagram [2,3].At elevated temperature, the interstitial atoms canbe released from the lattice and diffuse. Therefore,the stability under maximum operating tempera-tures must be determined and it must be knownhow long a component can be used under specificthermal load before undesirable properties occur.

Carbon steel 1C45 with 0.52 wt% C and heattreated with the standard procedures was used forinvestigations. The plasma pulses were generatedin a rod plasma injector (RPI) [4]. The samples wereirradiated with five nitrogen plasma pulses at anenergy density of about 5 J cm–2. The samples werecharacterized by: nuclear reaction analysis (NRA)14N(d,α)12C for the determination of retained ni-trogen dose and conversion electron Mössbauerspectroscopy (CEMS) for quantitative analysis ofthe identified phases. The annealing processeswere carried out using a tube furnace, with con-

trolled temperature and flow of the ambient gas –argon. The heat treatment parameters were: tem-perature between 100 to 300oC with a step of 50oCfor 1 h. In the investigating samples nitrogen re-tained a dose of 1.2x1017 cm–2. The standard devia-tion σ=2x1016 cm–2.

Relative changes of the determined parameterscharacterizing properties of the material are definedas:

[(AM – IM)/IM] x 100%where AM and IM are the values of the investigatedparameter for annealed and initial material, respec-tively.

After annealing, the relative surface nitrogenconcentration changes depending on the anneal-ing temperature (Fig.1). The surface nitrogen con-centration increased up to temperature of about

Fig.1. Changes of surface nitrogen concentration as a re-sult of annealing the modified samples.

were used in the investigations. The pulses weregenerated by rod plasma injector type of genera-tor described in detail in [4].

The energy density of plasma pulses was about5 Jcm-2, pulse duration – about 1 μs and numer ofpulses – 3. The energy was high enough to melt thenear surface layer, so the used element was dopedto the liquid metal. The samples were examinedby conversion electron Mössbauer spectroscopy(CEMS), X-ray diffraction (XRD) and secondary--ion mass spectroscopy (SIMS) techniques. Themain results of the detailed analysis of the experi-mental data can be summarized as follows:- Both nitrogen and carbon alone are capable of

forming normal and expanded austenite phasesγN and γC.

- Of all three alloying elements: carbon, chromiumand nitrogen, nitrogen is most effective in auste-nitization of both carbon and alloyed steels.

- Presence of nitrogen weakens the efficacy ofcarbon and chromium in austenite formation.

- Presence of carbon strengthens the efficacy ofchromium in austenite formation.This work was financed by the Polish Ministry

of Education and Science for scientific projectsunder contract No. 1147/T08/2005/29.

References[1]. Sartowska B., Piekoszewski J., Waliś L., Szymczyk W.,

Stanisławski J., Nowicki L., Ratajczak R., KopcewiczM., Kalinowska J., Barcz A., Prokert M.: Vacuum, 78,181-186 (2005).

[2]. Piekoszewski J., Sartowska B., Waliś L., Werner Z.,Kopcewicz M., Prokert F., Stanisławski J., KalinowskaJ., Szymczyk W.: Nukleonika 49, 2, 57-60 (2004).

[3]. Gavriljuk V.G., Berns H.: High nitrogen steels. Struc-ture, properties, manufacture, applications. Springer--Verlag, Berlin Heilderberg 1999, 376 p.

[4]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63,701-708 (2000).


contain any of austenite stabilizing element showsthe lowest (150oC) onset temperature of nitrogenexpanded austenite decomposition.

In conclusions: The surface nitrogen concen-tration in the top layer of modified carbon steelstarted its decreasing from 150oC due to releasingthe interstitial nitrogen atoms from fcc (face cen-tered cubic) nitrogen expanded austenite latticeand their diffusion into the surface and bulk of thesamples. The significant changes of the content ofidentified phases started at 150oC. The austenitiestransformed to the α-Fe phases. The nitrides areformed at the expense of nitrogen released fromthe fcc expanded austenite lattice. The modifica-tion effects in unalloyed steel 1C45 induced by theintense nitrogen plasma pulses are stable to thetemperature of about 150oC. This is the applica-tion limit, but below this temperature a materialcan be used without losing its required properties.

This work was financed by the Polish Ministryof Education and Science for scientific projectsunder contract No. 1147/T08/2005/29.

References[1]. Sartowska B., Piekoszewski J., Waliś L., Szymczyk W.,

Stanisławski J., Nowicki L., Ratajczak R., KopcewiczM., Kalinowska J., Barcz A., Prokert F.: Vacuum, 78,181-186 (2005).

[2]. Williamson D.L., Oztruk O., Glick S., Wei R., WilburP.J.: Nucl. Instrum. Meth. Phys. Res. B, 59/60, 737-741(1991).

[3]. Gavriljuk V.G., Berns H.: High nitrogen steels. Struc-ture, properties, manufacture, applications. Springer--Verlag, Berlin Heilderberg 1999, 376 p.

[4]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63,701-708 (2000).

[5]. Briglia Th., Terwagne G., Bodart F., QuaeyhaegenesC., D’Haen J., Stals L.M.: Surf. Coat. Technol., 80,105-108 (1999).

[6]. Jirásková Y., Blawert C., Schneeweiss O.: Phys. StatusSolidi A, 175, 537-548 (1999).

150oC and decreased for annealing at higher tem-peratures. The main reason for this fact could bereleasing of the interstitial nitrogen atoms fromthe nitrogen expanded austenite lattice at elevatedtemperature. It is likely that up to 150oC, nitrogendiffuses towards the surface. At a temperaturehigher than 150oC, the nitrogen atoms have higherenergy and can diffuse to the bulk of the sampleas well [5].

As a result of surface modification process, weobtained thin (about 1.5 μm) layers with the pres-ence of the identified phases α-Fe (ferrite and/ormartensite), γ0 (austenite in which iron atoms haveno nitrogen or carbon atoms in the nearest neigh-bourhood), expanded austenities γC, γN (austenitiesin which iron atoms have one or more carbon ornitrogen atoms in the nearest neighbourhood) andnitrides. CEMS results obtained for the heat-treatedsamples are presented in Fig.2. The phases trans-formation process started at annealing at 150oC.The content of all austenities (γ0, γC and γN) de-creases with temperature, while the contents ofα-Fe phases and nitrides increase. Decrease of theaustenitic phases content above 150oC has a rapid

character and these phases are no more presentabove 250oC. The content of α-Fe phases increasesby a factor of 2 at 300oC annealing. It is obviousthat this increase is of the expense of austeniticphases decomposition. For the same reason, weobserved also an increase of nitrides content by afactor of about 2. Released interstitial nitrogenatoms become available for the nitrogen phasesformation [5].

The presence and stability of nitrogen expandedaustenite determined in our experiments in steel1C45 are compared with the data reported in theliterature describing the alloyed steels: austeniticX6 (0.08% C, 17-19% Cr, 9-12% Ni) and ferriticX10 (0.12% C, 17-19% Cr) [6] (Fig.3). As it is seen,the γN phase is the most stable in X6 steel contain-ing both chromium and nickel alloying elements.It is less stable in chromium containing X10 steelwith the onset temperature of 250oC. As it couldhave been expected, our sample which does not

Fig.3. Changes of the nitrogen expanded austenite pres-ence in the modified surface layer of different kindsof steels as the result of annealing the samples.

Fig.2. Changes of the identified phases contents as the re-sult of annealing modified samples.


highest purity, strength, and resistance to solvents,acids, alkalies and heat. It is commonly used in thechemical, semiconductor, medical and defense in-dustries. A fine powder grade is also used as theprincipal ingredient of high-end paints for metals.PVDF is exhibiting efficient piezoelectric and pyro-electric properties. These characteristics make ituseful in sensor and battery applications [6,7].

The samples of PVDF membranes were irradi-ated with electron beam at the Institute of NuclearChemistry and Technology (INCT) using differentdoses. The mechanical properties: tensile strength

and elongation at break of the initial and irradiatedmaterials were tested using a universal testing ma-chine Instron 5565 (Instron Co., England) in theINCT. Membranes surface and fracture observationswere made using SEMs: JSM 840 (Jeol, Japan) andDSM 942 (Zeiss, Germany). The samples were fixedusing a conductive glue and then coated with a thinlayer of gold to reduce the charging which takes aplace during SEM observation.

Figure 1A presents the fractures of the investi-gated PVDF membrane produced using the methodwith liquid nitrogen. The deformation of polymericmaterial is clearly seen, so the observation of the

Specific template – track membranes can be usedto obtain the nano- and microstructures [1]. It is im-portant for these applications to know geometryparameters of the pores like sizes, shape and theirinner surface morphology [2]. A scanning electronmicroscopy technique (SEM) was used for the in-vestigations of surface and fracture of membrane.The proper preparation of samples for SEM ob-servations is very important in order to prevent de-struction the structure of the membrane during frac-ture preparation. The breaking membrane samplesat the liquid nitrogen temperature (77 K) did not

allow us to obtain undistorted cross-section. Theuse of other methods of sample preparation as elec-tron beam, gamma rays or UV irradiation allowsus to make them more brittle [3-5]. Preliminaryresults of investigations of polyvinylidene fluoride(PVDF) membranes after electron-beam irradia-tion are presented here.

Polyvinylidene fluoride is a highly non-reactiveand thermoplastic fluoropolymer. This is the rea-son to find new methods of destruction of this typeof polymer foils or membranes for the cleavageproduction for SEM fracture investigations. Its useis generally reserved for applications requiring the

ELECTRON-BEAM IRRADIATION OF PVDF MEMBRANESAS A METHOD FOR OBTAINING BRITTLE FRACTURES

FOR SEM OBSERVATIONSBożena Sartowska, Oleg Orelovitch1/, Andrzej Nowicki

1/ Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia

Fig.1. The fractures of PVDF membrane: A – initial, fractured in liquid nitrogen; B – irradiated with electron beam upto a dose of 603 kGy.

Fig.2. Results of mechanical strength measurements of PVDF membrane: A – initial, B – after electron-beam irradia-tion up to a dose of 603 kGy.

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shape and inner geometry of the channels is diffi-cult or even impossible. Figure 1B presents the frac-tures of a PVDF membrane subjected to the elec-tron-beam irradiation up to a dose of 603 kGy. Theplastically deformed parts of the material are notvisible. The shape and sizes of channels are clearlyseen, so the pores can be observed, measured andcharacterized.

Figure 2 presents the results of mechanicalstrength measurements. According to these dia-grams, we can determine the main parameters ofmaterial tensile properties: elongation at breake[%] and tensile stress [MPa]. The strength of themembrane decreases significantly after electron--beam irradiation. The elongation at breake (ten-sile strain) of irradiated membrane was only about1% at the 13 MPa of tensile stress, while for theinitial material these parameters were 25% at the35 MPa, respectively. This means that the investi-gated material became more brittle and the mem-brane breaks without distortion of its channel struc-ture and we obtain the cleavage without plasticdeformations.

In conclusion: using the irradiation with elec-tron beams, we can obtain a better SEM image ofpolymeric membrane fractures than obtained withliquid nitrogen.

References[1]. Sartowska B., Wawszczak D., Buczkowski M., Starosta

W.: Radiat. Meas., 40, 2-6, 790-793 (2005).[2]. Apel P.Yu.: Radiat. Meas., 34, 559-566 (2001).[3]. Orelovitch O.L., Apel P.Yu., Sartowska B.: Mater.

Chem. Phys., 81, 349-351 (2003).[4]. Orelovitch O.L., Apel P.Yu.: Microsc. Anal., 82, 11-13

(2003).[5]. Orelovitch O.L., Apel P.Yu., Sartowska B.: J. Microsc.,

224, 100-102 (2006).[6]. Zhang Q.M., Bharti V., Kavarnos G., Schwartz M.:

Poly(vinylidene fluoride) (PVDF) and its copolymers.In: Encyclopedia of smart materials. John Wiley & Sons,2002, pp. 807-825.

[7]. Vinogradov A., Schwartz M.: Piezoelectricity in poly-mers. In: Encyclopedia of smart materials. John Wiley& Sons, 2002, pp. 780-792.

Polypyrrole (PPy) belongs to conducting polymerswhich are the most stable in typical environmentalconditions and seems to be very interesting ma-terial for nanotechnology [1-4]. Presented resultsare a continuation of investigations carried out ear-lier. The first subject was connected with: deposi-tion of PPy nanotubules on track-etched membranes(TMs) and determination of the kinetics of theirwall thickness growth for time of deposition longerthan 7 min [4]. The second subject was connectedwith measurements of electrical parameters of PPynanotubules deposited into TMs [5].

In this work, the results are connected with: PPynanotubules formed in TM templates for timesof polymerization shorter than 5 min, determina-tion of permeability of deposited nanotubules andcovering of such structures with a thin copper layer.

The template-based synthesis of PPy was car-ried out into pores of TMs made of 10 μm thick

poly(ethylene terephthalate) (PET) films [4]. In or-der to prepare samples for measurements, proper

SELECTED PROPERTIES OF POLYPYRROLE NANOSTRUCTURESDEPOSITED IN TRACK-ETCHED MEMBRANE TEMPLATESMarek Buczkowski, Wojciech Starosta, Bożena Sartowska, Danuta Wawszczak

Fig.1. A scheme of the mould for PPy nanotubules deposi-tion in TMs membranes.

B

A

Fig.2. Nanotubules formed in pores of TM membrane (0.2μm pore size) after 2 min (A) and 3 min (B) of poly-merization process.


solutions were introduced to both sides of a mem-brane disc (for certain period of time) that hadbeen mounted in a plexiglas mould (Fig.1). As a

result of such procedure, discs 20 mm in diametercovered with PPy have been obtained (outer di-ameter of samples was 30 mm).

Scanning electron microscopy (SEM) measure-ments by using a Zeiss-Leo DS942 microscope

allowed to determine nanotubules wall thicknessand thickness of the PPy layer on membrane sur-faces. Selected SEM photographs (Fig.2) showfractures of the samples in liquid nitrogen in caseof time of polymerization, respectively 2 and 3 min.Dependence of nanotubule wall thickness vs. timeof polymerization is shown in Fig.3 (for times equalto or longer than 7 min; results are taken from pre-vious work). It is seen that the first stage of thespeed of nanotubules formation is higher than inthe next stage. This speed is equal to 20.3 nm/minand is 1.7 times higher than in the next stage. Thick-ness of PPy layers on the template surfaces for dif-ferent times of polymerization is given in Table 1.

The value of permeability is an important par-ameter in some applications, for instance, in micro-filtration devices. Permeability for samples with

different wall thickness of nanotubules in TMs withpore diameters 0.2 and 1.3 μm was determined at

Table 2. Permeability of nanotubules deposited on pores of TMs 0.2 μm at an air pressure of 0.5 bar.

Table 3. Permeability of nanotubules deposited on pores of TMs 1.3 μm at an air pressure of 0.5 bar.

Table 1. Dependence of PPy layer thickness on TM vs. timeof polymerization for both sides of a membranesample (pore size – 1.3 μm).

Fig.4. The copper layer sputtered on the membrane surface by using a glow vacuum discharge: (A) membrane pore size– 0.2 μm, (B) membrane pore size – 1.3 μm.

Fig.3. Kinetic curve of PPy nanotubules growth into poresof the TM (initial pore size – 1.3 μm).

A B


an air pressure of 0.5 bar. For TMs with a pore sizeof 0.2 μm, the initial permeability was equal to 0.70l/(min·cm2). Values of the permeability for differ-ent wall thickness of PPy nanotubules depositedin such pores are given in Table 2. It was calculatedthat by decreasing the internal pore diameter 6.3times (from 200 to 32 nm), the permeability de-creased 2.9 times.

For TMs with a pore size of 1.3 μm, the initialpermeability was equal to 14.8 l/(min· cm2). For dif-ferent wall thickness of PPy nanotubules depositedin pores, the permeability is given in Table 3. Inthis case, decreasing of the internal pore diameter6.6 times (from 1300 to 198 nm) caused decreas-ing of the permeability 10.4 times.

Attempts were taken up concerning the cover-ing of samples with deposited PPy nanotubules bythin metallic layer. This is important matter be-cause samples with deposited PPy can be appliedas sensors and in such case it is necessary to intro-duce electrical connection with an outer circuit.Introductory experiments were carried out withglowing sputtering of copper (in the “Surftec” s.c.,Warszawa). SEM photographs (Fig.4) show thesputtered copper layer in case of two types of samples

with PPy nanotubules: TM membrane with pores0.2 μm (Fig.4A) and 1.3 μm (Fig.4B). The thick-ness of copper layers was similar in both cases: 0.7and 1.2 μm, respectively, but the structure of theselayers was different. In case of smaller size of thepores in template, the surface of the copper layerwas smoother.

The authors would like to thank Mr Adam Le-ciejewicz – head of the “Surftec” s.c. for the coppersputtering of membrane samples by using glowvacuum discharge.

References[1]. Nakata M., Kise H.: Polym. J., 25, 91 (1993).[2]. Kohli P., Martin C.R.: Curr. Pharm. Biotechnol., 15,

441-450 (2004).[3]. Zhitariuk N.J. et al.: Nucl. Instrum. Meth. Phys. Res.

B, 105, 204-7 (1995).[4]. Starosta W., Buczkowski M., Sartowska B., Wawszczak

D.: Nukleonika, 51, Suppl. 1, S35-S39 (2006).[5]. Buczkowski M., Wawszczak D., Starosta W.: Electrical

parameters of polypyrrole nanotubules deposited insidetrack-etched membrane templates. In: INCT AnnualReport 2004. Institute of Nuclear Chemistry and Tech-nology, Warszawa 2005, pp. 93-94.

SOL-GEL-DERIVED HYDROXYAPATITE AND ITS APPLICATIONTO SORPTION OF HEAVY METALS

Andrzej Deptuła, Jadwiga Chwastowska, Wiesława Łada, Tadeusz Olczak,Danuta Wawszczak, Elżbieta Sterlińska, Bożena Sartowska, Marcin Brykała,

Kenneth C. Goretta1/

1/ Argonne National Laboratory, USA

Hydroxyapatite (HA, Ca10(PO4)6(OH)2) is the ma-jor inorganic constituent of biological hard tissuessuch as bones and teeth. Owing to its structure andchemical composition this material also shows ahigh capacity for ion exchange. The properties ofsynthetic hydroxyapatites depend greatly on themethod of their preparation. In most publishedwork, hydroxyapatites obtained by precipitationmethods have been studied. These hydroxyapatiteshave been examined as new inorganic cation ex-changers [1-6] and anion exchangers [7,8]. Teamsfrom Argonne National Laboratory have studiedengineering aspects of HA and use of variousphosphates for containment of radioactive waste[9-11].

The principal goal of this work was a study ofadsorption of heavy metal ions on HA microspheresand monolithic ceramics to address the possibilityof application to separation of various metal ionsfrom water and liquid wastes. Hydroxyapatite in theform of microspheres was prepared by a proprietarysol-gel method [12,13]. For fabrication of HA mono-liths, we applied a second proprietary method. Thesynthesis processes consisted of preparation of solswith the use of a very strong complexing agent –ascorbic acid (ASC) [14,15].Synthesis

Starting sols were prepared by ultrasonic mix-ing of concentrated solutions of calcium acetate

(1.7 M) with 85% H3PO4, followed by emulsifica-tion in dehydrated 2-ethyl-1-hexanol. Drops ofemulsion were gelled by extraction of water withthis solvent. Details of the laboratory equipment(50 g/h) and microspheres formation have beendescribed [12,16,17]. For synthesis of the powderfor the monoliths, we modified the sol-gel processdescribed in [15], using inexpensive CaO and H3PO4as starting ingredients. In brief, 28.054 g of CaOwas dissolved in 150 mL of deionized water and44 g of ASC was dissolved in 500 mL of deionizedwater. The solutions were blended with 20 mL ofconcentrated H3PO4 and 150 mL of deionizedwater. The pH was adjusted to 7 by addition ofNH4OH. Evaporation was followed by drying atroom temperature (RT) and final heating of mono-liths in air for 2 h soak at 900oC. The sedimenta-tion rate of the spherical powders of HA was ap-proximately 20 times greater than for irregularlyshaped powders of similar size distribution. Theresulting spherical powders and monoliths areshown in Fig.1.

On the basis of published information [16], weestimate the cost of producing HA microspheresby our method for a projected scale of 1 kg h–1 tobe approximately 170 USD/kg. This price is com-parable to those for irregularly shaped commer-cial HA powders (Sigma Chemical Company (art.C 4507) = 180 USD/kg; Merck (index 11.1701) =


150 USD/kg). Merck also offers microspheres (di-ameter 75-100 μm) at approximately 1700 USD/kg.

For column-based sorption experiments, powderfractions of approximately 200 mesh were separatedby sedimentation. The concentrations of stock sol-utions of metals were 1 mg cm–1. The solutions wereprepared by dissolving metallic compounds in 1 MHCl. A test water solution of the following com-position [mg dm–3] was used: Na+ – 15; K+ – 4; Mg2+

– 20; Ca2+ – 55; Cl– – 125; SO42– – 80; Zn2+ – 0.2;

Cd2+, Pb2+, Ni2+, Co2+, Cu2+, and Mn2+ – 0.1.Solubility of hydroxyapatite

Solubility was estimated under conditions simi-lar to those of metal sorption: 0.2 g of HA wasshaken with 20 mL of solution of suitable pH for30 min at 20oC. The solution was then filtered off.Ca was measured by atomic absorption spectro-metry (AAS) and P by spectrophotometry, asphosphoromolybdate with reduction to blue. Mea-surements of the Ca and P eluted by solutions ofpH within the range of 0-9 revealed that the solu-bility of HA increased with decreasing pH (Fig.2).The amount of Ca eluted by 1 M HCl from 1 g ofHA was ca. 0.5 mg Ca, which corresponds to 12mmole per one mole HA. The solubility decreasedwith increasing pH, e.g. from 2.7 to 0.8 mmole Caper one mole HA for pH=5-9. The concentrationof P in the solutions was much lower than that ofCa: the P eluted by 1 M HCl was equal to ca. 0.067mg g–1 HA (2.2 mmole per mole).

It may be concluded that a greater number ofCa cations than P anions release into solution whenpH decreases, which results in a decrease in theCa/P mole ratio in the solid phase. These resultscorrespond with measurements of the solubility ofHA reported elsewhere [5,18].Batch sorption experiments

The influence of pH on the sorption of the se-lected elements, and the sorption kinetics for Cu(II)and Ni(II), were studied by the batch method. Asolution for each element, containing 100 μg of theelement, was adjusted to a suitable pH by additionof HCl or NaOH and transferred into a 50 cm3

separatory funnel. The final volume of the solutionwas 20 cm3. Then 0.5 g of the HA was added andmechanically shaken for 30 min. The solution wasfiltered then and the sorbent was washed twice with2 cm3 portions of a solution of the same pH. Thewashings were combined with the filtrate. The con-centration of each element studied was determinedby AAS with flame atomization or by spectrophoto-metry. The amount of the element retained on thesorbent was calculated from the difference betweenthe amounts in the original solution and in the fil-trate.

For kinetic studies, similar experiments wereperformed for two elements – Cu(II) and Ni(II) –at a suitable pH and a shaking time within a 5-30min interval. The retention capacities for Cu(II)and Pb(II) were also determined by the batchmethod. Detailed conditions of these experimentsare shown in Table; amount of sorbent – 0.5 g,

------3cm ------

Fig.2. Solubility (as concentration, c) of HA at various pHlevels.

Fig.1. Sol-gel-derived HA produced in the forms of microspheres (A) and fired monolith (B).

Table. Estimations of retention capacity of elements onHA.

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then washed with 10 cm3 of solution of the samepH. The washings were combined with the efflu-ent. The element studied was determined in thecombined solution.

The test water samples, 100 or 200 cm3 each,were adjusted to pH=5. The solution was thenpassed at the flow rate of 0.5 cm3 min–1 throughthe column filled with 1.0 g of HA (previouslywashed with water, pH=5). The efficiency of sorp-

volume of liquid phase – 20 cm3, original concen-tration of metal – 0.5 mg cm–3.Column sorption experiments

A glass column, 4 mm inner diameter, was filledwith 0.5 or 1 g HA and conditioned with a solutionof a suitable pH. A sample containing 100 μg ofthe element studied, adjusted to a suitable acidity,was passed through the column under pressure ata flow rate of 0.3-2.2 cm3 min–1. The column was

Fig.3. Retention of elements in solutions of various pH (pH measured before sorption); monolithic HA was used in onlythree sets of experiments (top three plots).


tion was checked by determining the metal con-centration in the elutant, with the use of the AASmethod with flame atomization.

The kinetic sorption was rapid: equilibrium wasattained within a few minutes. The effect of shak-ing time was established for Cu(II) and Ni(II).Obtained data indicated that the equilibrium ofsorption process is attained in 5 min. This rapidequilibration is in contrast to the previously reportedwork with HA, for which the times for attainingthe equilibrium were much longer (1-48 h) [4,5] andeven 20 days [3].

The main results of our experiments are shownin Fig.3, as the dependence of sorption upon thepH of the original solution. The pH of the solutionafter sorption increased, probably owing to a par-tial dissolution of HA. The retention of most ele-ments studied was approximately 94-100%, in themost suitable acidity ranges. Only the MnO4

– ionsexhibited low retention; the maximum was 47% ina 1 M H2SO4 solution. The sorption of Cr(VI),which was present in solution as anions, and thatof Sb(V), As(V), and Mo(VI), which have ampho-teric character with a predominance of acidic prop-erties, probably followed anion exchange betweenthe hydroxyl ions of the lattice and the metal an-ions in the solution.

The optimum conditions for the column pro-cess were established for Cu(II). The influencesof flow rate and sample volume on the sorptionefficiency were determined. The process of sorp-tion was carried out under pressure in the glasscolumn filled with 0.5-1 g of HA. It was found thatflow rates to 2.5 mL min–1 and sample volumes to200 mL did not deteriorate the efficiency of Cusorption.

The sorption responses of the group of diva-lent metal ions (Cu, Cd, Pb, Ni, Co, and Mn) fromthe artificially prepared test water were also studiedby a dynamic method. Under the conditions estab-lished (pH – 5, flow rate – 0.5 cm3 min–1, samplevolume – 100 cm3, 1 g of HA), all of the metalsstudied were quantitatively adsorbed.Retention capacity of hydroxyapatite

The conditions and the results of determina-tion of the retention capacity for Cu(II), Pb(II),and U(VI) are show in Table. It can be concludedthat the capacities of HA materials that werestudied were rather low, equal to 3 mg of Cu2+, 10mg of Pb2+, and 12 mg of U(VI) per 1 g of HA.The retention capacity of the monolithic HA wassignificantly higher: for U(VI) it was approximatelythree times higher than the values that were ob-tained for spherical HA.Discussion – mechanism of sorption

The sorption of metal cations can be achievedmainly in two ways: ion exchange and ion adsorp-tion. The ion exchange mechanism is generallybelieved to take place in the case of sorption ofheavy metals on HAs [2,3,5]. Moreover, Xu et al.[19] proposed that the most important sorptionmechanism may be surface complexation and co-precipitation, possibly accompanied by ion exchangeand solid-state diffusion. Furthermore, in the workby Reichert and Binner [4], ion adsorption was pro-

posed as a mechanism for ion removal; ion exchangewas not observed, but it could not be completelyruled out.

The amount of Ca2+ released during the sorp-tion can be used as an indicator of either ion ex-change or ion adsorption. If ion exchange takesplace, the molar ratio between the divalent metalcation retained in the solid phase and Ca releasedinto the solution must be close to one. If this ratiois less than one, then some adsorption must havetaken place.

In the present work, for both Ca/Cu and Ca/Ni,the molar ratio was equal to 0.3. These results sug-gest that for the HA materials studied the predomi-nant process in the sorption of metal cations wassurface adsorption, possibly accompanied by ionexchange.

Synthetic HA synthesized by sol-gel methodsand produced in the form of microspheres or ir-regularly shaped powders that were processed intomonoliths offered the possibility for separation ofvarious metal cations and anions. In contrast to HAspreviously reported upon, the sorption kinetics wasfast; equilibrium of sorption was attained within afew minutes.

The cost to produce these materials in irregu-larly shaped powders (monoliths) was estimated tobe more than 10 times lower than spherical powdersand HA powders now offered commercially.

The mechanism of cation sorption on the HAwas determined to be primarily ion adsorption,possibly accompanied by ion exchange. The HAstudied is a suitable material for the separation ofthe group of metals studied from natural waters.However, retention capacity was not high (3 mgof Cu and 10 mg of Pb per 1 g of HA), which wouldbe a disadvantage for possible applications of theHA as, for example, a filter material to sewage treat-ment. The retention capacity for U(VI) of mono-lithic HA was much better for spherical HA, ap-proximately 3 times higher. We recommend thatthe monolithic form HA should be examined forimmobilization of U from nuclear wastes.

References

[1]. Suzuki T., Hatsushika T., Hayakawa Y.: J. Chem.Soc., Faraday Trans., 77, 1059 (1981).

[2]. Suzuki T., Hatsushika T., Miyake M.: J. Chem. Soc.,Faraday Trans., 78, 3605 (1982).

[3]. Suzuki T., Ishigaki K., Miyake M.: J. Chem. Soc.,Faraday Trans., 80, 3157 (1984).

[4]. Reichert J., Binner J.G.P.: J. Mater. Sci., 31, 1231(1996).

[5]. Jeanjean J., Fedoroff M., Faverjon F., Vincent U.,Corset J.: J. Mater. Sci., 31, 6156 (1996).

[6]. Jeanjean J., Vincent U., Fedoroff M.: J. Solid StateChem., 108, 68 (1994).

[7]. Wright G.: Ann. Chim. Fr., 5, 39 (1970).[8]. Young R.A.: In: Proceedings of the 2nd International

Congress on Phosphorus Compounds (IMPHOS).Paris 1980, p. 73.

[9]. Singh D.,. Wagh A.S, Cunnane J., Mayberry J.: J.Environ. Sci. Health A, 32, 527 (1997).

[10]. Singh D., de la Cinta Lorenzo-Martin M., RoutbortJ.L, Gutiérrez-Mora F., Case E.D.: Int. J. Appl.Ceram. Technol., 2, 247 (2005).


preparing of high temperature superconductors. PolishPatent No. 172618 (1997).

[16]. Deptuła A, Łada W., Olczak T., Sartowska B.,LeGeros R.Z., LeGeros J.P.: Complex sol-gel process(CSGP) preparation of calcium phosphate bioma-terials (powders, monoliths, fibres). In: Bioceramics11. Eds. R.Z. LeGeros, J.P. LeGeros. World Scientific,Singapore 1998, p. 743.

[17]. Deptula A., Chmielewski A.G.,. Wood T.E.: Sol-gelceramic beads and bubbles – a historical perspective,modern fabrication and cost analysis. In: 9th CIMTECProceedings. Part D. Ed. P. Vincenzini. Techna, Faenza1999, p. 771.

[18]. Verbeek R.M.H., Steyaer H., Thun H.P., Verbeek F.:J. Chem. Soc., Faraday Trans., 76, 209 (1980).

[19]. Xu Y., Schwartz F., Traina S.J.: Environ. Sci. Technol.,28, 1472 (1994).

[11]. Goretta K.C., Singh D., Tlustochowicz M., CuberM.M., Burdt M.L., Jeong S.Y., Smith T.L.,. Wagh A.S.,Routbort J.L.: Mater. Res. Soc. Symp. Proc., 556, 1253(1999).

[12]. Deptuła A., Łada W., Olczak T., Borello A., AlvaniC., Di Bartolomeo A.: J. Non-Cryst. Solids, 147&148,537 (1992).

[13]. Alvani C., Borello A., Deptula A., Lorenzini L., Orru’L.: Method for preparing of irregularly shaped andspherical powders of calcium phosphates, especiallyCa-hydroxyapatite. Italian Patent 01245400 (1994).

[14]. Deptuła A, Łada W., Olczak T., LeGeros R.Z.,LeGeros J.P.: Method for preparing of calcium phos-phates layers, especially hydroxyapatites. Polish PatentNo. 180602 (2000).

[15]. Deptuła A., Łada W., Olczak T., Lanagan M.T.,Dorris S.E., Goretta K.C., Poeppel R.B.: Method for

Nanocrystalline materials can offer several alter-natives to the classic bulk laser crystals. Sol-gelmethods are used for producing homogeneoussamples at low temperatures.The mechanism of selfignition

Sol-gel methods are used for producing homo-geneous samples at low temperatures. Novel syn-thesis of carbon-free nanocomposites of KYW andKYW:Yb (1 mol%) was elaborated by introduc-ing a selfignition (SI) step. The SI mechanism isvery complex and strongly related to the drying andheating conditions. Obviously the SI step can beeasily obtained without a drying step. However, acontrolled drying step is necessary in order to avoidthe foaming effect which causes a 10-20 fold in-

crease of the powder volume. This effect can besuppressed if the drying time is increased and the

drying takes place under vacuum conditions. Thedrawback of the prolonged drying time is relatedto the risk that the SI process might disappear. Ascan be seen in the upper part of Fig.1, sampleB6Pw-1 extracted from the running furnace at230oC is black in colour. Further heating to 300oCproduced a white powder with only small gray in-clusions, indicating that SI has occurred. After afinal treatment at 550oC, sample B6Pw-2 is snow--white. In contrast, sample B6Pw-4 heated slowly(lower part of Fig.1) does not exhibit SI and, underthe same firing conditions, became deep gray in-dicating high carbon content.

Final thermal treatment parameters have beenselected on the basis of differential thermal analy-

PHYSICAL AND CHEMICAL PROPERTIES OF YTTERBIUMDOPED KY(WO4)2 NANOCRYSTALS

Andrzej Deptuła, Mieczysław T. Borowiec1/, Vladimir P. Dyakonov1/, Wiesława Łada,Tadeusz Olczak, Danuta Wawszczak, Pavlo Aleshkevych1/, Wiktor Domuchowski1/,

Tetyana Zayarnyuk1/, Marek Barański1/, Henryk Szymczak1/, Marcin Brykała1/ Institute of Physics, Polish Academy of Sciences, Warszawa, Poland

Fig.1. Samples of KY(WO4)2 gels is various stages of thethermal treatment.

Fig.2. The representative TG (thermogravimetry) and DTAtraces of the gel samples B27 (650oC, 5 h, 2oC/min,SI) and KY(WO4)2+Yb3+, 650oC, 5 h, 2oC/min, SI).


sis – DTA (Fig.2). As can be seen (line a) at 230oC,the samples extracted from the running furnaceare black. But farther heating results in selfignition.The sample taken out immediately after SI is white,only with small gray inclusions. However, afterfinal treatment the sample is snow-white. In con-trast, a sample heated slowly (line b) does not ex-hibit SI and, after the same firing conditions isdeeply gray, indicating a high carbon content.XRD and ESR investigations of nanocrystals

The expected monoclinic phase C2/c of theKYW nanocomposites was confirmed using X-ray

diffraction (XRD) technique (Fig.3). Unit cellparameters and size of grain L for various samples

are presented in Table. The electron spin resonance(ESR) spectrum of the B6Pw-2 sample shows no

resonance lines, meaning the absence of paramag-netic centra in this sample (very high “spectral”purity). On the other hand, the spectrum of theB8Yb sample exposes wide resonance absorption.This absorption is a result of the superposition ofthe single resonance lines of the Yb ions averagingon angles (Fig.4).IR spectra of KY(WO4)2 nanocomposites

The infrared (IR) spectra of the synthesizedsamples were obtained from a KBr pellet using a

BRUKER-EQUINOX 55 spectrometer. For semi--quantitative evaluation of the carbonate contentin the synthesized materials it was necessary to useadmixtures of Na2CO3 powder.

In the gels dried at 230oC (B6Pw-1 and B6Pw-3),only a very weak and broad -Me-(=)O band wasobserved in the range 600-1000 cm–1. A very strongband near 1400 cm–1 (assigned to σOH) indicates thepresence of (Me)-OH groups. These, together withmolecular H2O bonds (σ, 1600 cm–1; ν, 2900-3600cm–1) form a gel network (hydrogen bonds and -O-bridging bonds). Nitrate and carbonate bands werenot observed. The absence of bands characteristicof organic substances (e.g. C-H bands at 2800-3000cm–1 related to ascorbic acid, ASC, and productsof its decomposition), indicated that the ASC de-composition at this temperature is complete. Thisis a very important result if compared to other sys-tems (e.g. LiNixCo1-xO2), where carbonates remainedafter ASC decomposition and strongly hydratedthe final compounds. The lack of organic compounds(no –C-H bands) in the KYW and KYW:Ybsamples clearly indicates that the morphology ofthe dried gels is responsible for the occurrence of

Fig.3. X-ray spectrum for samples B27.

Fig.4. The EPR spectra for samples B6Pw-2 (KY(WO4)2,SI – 550oC, 10 h) and B8Yb (KY(WO4)2+1%molYb, SI – 550oC, 10 h).

Table. Lattice parameters of decarbonized nanocomposites.

Fig.5. The IR spectra of B6Pw-2 sample (KY(WO4)2, SI –550oC, 10 h).


The processes of gel drying produce xero- or aero--gels, depending on the method used. The methodof xero-gel production is lyophilization or frozen--drying, i.e. evaporation of the solvent at low press-ure, from the frozen gelator skeleton. If there is nocollapse, the gelator structure, with an enormoussurface area and a very small pore size, is main-tained. But such drying process is accompaniedwith unhindered shrinkage that can lead to struc-tural collapse of the gelator network structure, re-sulting in formation great, compact, surface-typeclusters. The aero-gel is produced by careful dryinga wet gel in various environments, often in super--critical conditions, and/or with solvent exchange.The gel does not shrink, so the fragile gelator net-

work does not collapse and the aero-gel is highlyporous. Both processes can be complex and many--staged [1].

The weak, physical gels, as it is known, can dis-integrate upon touching. So, the process of dryingcan be expected as having a more essential influ-ence on their structure.

The main goal of this work was to check, usingthe small angle X-ray scattering (SAXS) method,the influence of drying on monosaccharide gelstructure and to consider the rightness of applica-tion of microscopic results to the description ofwet monosaccharide gels structure.

The gel, formed from a methyl-4,6-O-benzy-lidene-α-D-glucopyranoside gelator with diphenyl

SAXS STUDY OF XERO- AND AERO-GELSFORMED FROM MONOSACCHARIDE GELATORS

Helena Grigoriew, Dagmara K. Chmielewska

tals. The IR spectra of synthesized samples wereobtained.

This work was supported by the Eueopean Union(project DT-CRYS, NMP3-CT-2003-505580) andthe Polish State Committee of Scientific Research(KBN) (decision of project No. 72/E-67/SPB/6PR/DIE 430/2004-2006).

the SI process. From the IR spectra (Fig.5), itseems that high-purity double tungstate structurescan be easily obtained by introducing an SI step.The best example is sample B6Pw-2.

The good quality nanocomposites of KY(WO4)2and KY(WO4)2+1%mol Yb have been synthesized.Electron spin resonance studies in the X band havebeen performed on KYW and KYW:Yb nanocrys-

Fig.1. Fractal curves for weaker apolar gels: A – wet, B – xero, C – aero. The straight-line parts of the curves are markedby lines with their slopes.


ether as a solvent, was prepared [2]. The gelator isan example of one of the smallest monosaccharidemolecule, which is apolar as well as the solvent is.So, very weak mutual interactions in the gel struc-ture can be expected. The next gel was built of me-thyl-4,6-O-(p-nitrobenzelidene)-α-D-glucopyrano-side gelator with water as a solvent. Both materialsare polar and the gelator molecule size is not verysmall among monosaccharides. This gel structureis expected to be stronger than the first one. Bothgelators were prepared by us according to [2,3]. Thegels were prepared in the same way, as used in ourearlier works [4,5]: a mixture composed of a gelatorand a solvent was heated in a closed, capped tubeuntil the gelator dissolved. The gelator concen-tration was in the range 1-1.5% [g/mL]. Aero-gelswere produced by leaving the obtained gels in openvessels till they become dry. Xero-gels were pro-duced by frozen-drying of the gels in a Labconcolyph.lock 1l apparatus at about -50oC and 10 mmHg.

The wet gel samples for SAXS measurementswere prepared by putting them in thin-walled cap-illaries ( Hilgenberg, 2 mm diameter, 0.01 mm wallthickness), then sealed.

The measurements were carried out at theULTRA-SAXS BW-4 wiggler beamline, Hasy-lab-DESY synchrotron, BW4 beamline. The col-lected ultra small angle X-ray scattering (USAXS)measurements were subjected to pie integration,

and, after normalization, to subtraction of thebackground which was the USAXS signal due tothe solvent in the capillary. To obtain a wide rangeof scattering angles (USAXS-SAXS), each samplewas measured at two different sample-detector dis-tances (4 and 12 m), and both measurements werejoined, using OTOKO program, to get one curveover the whole range.

For weak glucose gel, G, the first slope of log-logcurve (Fig.1A), of dm=1.6 is generated by loose,mass fractal built according to DLCA (diffractionlimited cluster aggregation) mechanism. The sur-face fractal slope of ds=2.9, (ds=6 – slope) meansvery uneven and developed surface. From thefractal curve, also two sizes, typical of fractal struc-ture can be evaluated: at Guinier crossover – radiusof gyration of fractal aggregate, Rg=109 nm andat Porod crossover – size of primary particle, a=10nm.

The essential change of fractal curve for xero--gel (Fig.1B) seems to be caused by drying-inducedstress that results in collapse and formation oflarge-scale morphological features. Their size is toolarge to be visible by X-rays, and small-s scatter-ing is related to surface fractal with dimension ds≈2,characteristic of smooth, sharp interface. After thissurface fractal range, for bigger angles, the cross-over is showed, at 17 nm, and then mass fractalrange, of dm=2.45. The same run of aero-gel fractalcurve (Fig.1C) is observed, also with crossover at

Fig.2. Fractal curves for stronger polar gels: A – wet, B – xero, C – aero. The straight-line parts of the curves are markedby lines with their slopes.


17 nm. Only the followed mass range slope issmaller and is equal to dm=1.8, i.e. there is moreloose structure.

So, in our case, the collapse takes place not onlyat the xero-gel formation, where it is due to a strongshrinkage during emptying fractal structure frommaintaining it solvent molecules, but also at aero--gel formation, where the evaporated solvent mol-ecules are replaced by their vapor and finally byair, so stresses should be much smaller. These ob-servation confirmed a big weakness of monosac-charide gel structure.

Whereas, for a stronger para-glucose gel withwater, P, the fractal curve (Fig.2A) begins, the partgenerated by mass fractal of dm=2.9 is much denserthan for G gel, built according to another, RLCA(reaction limited cluster aggregation) mechanism.The Porod bend at 160 nm and then surface fractalof ds=2.05 means that the primary particle is muchgreater, than for G gel, and of smooth surface. Thiscan be expected, because the polarity of both gelconstituents can activate enthalpic forces that favora large scale phase separation [1].

The log-log curve of related P xero-gel (Fig.2B)is close to the curve, obtained for G xero-gel withlong, straight-line segment of surface fractal withclose interface. This run of the curve suggest a simi-lar collapse as caused by G-xero-gel formation.

But for the P aero-gel there is no similarity withthe G aero-gel structure. No collapse is observed.

Visible three ranges of the fractal curve (Fig.2C)are related to a small primary particle, smaller thanin the wet P gel (a=63 nm in comparison witha=160 nm), of very uneven surface (in compari-son with very smooth one). The particles formloose fractal generated by DLCA mechanism, andnot dense by RLCA mechanism. Such structure isnot a modification of the previous wet gel struc-ture and must be formed during drying from thebeginning. This behavior could be explained by theOstwald ripening [1] including dissolutions andprecipitations, and the resulting structure is formedby these competing interactions.

All dried gels, xero-gels and aero-gels, obtainedby us from the monosaccharide gels, are of essen-tially changeable structures in comparison with therelated wet gels.

References[1]. Brinker C.J., Scherer G.W.: Sol-gel science: The

physics and chemistry of sol-gel processing. AcademicPress, Boston 1990.

[2]. Sakurai K., Jeong Y., Koumoto K., Friggeri A.,Okamoto S., Inoue K., Shinkai S.: Langmuir, 19, 8211(2003).

[3]. Gronwald O., Sakurai K., Luboradzki R., Kimura T.,Shinkai S.: Carboch. Res., 331, 307 (2001).

[4]. Grigoriew H., Luboradzki R., Cunis S.: Langmuir, 20,7374 (2004).

[5]. Grigoriew H., Luboradzki R., Gronkowski J.: J. Non--Cryst. Solids, 352, 3052 (2006).

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS156

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS

Quite often there exists a need for measurementof radon 222Rn and thoron 220Rn concentration in air.Such continuous measurements can be done withtwo scintillation cells (Lucas cells) [1] connectedin series and air flow forced through the cells. Be-tween the first and the second cell a delay of airflow is so placed that thoron with its 55 s half-lifedisintegrates. The first cell detects radon and thoron,the second radon only. From these two readings,concentration of radon and thoron can be deter-mined. Another method of measurement of radonand thoron is spectrometry of alpha radiation ofdecay products [2]. The alpha radiation of 218Po(6.0 MeV) is used for measurement of 222Rn, and216Po (6.78 MeV) alpha radiation for measurementof 220Rn.

The aim of the presented investigations was thedevelopment of a gauge model for measurementof radon and thoron with a single Lucas cell. Agauge for measurement of radon concentration inair, MR-1, employing the Lucas cell as alpha ra-diation detector was developed earlier. Additionalfunction for measuring thoron concentration in airshould widen its applications.

Thoron laden and radon laden air are forcedto flow at a rate of 1 dm3/min through the Lucascell for a period of 10 min, simultaneously countrate from the Lucas cell is measured. After 10 min,

the air flow is switched off. Count rate is measuredat two time intervals from 1 to 10 min and from 20to 30 min. The time intervals are a compromisebetween the length of measuring cycle and therandom errors that are made smaller with increas-ing counting time. The relation between the count

MEASUREMENT OF 222Rn AND 220RnWITH SINGLE SCINTILLATION CELLBronisław Machaj, Piotr Urbański, Jakub Bartak

Fig.1. Simulated alpha activity deposited on the walls ofLucas cell when 1 dis/min of radon is flowing throughthe cell during 10 min. The curve in the period 1-10min is disturbed due to air flow (lower deposition of218Po inside the cell). Decay series of 222Rn →218Po→214Pb→214Bi (214Po) was simulated. Alpha activity of222Rn+218Po+214Po against time is shown in this Fig.

Fig.2. Simulated alpha activity deposited on the walls ofLucas cell when 1 dis/min of 220Rn is flowing throughthe cell during 10 min. Decay series of 220Rn→216Po→212Pb→212Bi was simulated. Alpha activity of220Rn+216Po+212Bi(212Po) against time is shown inthis Fig.

Fig.3. Measured count rate against time (broken line)and simulated count rate corresponding to real(reference) radon concentration – 53.09 dis/min(continuous line). n1=sum(r(1:10))=683 counts,n2=sum(r(20:20))=1287 counts, from y=m\n:222Rn=56.0 dis/min, 220Rn=-1.85 dis/min.


numbers n1 and n2 at the two time intervals andthe alpha activity deposited inside on the walls ofthe cell are given by:

n1=(m11·A+m12·B)·ε (1)n2=(m21·A+m22·B)·εwhere: A – radon alpha activity, B – thoron alphaactivity, ε – deposition and detection efficiency.The coefficients m11...m22 are determined from thesimulated activity of alpha radiation [3-5] (Figs.1and 2). The coefficients m11, m12 are equal to thetotal (sum) alpha activity at 1-10 min interval fromradon and thoron, respectively, and m21, m22 to thetotal alpha activity at an interval of 20-30 min fromradon and thoron. After computation of the coef-ficients, the m matrix of coefficients is equal to:m = |12.80 18.25|

|22.98 0.0218|and equation (1) can be rewritten as:

n1 = (12.80·A + 18.25·B)·ε (2)n2 = (22.98·A + 0.0218·B)·εConcentration of radon A and thoron B computedfrom equations (2) is given by matlab function:

y = m·ε\n = |A| [dis/min] (3)|B|

where n = |n1||n2|

Employing Cramer rules, concentration of radonand thoron can be given in a more convenient formfor microprocessor processing:

A = (-0.000049·n1 + 0.0435·n2)/ε [dis/min] (4) B = (0.0548·n1 – 0.0305·n2)/e

Random error due to fluctuations of count numbercalculated from the relation for propagation oferrors:

2 2 2 2 21 2

1 2

y ys (y) ( ) s (n ) ( ) s (n )n n∂ ∂

= +∂ ∂ (5)

Table. Results of radon and thoron measurement.

Fig.5. Measured count rate against time (broken line) andsimulated alpha count rate corresponding to refer-ence thoron concentration – 1323 dis/min (continu-ous line). n1=25635 counts, n2=48.6 counts; fromy=m\n: 222Rn=0.8 dis/min, 220Rn=1404 dis/min.

Fig.4. Measuring arrangement for thoron: AP – air pump1 dm3/min, TS – thoron source, AF – air filter, LC –Lucas cell, MR-1 – radon radiometer, pgc – blackrubber pipe.

The mean ratio of columns 4/6, for measurements mr62...mr65, is 1.003, which means that the computed concentrationy=m\n of radon is correct. The ratio of columns 5/7, for measured mr53, mr147, mr150 is 1.04, which means that thecomputed concentration y=m\n of thoron is too high by 4%. This error can be corrected by dividing the thoron concen-tration from y=m\n by 1.04.Negative values of “cross talk” from radon concentration into thoron concentration for measurements of mr62...mr65can be neglected (no negative concentration exists). “Cross talk” from the thoron concentration into radon concentra-tion is <1.5% of the indicated radon concentration.


is equal to 0.209 dis/min for 222Rn and 0.234 dis/minfor 220Rn at ε=1 and radon and thoron concentra-tion equal to 1 dis/min.

Radon laden air was forced to flow 1 dm3/min,within 10 min, across an air filter through the Lucascell φ54x74 mm (0.17 dm3) that was installed in anMR-1 radon monitor and was placed inside a radonchamber with known radon concentration. Simul-taneously, pulse count rate of the Lucas cell wasmeasured in the time period up to 220 min. Themeasured count rate (broken curve) is shown inFig.3. The simulated count rate (smooth curve)corresponds to the reference radon concentrationwhich is equal to 53.09 dis/min at ε=1. Computedradon concentration from y=m\n is 56.0 dis/min.Similarly, thoron was forced to flow through theLucas cell (Fig.4), and count rate was measured.Thoron source was ventilated until radiation equi-librium was reached and the outlet of thoron sourcewas connected to an air filter at the moment of start-ing count rate measurement. The 232U source is anold source and is in radiation equilibrium with 228Thand 224Ra.The measured and simulated count of thoron isgiven in Fig.5. The reference concentration at ε=1

ware allows for programming parameters of thegate such as permissible contamination level, timeof measurement, date and time setting etc. Thegauge program allows also for quick checkup ofproper operation of the gate.

The principle of operation of the gate is illus-trated in a block diagram in Fig.1. Fifteen propor-

Fig.1. Block diagram of DSP-15: S1-S15 – proportionalcounter LND 49741, W1-W15 – charge preamplifier,E1-E15 – pulse discriminator, PLI1-PLI15 – pro-grammable pulse counter, CZK – card reader, RS232– serial port RS232, RS485 – serial port RS485, USB– universal series bus, GL – loudspeaker, M – gatemonitor, uP – microprocessor system, IR bra – IRcontrol of a person presence in the gate, IR in – IRcontrol at the input to the gate, IR out – IR controlat the exit from the gate, IR S1 – IR control of S1(left hand), IR S4 – IR control of S4 (right leg).

A common procedure of checking if personnelinvolved in handling open radioisotopes is notcontaminated is installment of a dosimetric gate[1-3] and obligatory checkup of all the employees.A new dosimetric gate DSP-15 was developed inthe Department of Radioisotope Instruments andMethods, Institute of Nuclear Chemistry and Tech-nology. The gate is designed for fast radioactivecontamination measurement of the personnel leav-ing the area under dosimetric control where openradioisotope sources are handled. The contamina-tion is measured by proportional counters for betaand gamma radiation located in the gate. Addition-ally, the gate is equipped with a local monitor dis-playing the state of the gate and measuring resultsof the last measurement. In case contamination ofa person or a passage of an unauthorized personthrough the gate takes place, this incident is detectedby an acoustic alarm. The gate is also equippedwith relays (contacts closed or open) that can, e.g.block the exit of a contaminated person.

Automatic registration of staff is accomplishedby means of a proximity card presented against acard reader of the gate. The gate is prepared foroperation in the monitoring system. Each measur-ing result is sent immediately to an external com-puter of the monitoring network, and is stored isthe gate memory. Three modes of operation can beprogrammed: a) obligatory contamination mea-surements of persons entering and leaving the areaunder control, b) no obligatory contamination mea-surement of persons entering and leaving the areaunder control, c) obligatory contamination checkupof persons leaving the area under control. The soft-

is equal to 1323 dis/min. Computed thoron con-centration from y=m\n is equal to 1404 dis/min.Results of a series of measurements are given inTable.

Measurements and computations carried outconfirm that radon and thoron concentration inair can be measured with a single Lucas cell. Al-though the investigations were done on the as-sumption of detection efficiency ε=1, however, themethod is valid also for ε different from 1.

References[1]. Coleman R.L.: A method for concurrent and continu-

ous measurement of Rn-222 and Rn-220 using scintil-lation cell. Oak Ridge National Laboratory ReportNo. ORNL/TM-2002/37.

[2]. Rad7. Electronic radon detector. Durridge Company.www.durridge.com.

[3]. Machaj B., Bartak J.: Nukleonika, 43, 2, 175-184(1996).

[4]. Machaj B., Urbanski P.: Nukleonika, 47, 1, 39-42(2002).

[5]. Machaj B., Urbanski P.: Nukleonika, 49, 3, 123-129(2004).

DOSIMETRIC GATE DSP-15Edward Świstowski, Jan Mirowicz, Piotr Urbański, Jan Pieńkos


tional counters for measurement of beta and gammaradiation are used in the gate. Four counters S1...S4serve for measurement of contamination of legsand hands. Five counters S6...S10 located at thefront column are used for measurement of contami-nation of front clothes of a person, and another fivecounters S11...S15 placed at the rear column areused for measurement of back clothes of a person.Each measuring channel contains charge preampli-fier, pulse discriminator and pulse counter underthe control of microprocessor system. The gate cardreader CZK serves for reading identification num-ber of the person and for reading two special cardsSETTINGS and DOSIMETRY. When SETTINGcard is read out a menu is displayed allowing forsetting measuring parameters of the gate. Present-ing DOSIMETRY card against card reader modeof operation of the gate is selected and the gate ismade ready for contamination measurements.Measurement of contamination starts when iden-tification card of a person is presented against thecard reader. Measuring results are stored in thememory of the gate, are displayed on the screenof a local monitor M, and are sent to an externalcomputer through a serial port RS485. A universalseries bus USB connects a laptop to the gate thatenables to read out measuring results stored in thegate memory.

Number of registered pulses by the probesS1...S15, that are proportional to the contamina-tion, are compared with the permissible (pro-grammed) level of contamination. In case whenexcessive contamination is detected, the counterthat detected the contamination is shown, alarmin sounded and the exit from the area under con-trol is blocked.

The gate is equipped with IR (infrared) controlsto check if a person the contamination of whom isto be measured is present inside the gate, and if hislegs and hands are in correct position. Addition-ally there are two other IR controls at the entranceand exit from the gate (entrance and exit from thearea under control). The gate is also equipped withmovement and dusk sensors for automatic switch-ing on light. A general view of the gate is shown inFig.2.

The main parameters of the gate are following:- contamination detected – beta and gamma radia-

tion;- radiation detector – LND 49741, proportional

counter, xenon filled, 3 mg/cm2 window, 115 cm2

area;- sensitivity for 60Co – 600 cps/mR/h;- background measuring time – 1 s;- contamination measuring time – 1...9 s program-

mable;- memory capacity – 500 measurements stored in

memory.

References[1]. Sirius-4 serries. Hand and foot surface contamination

monitors. www.canberra.com/products/575.asp.[2]. Argos-2. Whole body beta or alpha + beta surface con-

tamination moniotor. Hand and foot surface contami-nation monitors. www.canberra.com/products/566.asp.

[3]. Dosimetric stand SD-50B. http://www.zami.com.pl.

Fig.2. A general view of the gate.

GAMMA THIN LAYER CHROMATOGRAPHY ANALYZER SC-05Edward Świstowski, Bronisław Machaj, Ewa Kowalska, Jan Pieńkos, Ewa Gniazdowska

Thin layer chromatography (TLC) is a techniquevery often used in chemistry for identifying com-pounds, determining their purity, and following theprogress of reactions. It is also a good method foroptimization of the solvent system for a given sep-aration problem [1]. TLC technique is faster andsimpler than column chromatography and requiressamples of much lower volume. Analysis of com-pounds that are labelled with isotopes emittinggamma or beta radiation can be measured withanalyzers equipped with sensitive radiation detec-tors [2]. Such analyzers enables fast and accuratescanning of prepared strips with investigated com-

pounds and the result of analysis can be shown inthe form of diagrams.

A gamma TLC analyzer, type SC-05, was de-veloped and was constructed in the Departmentof Radioisotope Instruments and Methods, Instituteof Nuclear Chemistry and Technology (INCT). Ageneral view of the analyzer is shown in Fig.1. It isa laboratory instrument, with small dimensionswhose parameters allow for its wide application inchemical and pharmaceutical laboratories, employ-ing radioactive isotopes, and in nuclear medicine.The analyzer can analyze strips 20 cm long with anisotope labelled compound deposited on the strip.


Gamma isotopes: 125I, 131I, 111In, 188Re, 99mTc andothers with radiation energy 15-510 keV can beanalyzed. The radiation is collimated with a Pb slotcollimator 2.5x25 mm, 20 mm thick. An NaI(Tl)φ25x25 mm scintillator is used as radiation detec-tor. Linear stage with the strip analyzed is movedin relation to the detector in 1 mm steps by a stepmotor. Counting time of one step is programmedin the range: 0.5, 1, 3, 6 s. The measuring result ofeach step is displayed on the analyzer display, andis stored in the analyzer memory. The measuring

results stored in the memory are sent through aserial port to an external computer. Up to 50 dia-grams can be stored in the memory. Three fixedwindows for 125I, 131I, 99mTc and one programmablewindow in the range 15-510 keV are accessible forthe user. The measuring results stored in the memorycan be called from the memory and can be reviewedon analyzer display in the form of a diagram togetherwith the date, time and parameters of the measure-ment. A fragment of the diagram (peak) can be se-lected and the number of counts in the selectedfragment is automatically displayed.

To ensure stable operation of measuring chan-nel of the analyzer, automatic gain control circuitis used. Light emitting diode (LED) is used as ref-erence signal. During gain control process, theamplitude of LED pulse is measured and the highvoltage of photomultiplier tube is changed until acorrect pulse amplitude is achieved. Automaticgain control is activated after mains voltage isswitched on, and later before start of analysis of anew strip.

One of the SC-05 analyzers was installed in theDepartment of Radiochemistry of the INCT whereit is used for routine investigations. Example chro-matograms achieved with the help of the analyzerare shown in Fig.2.

References[1]. http://www.raytest.de/radiochromatography/products/

Rita-Star.[2]. http://www.chem.ucla.edu/~bacher/General/30BL/

tips/TLC1.html.

Fig.2. TLC carried out to check the progress of aS3(99mTcO)SPh complex formation [S3=S(CH2CH2SH)2]:A – TLC of pertechnetate obtained from a 99Mo/99mTcgenerator-Amersham (heptavalent technetium), B– TLC of 99mTcO-ethylene glycol complex (penta-valent technetium), C – TLC of intermediate com-plex 99mTcO-thiophenol, D – TLC of mixed-ligandcomplex S3(99mTcO)SPh.

Fig.1. A general view of gamma TLC analyzer SC-05.

INVESTIGATION OF DUST POLLUTION IN ASSEMBLING HALLOF TV SETS

Jan Pieńkos, Piotr Urbański

It is well known that airborne dust pollution has aharmful influence on human being health. Becauseof that, a maximum permissible level of dust pol-

lution was set, and dust concentration in the air ismeasured. The smaller is the diameter of the dustparticles, the more deeply the particles can pen-


etrate into the lung. Average daily permissible levelof dust concentration in ambient air with particlediameter <10 μm is set to 50 μg/m3.

Air dust pollution is important not only fromthe point of view of human being protection. It isalso important from the point of view of clean air

that is required in some industries. On request ofa producer of TV set, measurements of dust con-centration were measured inside assembling hallto investigate what is the dust pollution and how itvaries. The AMIZ-2004G monitor for automaticmeasurement of airborne dust pollution of ambi-ent air was used to investigate the dust concentra-tion in the air. The dust monitor was located in themiddle of the assembling hall between the trans-porters moving the TV sets (Fig.1). The principleof operation of the monitor employs attenuationof beta radiation from 147Pm by the dust depositedon an air filter to determine the mass of dust. Vol-ume of the air from which the dust is deposited onthe filter is proportional to the time of deposition(the flow of air through the filter is kept constant).Dust concentration is the ratio of the dust mass tothe volume of air. The measurements were carriedout in the period of seven days. Total dust air inletwas installed in the dust monitor. Thus, all the dustparticles without limitation of their diameter weredeposited on the air filter. The monitor was set tocontinuous automatic mode of operation with 1 hdust deposition on the air filter. The measuringresults were stored in the monitor memory. The dustmonitor was equipped with wireless transmission

of measuring results to an external PC computer.Operation of the dust monitor was controlled bythe stuff of the Institute of Nuclear Chemistry andTechnology (INCT) and the measuring results werealso available by the INCT, although the distanceof assembling hall from Warsaw was more than 200km. Work in the assembling hall was carried out

in two shifts from 6 to 22 h. Measuring results forthe first 4.5 days, illustrating how high was the dustconcentration in μg/m3, and how the dust concen-tration varied within these days are shown in Fig.2.Similar dust concentration and similar variationsof dust concentration were observed in the remain-ing days of investigations. On analyzing the diagramof dust concentration, the following observationscan be made:- Dust concentration during work hours is high,

single readings reaching up to 150 μg/m3, andthe average 80-100 μg/m3. At night, when therewas no work activity the dust concentration wasmuch lower and fell to less than 50 μg/m3, andon Sunday even to 30 μg/m3.

- It is up to the producer of TV sets to decide ifthe recorded levels of dust concentration can beaccepted as sufficiently low, or appropriate stepsshould be undertaken to decrease the dust con-centration.

- The dust monitor AMIZ-2004G proved to bean appropriate instrument for checkup measure-ments of dust concentration inside of some in-dustrial halls.

Fig.1. Localization of dust monitor in the assembling hall.

Fig.2. Dust concentration inside assembling hall.

COMMERCIAL APPLICATION OF ELECTRON BEAM ACCELERATORSAT R&D AND SERVICE CENTER

Andrzej G. Chmielewski, Wojciech Migdał, Zbigniew Zimek, Iwona Kałuska,Sylwester Bułka

type, 2 MeV and 20 kW beam power (supportedby the International Atomic Energy Agency –IAEA, 1988);

- demonstration facility for flue gas treatmentwith flow rate up to 20 000 Nm3/h, with two elec-tron accelerators ELV 3A type 0.7 MeV and 50kW beam power each (supported by the IAEA),located at the power station “Kawęczyn” (1991);

Two pilot plant installations have been built at theInstitute of Nuclear Chemistry and Technology(INCT) to carry out R&D studies, to evaluate tech-nical and economical requirements for industrialfacilities and to provide radiation processing ser-vice on a semi-industrial scale:- pilot plant installation for polymer modification,

equipped with an electron accelerator ILU-6


and two industrial plants:- radiation sterilization plant equipped with a

microwave linac ELEKTRONIKA 10/10 withelectron energy of 10 MeV and an average beampower of 15 kW (1993);

- food irradiation plant with two 10 MeV electronaccelerators: PILOT with 1 kW and ELEKTRONI-KA 10/10 with 10 kW of beam power (1992) [1].The commercial irradiation plant was built to

satisfy growing demands for irradiation service. Afacility equipped with the electron acceleratorELEKTRONIKA 10/10 was put into operation atthe INCT in 1993. The accelerator was manufac-tured in NPO “Toriy” (Moscow, Russia). 10 MeVelectron energy and up to 15 kW average beampower is applied for radiation processing This ac-celerator is based on the running wave accelerat-ing section and is placed vertically to avoid bend-ing magnet and beam power losses related to itsapplication and a high average power magnetronwas used as a source of microwave energy.

The microprocessor controlled roller and beltconveyor system is used to carry boxes with typicalsize 580x460x200 mm. The speed of the conveyorsection located at the irradiation chamber, wherea stainless steel belt was applied, can be varied con-tinuously within the range 0.3-7 m/min. Additionalequipment for two-sided irradiation can be usedwhen necessary. The rubber belts are used for trans-porting boxes between basement and ground levels.Continuous monitoring of electron beam parametersand speed of the conveyor were foreseen to fulfilroutine monitoring requirements. Upgraded accel-erator control system for delivering required doseand data acquisition for sterilization process havebeen implemented. Figure 1 shows the block dia-gram of the accelerator installation with pointedout devices being under computer control.

In Poland till the end of 50s of the XX century,the research activities in the field of food irradia-tion were rather of basic research type. Practicalapplications of food irradiation on a commercialscale started in plant in 1993. The plant was estab-lished in the scope of government programme andwas equipped with two linear electron accelerators:PILOT (10 MeV, 1 kW) and ELEKTRONIKA (10MeV, 10 kW) [2,3].

Actually, permission by the Ministry of Healthin Poland was granted for irradiation of the fol-lowing kind of products: potatoes, onions, garlic,mushrooms, spices and dried vegetables.

The role of the plant is to promote food irra-diation technology in Poland by:- development of new radiation technologies for

the preservation and hygienization of food prod-ucts;

- development of radiation technologies for thehygienization of natural components utilized inthe cosmetic industry;

- development of radiation technologies for thehygienization of natural product utilized in thepharmaceutical industry;

- development and standardization of control sys-tem for electron beam processing of food andother products;

- organization of local (national) and/or interna-tional workshops and symposia devoted to tech-nical, technological and economical aspects offood irradiation.Figure 2 shows the block diagram of the accel-

erator installation at the plant for food irradiation.In both irradiation plants a computer system hasbeen installed which assures delivery of the desireddose of electrons 9.0-9.5 MeV by controlling accel-erator parameters with the use of an analog-digitalsteering system and collecting data under technol-ogical conditions. Basing on the dose measurementsat the adjusted parameters and actual conveyorspeed, the system calculates the dose on-line thatis stored at computer hard disc.

The system enables simultaneous on-line con-trol of irradiation parameters dedicated to foodproducts in agreement with the EC Directives1999/2/EC, 1999/3/EC and Decree of the Ministryof Health dated 15.01.2003 and to medical devicesin agreement with ISO 13485 and ISO 11137.

Dosimetric systems used in both plants aretraceable by the accreditated Laboratory for Mea-surements of Technological Doses.

In conclusion, two plants (one for sterilizationand the second for food irradiation) equipped withlinear accelerators 10 MeV, 10 kW have been op-erated for more than ten years. Technical andeconomical feasibility of the electron beam tech-nology for these applications have been demon-strated.

Fig.1. Block diagram of the accelerator installation at theplant for radiation sterilization.

Fig.2. Block diagram of the accelerator installation at theplant for food irradiation.

HV Pulse Power Supply RF PowerGenerator

Magnetron

Electron Gun

AcceleratingSection

Vacuum Pump

ScanningHorn

ScanningCoils

EB ExtractionWindow

Conveyor

MotorSteering

Interfaces &Signal Processing

Control System Console

*

**

*

* Most important signal sourcesfor irradiation process status evaluation


Quality assurance and quality control proce-dures following all ISO and EN standards are fullyimplemented. The accredited laboratory for tech-nological dosimetry, beside routine laboratoriesled to the establishment of high level quality controlsystem.

Well prepared and implemented technical, eco-nomical and quality systems are inseparably con-ditions for the establishment of food irradiation andsterilization facilities.

used as a source of electrons in this particular struc-ture. The triode electron gun was designed and madeby the accelerator manufacturer “Toriy” company(Moscow, Russia).

Electron gun construction modification is necess-ary to meet the requirements for standing wave struc-

ture applied in a new accelerator. The followingmodifications were introduced in vacuum area ofthe triode electron gun:- enlargement of the distance “L” between the

cathode and the grid from 1 to 3.6 mm (Fig.1);- enlargement of the distance “A” between the

grid and the anode from 20 to 35 mm (Fig.1);

Main assembly of new electron accelerator whichis under construction at the Institute of NuclearChemistry and Technology is standing wave accel-erating structure operated at a frequency of 2856MHz. The accelerating structure was provided by“Lepton JSCo” company (St. Petersburg, Russia)

under the technical cooperation project supportedby the International Atomic Energy Agency. Elec-tron beam emitted from an electron gun is intro-duced to the first resonator area of the accelerat-ing structure. The electron beam parameters shouldbe compatible with electrical specification of thestructure (Table). Table contains the data relatedto parameters of the electron beam which is intro-duced in the first resonator area of “Elektronika10/10” accelerator. In that case the acceleratingstructure is designed for travelling wave operatingmode at a frequency of 1863 MHz. The triode elec-tron gun with a spherical impregnated cathode is

References[1]. Zimek Z., Rzewuski H., Migdal W.: Nukleonika, 40,

3, 93-113 (1995).[2]. Migdal W., Walis L., Chmielewski A.G.: Radiat. Phys.

Chem., 42, 1-3, 567-570 (1993).[3]. Migdal W., Maciszewski W., Gryzlow A.: Radiat. Phys.

Chem., 46, 4-6, 749-752 (1995).

ELECTRON GUN FOR 10 MeV, 10 kW ELECTRON ACCELERATORZygmunt Dźwigalski, Zbigniew Zimek

Fig.2. Electron gun – additional element.Fig.1. Electron gun – distances between electrodes.

Table. Electron beam parameters.


- additional element whose shape beam dimen-sions was incorporated (Fig.2).The modification should allow to obtain desir-

able shape of the electron beam shown in Fig.3.Shapes of the equipotential lines are congenial toreal shapes of the lines in the electron beam area,

but the lines differ from the real ones and far fromthe beam area. It is due to the accepted mathemati-cal model.

The electron gun main insulator, made fromsilicon rubber, operating in air, could be not suffi-cient in the new working environment at the high-est electrical strength. Electrical strength of theinsulator is too low, especially in long-term exploi-tation. Due to that, additional insulating part,made from acrylic glass or epoxy glass will be in-corporated (Fig.4). The glass ring will be connectedconstantly with the main insulator. Electrical strengthof such a modified insulator will be much higherthan 50 kV.

Fig.3. Electron gun – equipotential lines and electron tra-jectories.

Fig.4. Electron gun – silicon rubber insulator and addi-tional insulator.

THE INCT PUBLICATIONS IN 2006 165

THE INCT PUBLICATIONS IN 2006

ARTICLES

1. Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Orelovitch O.L., Sartowska B.Structure of polycarbonate track-etch membranes: origin of the “paradoxical” pore shape.Journal of Membrane Science, 282, 393-400 (2006).

2. Asmus K.-D., Hug G.L., Bobrowski K., Mulazzani G., Marciniak B.Transients in the oxidative and H-atom-induced degradation of 1,3,5-trithiane. Time-resolved studiesin aqueous solution.Journal of Physical Chemistry A, 110, 9292-9300 (2006).

3. Bartłomiejczyk T., Iwaneńko T., Wojewódzka M., Woliński J., Zabielski R., Kruszewski M.Differential action of ghrelin and leptin, a human metabolism and energy regulators, on the lymphocytesusceptibility to oxidative stress.Journal of Physiology and Pharmacology, 57, Suppl. 2, 118 (2006).

4. Bartłomiejczyk T., Iwaneńko T., Wojewódzka M., Woliński J., Zabielski R., Kruszewski M.Ghrelin administration sensitizes blood mononuclear cells to oxidative stress.Journal of Physiology and Pharmacology, 57, Suppl. 2, 119 (2006).

5. Bartoś B., Bilewicz A.Effect of crown ethers on Sr2+, Ba2+, and Ra2+ uptake by tunnel-structure ion exchangers.Solvent Extraction and Ion Exchange, 24, 261-269 (2006).

6. Barysz M., Kędziera D., Leszczyński J., Bilewicz A.Structure and hydrolysis of the heavy alkaline earth cations: relativistic studies.International Journal of Quantum Chemistry, 106, 2422-2427 (2006).

7. Bilewicz A., Bartoś B., Misiak R., Petelenz B.Separation of 82Sr from rubidium target for preparation of 82Sr/82Rb generator.Journal of Radioanalytical and Nuclear Chemistry, 268, 3, 485-487 (2006).

8. Bojanowska-Czajka A., Drzewicz P., Kozyra Cz., Nałęcz-Jawecki G., Sawicki J., Szostek B.,Trojanowicz M.Radiolytic degradation of herbicide 4-chloro-2-methyl phenoxyacetic acid (MCPA) by γ-radiation forenvironmental protection.Ecotoxicology and Environmental Safety, 65, 265-277 (2006).

9. Bojanowska-Czajka A., Drzewicz P., Nałęcz-Jawecki G., Sawicki J., Trojanowicz M.Zastosowanie promieniowania jonizującego do degradacji wybranych pestycydów w wodach i ściekach(Application of ionizing radiation to the decomposition of selected pesticides in waters and sewages).Postępy Techniki Jądrowej, 49, 1, 26-31 (2006).

10. Bonilla F.A, Skeldon P., Thompson G.E., Piekoszewski J., Chmielewski A.G., Sartowska B.,Stanisławski J.Corrosion resistant Ti-Pd surface alloys produced by high intensity pulsed plasma beams. Part 2. Depo-sition by pulsed implantation doping mode with palladium implantation using a MEVVA source.Surface and Coatings Technology, 200, 4684-4692 (2006).

11. Bonilla F.A, Skeldon P., Thompson G.E., Piekoszewski J., Chmielewski A.G., Sartowska B.,Stanisławski J., Bailey P., Noakes T.C.Q.Corrosion resistant Ti-Pd surface alloys produced by high intensity pulsed plasma beams. Part 1. Depo-sition by pulsed erosion and vacuum evaporation/pulsed implantation doping modes.Surface and Coatings Technology, 200, 4674-4683 (2006).


12. Brzóska K., Iwaneńko T., Wojewódzka M., Woliński J., Kruszewski M.Differential action of human metabolism regulators on the lymphocyte susceptibility to oxidative stress.Acta Biochimica Polonica, 53, Suppl. 1, 172 (2006).

13. Brzóska K., Kruszewski M., Szumiel I.Nonhomologous end-joining deficiency of L5178Y-S cells is not associated with mutation in the ABCDEautophosphorylation cluster.Acta Biochimica Polonica, 53, 1, 233-236 (2006).

14. Brzóska K., Męczyńska S., Kruszewski M.Iron-sulfur clusters proteins: electron transfer and beyond.Acta Biochimica Polonica, 53, 4, 685-691 (2006).

15. Brzóska K., Męczyńska S., Kruszewski M.Non-haem iron proteins: new functions of old pals.Acta Biochimica Polonica, 53, Suppl. 1, 112 (2006).

16. Chmielewska D.K., Łukasiewicz A., Michalik J., Sartowska B.Silica materials with biocidal activity.Nukleonika, 51, Suppl. 1, s69-s72 (2006).

17. Chmielewski A.G.Worldwide developments in the field of radiation processing of materials in the down of 21st century.Nukleonika, 51, Suppl. 1, s3-s9 (2006).

18. Chmielewski A.G., Licki J., Pawelec A., Tymiński B., Zimek Z.Operational experience of the industrial plant for electron beam flue gas treatment.Ecological Chemistry and Engineering, 13, 10, 1057-1063 (2006).

19. Chmielewski A.G., Palige J., Zakrzewska-Trznadel G.Izotopy widzą wszystko (Isotopes see everything).Almanach Ekologii, 122-124 (2006).

20. Chmielewski A.G., Tymiński B., Pawelec A., Palige J., Dobrowolski A.Modelowanie przepływu gazu w reaktorze do oczyszczania spalin metodą radiacyjną z użyciem metodCFD (Modelling of gas flow in a reactor for electron beam flue gas treatment using CFD methods).Prace Naukowe Instytutu Inżynierii Chemicznej PAN, 7, 59-71 (2006).

21. Chwastowska J., Danko B.Analiza materiałów środowiskowych (Analysis of environmental materials).Ekologia, 4, 38-39 (2006).

22. Cieśla K., Salmieri S., Lacroix M.γ-Irradiation influence on the structure and properties of calcium caseinate-whey protein isolate basedfilms. Part 1. Radiation effect on the structure of proteins gels and films.Journal of Agricultural and Food Chemistry, 54, 6374-6384 (2006).

23. Cieśla K., Salmieri S., Lacroix M.γ-Irradiation influence on the structure and properties of calcium caseinate-whey protein isolate basedfilms. Part 2. Influence of polysaccharide addition and radiation treatment on the structure and func-tional properties of the films.Journal of Agricultural and Food Chemistry, 54, 8899-8908 (2006).

24. Cieśla K., Salmieri S., Lacroix M.Modification of the properties of milk protein films by gamma radiation and polysaccharide addition.Journal of the Science of Food and Agriculture, 86, 908-914 (2006).

25. Dalivelya O., Savina N., Kuzhir T., Buraczewska I., Wojewódzka M., Szumiel I.Effects of an antimutagen of 1,4-dihydropyridine series on cell survival and DNA damage in L5178Ymurine sublines.Nukleonika, 51, 3, 141-146 (2006).

26. Danilczuk M., Lund A., Sadło J., Yamada H., Michalik J.Conduction electron spin resonance of small silver particles.Spectrochimica Acta A, 63, 189-191 (2006).

167THE INCT PUBLICATIONS IN 2006

27. Danilczuk M., Pogocki D., Lund A., Michalik J.EPR and DFT study on the stabilization of radiation-generated methyl radicals in dehydrated Na-Azeolite.Journal of Physical Chemistry B, 110, 24492-24497 (2006).

28. Danko B., Samczyński Z., Dybczyński R.Analytical scheme for group separation of the lanthanides from biological materials before their deter-mination by neutron activation analysis.Chemia Analityczna, 51, 527-539 (2006).

29. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysocka A.I.Isotope effects of gallium and indium in cation exchange chromatography.Nukleonika, 51, 4, 217-220 (2006).

30. Deperas-Kamińska M., Szumiel I., Wójcik A.Elementy radiologii dla pilota Pirxa (Elements of radiobiology for pilot Pirx).Kosmos, Problemy Nauk Biologicznych, 55, 4, 337-345 (2006).

31. Deptuła A., Chwastowska J., Łada W., Olczak T., Wawszczak D., Sterlińska E., Sartowska B.,Goretta K.C.Sol-gel-derived hydroxyapatite and its application to sorption of heavy metals.Advances in Science and Technology, 45, 2198-2203 (2006).

32. Deptuła A., Dubarry M., Noret A., Gaubicher J., Olczak T., Łada W., Guyomard D.Atypical Li1.1V3O3 prepared by a novel synthesis route.Electrochemical and Solid-State Letters, 9, 1, A16-A18 (2006).

33. Deptuła A., Łada W., Olczak T., Chmielewski A.G.Application of Pt/Al2O3 catalysts produced by sol-gel process to uranyl ion reduction.Nukleonika, 51, Suppl. 1, s79-s82 (2006).

34. Filipczak K., Woźniak M., Ulański P., Olah L., Przybytniak G., Olkowski R.M., Lewandow-ska-Szumieł M., Rosiak J.M.Poly(ε-caprolactone) biomaterial sterilized by e-beam irradiation.Macromolecular Bioscience, 6, 261-273 (2006).

35. Filipiuk D., Fuks L., Majdan M.Biosorpcja jako metoda usuwania i odzysku metali ciężkich z wodnych ścieków przemysłowych(Biosorption as a new method for sequestering heavy metals in industrial aqueous effluents).Przemysł Chemiczny, 85, 6, 417-422 (2006).

36. Fuks L., Filipiuk D., Majdan M.Transition metal complexes with alginate biosorbent.Journal of Molecular Structure, 792-793, 104-109 (2006).

37. Fuks L., Polkowska-Motrenko H.Interlaboratory comparison of the determination of 137Cs and 90Sr in water, food and soil: preparationand characterization of test materials.Nukleonika, 51, Suppl. 2, s27-s31 (2006).

38. Głuszewski W.Nowe zakłady produkcji polietylenu PE i polipropylenu PP (New works for the production of poly-ethylene (PE) and polypropylene (PP).Postępy Techniki Jądrowej, 49, 2, 40-43 (2006).

39. Głuszewski W.Rak płuca. Wczesne wykrycie = dłuższe życie (Lung cancer. Early detection=longer life)Postępy Techniki Jądrowej, 50, 4, 29-31 (2006).

40. Głuszewski W., Panta P.P., Kubera H.Wpływ promieniowania jonizującego na właściwości materiałów opakowaniowych (Effect of ionizingradiation on the properties of packaging materials).Opakowanie, 9, 24-26 (2006).


41. Głuszewski W., Zagórski Z.P.Zastosowanie chromatografii gazowej (GC) w badaniach modyfikacji radiacyjnej polipropylenu (Ap-plication of gas chromatography to the investigation of radiation chemistry of polypropylene).Czasopismo Techniczne. Mechanika, 6, 190-192 (2006).

42. Głuszewski W., Zagórski Z.P.Zdolności przerobowe akceleratorów IChTJ do obróbki radiacyjnej (Production capacity of the INCTaccelerators for radiation processing).Kauczuki Naturalne i Syntetyczne, 3, 28-30 (2006).

43. Gniazdowska E., Kraus W., Emmerling F., Spies H., Stephan H.Tetrabutylammonium bis(2-amidobenzenethiolato-κ2S,N)oxorhenate(V).Acta Crystallographica E 62, m1197-m1199 (2006).

44. Grądzka I.Mechanizmy i regulacja programowanej śmierci komórek (Mechanisms and regulation of the pro-grammed cell death).Postępy Biochemii, 52, 2, 157-165 (2006).

45. Grigoriew H., Luboradzki R., Gronkowski J.USAXS studies of monosaccharide gels. I. Dependence of the glucofuranose-based gel structure onthe gelator concentration.Journal of Non-Crystalline Solids, 352, 3052-3057 (2006).

46. Gryz M., Starosta W., Leciejewicz J.Bis(μ-pyridazine-3,6-carboxylato-κ4N,O:N’,O’)-bis[diaquazinc(II)].Acta Crystallographica E, 62, m3470-m3472 (2006).

47. Gryz M., Starosta W., Leciejewicz J.trans-Diaquabis(pyridazine-3-carboxylato-κ2N,O)-magnesium(II) dihydrate.Acta Crystallographica E, 62, m123-m124 (2006).

48. Grzesiuk W., Nieminuszczy J., Kruszewski M., Iwaneńko T., Płazińska M., Bogdańska M.,Bar-Andziak E., Królicki L., Grzesiuk E.DANN damage and its repair in lymphocytes and thyroid nodule cells during radioiodine therapy inpatients with hyperthyroidism.Journal of Molecular Endocrinology, 37, 527-532 (2006).

49. Khayet M., Mengual J.I., Zakrzewska-Trznadel G.Direct contact membrane distillation for nuclear desalination. Part II: experiments with radioactivesolutions.International Journal of Nuclear Desalination, 2, 1, 56-73 (2006).

50. Konarski P., Ćwil M., Piekoszewski J., Stanisławski J.SIMS characterisation of superconductive MgB2 layers prepared by ion implantation and pulsed plasmatreatment.Applied Surface Science, 252, 7078-7081 (2006).

51. Kornacka E., Kozakiewicz J., Legocka I., Przybylski J., Przybytniak G., Sadło J.Radical processes induced in poly(siloxaneurethaneureas) by ionising radiation.Polymer Degradation and Stability, 91, 2182-2188 (2006).

52. Kornacka E., Kozakiewicz J., Przybytniak G.Odporność radiacyjna aromatycznych poliuretanów przeznaczonych do zastosowań medycznych (Ra-diation resistance of aromatic polyurethanes for medical applications).Inżynieria Biomateriałów, 58-60, 143-145 (2006).

53. Kornacka E.M., Przybytniak G., Święszkowski W.Wpływ stopnia krystaliczności na stabilność radiacyjną UHMWPE (The influence of crystallinity onradiation stability of UHMWPE).Inżynieria Biomateriałów, 58-60, 146-149 (2006).


54. Krejzler J., Narbutt J., Foreman M.R.St J., Hudson M.J., Casensky B., Madic C.Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of n-triden-tate heterocycles and chlorinated cobalt dicarbollide.Czechoslovak Journal of Physics, 56, Suppl. D, D459-D467 (2006).

55. Lankoff A., Banasik A., Duma A., Ochniak E., Lisowska H., Kuszewski T., Góźdź S., Wójcik A.A comet assay study reveals that aluminium induces DNA damage and inhibits the repair of radia-tion-induced lesions in human peripheral blood lymphocytes.Toxicology Letters, 161, 27-36 (2006).

56. Lankoff A., Bialczyk J., Dziga D., Carmichael W.W., Grądzka I., Lisowska H., Kuszewski T.,Góźdź S., Piorun I., Wójcik A.The repair of gamma-radiation-induced DNA damage is inhibited by microcystin-LR, the PP1 andPP2A phosphate inhibitor.Mutagenesis, 21, 1, 83-90 (2006).

57. Lankoff A., Bialczyk J., Dziga D., Carmichael W.W., Lisowska H., Wójcik A.Inhibition of nucleotide excision repair (NER) by microcystin-LR in CHO-K1 cells.Toxicon, 48, 957-965 (2006).

58. Lankoff A., Wójcik A., Fessard V., Meriluoto J.Nodularin-induced genotoxicity following oxidative DANN damage and aneuploidy in HepG2 cells.Toxicology Letters, 164, 239-248 (2006).

59. Liniecki J., Wójcik A.20 lat po awarii w Czarnobylu. Co dziś wiemy o następstwach zdrowotnych? (20 years after the Chernobylaccident. What we know today about the radiological consequences?)Postępy Techniki Jądrowej, 49, 1, 2-8 (2006).

60. Lisowska H., Lankoff A., Wieczorek A., Florek A., Kuszewski T., Góźdź S., Wójcik A.Enhanced chromosomal radiosensitivity in peripheral blood lymphocytes of larynx cancer patients.International Journal of Radiation Oncology, Biology, Physics, 66, 4, 1245-1252 (2006).

61. Łyczko K., Narbutt J., Paluchowska B., Maurin J.K., Persson I.Crystal structure of lead(II) acetylacetonate and the structure of the acetylacetone solvated lead(II)ion in solution studies by large-angle X-ray scattering.Dalton Transactions, 3972-3976 (2006).

62. Mádl M., Kunicki-Goldfinger J.J.Eiland: Georg Gundelach and the glassworks on the Dìèin Estate of count Maximilian Thun-Hohenstein.Journal of Glass Studies, 48, 225-247 (2006).

63. Majkowska A., Bilewicz A.Formation kinetics and stability of some TRI and tetraaza derivative complexes of scandium.The Quarterly Journal of Nuclear Medicine and Molecular Imaging, 50, Suppl. 1 to issue 1, 45 (2006).

64. Markowicz S., Niedzielska J., Kruszewski M., Ołdak T., Gajkowska A., Machaj E.K., Skurzak H.,Pojda Z.Nonviral transfection of human umbilical cord dentritic cells is feasile, but the yield of dendritic cellswith transgene expression limits the application of this method in cancer immunotherapy.Acta Biochimica Polonica, 53, 1, 203-211 (2006).

65. Męczyńska S., Lewandowska H., Kruszewski M.The role of lysosomal iron in dinitrosyl iron complexes formation.Acta Biochimica Polonica, 53, Suppl. 1, 192 (2006).

66. Orelovitch O.L., Apel P.Yu., Sartowska B.New methods of track membrane treatment in the preparation of samples for further observation withscanning electron microscopy.Journal of Microscopy, 224, 100-223 (2006).

67. Palige J., Dobrowolski A., Owczarczyk A., Chmielewski A.G., Ptaszek S.Badania znacznikowe i CFD procesu sedymentacji osadu w osadniku prostokątnym (Tracer and CFDinvestigations of sedimentation processes in a rectangular settler).Inżynieria i Aparatura Chemiczna, 6a, 181-182 (2006).


68. Palige J., Dobrowolski A., Owczarczyk A., Chmielewski A.G., Ptaszek S.Badania znacznikowe i CFD struktury przepływu ścieków w osadnikach prostokątnych dla różnychgeometrii napływu i wypływu ścieków (Tracer and CFD investigations of flow structure for two waste-water inputs and outputs configurations in rectangular settler).Inżynieria i Aparatura Chemiczna, 5a, 104-107 (2006).

69. Pawlukojć A., Natkaniec I., Bator G., Sobczyk L., Grech E., Nowicka-Scheibe J.Low frequency internal modes of 1,2,4,5-tetramethylbenzene, tetramethylpyrazine and tetramethyl-1,4-benzo-quinone INS, Raman, infrared and theoretical DFT studies.Spectrochimica Acta Part A, 63, 766-773 (2006).

70. Pawlukojć A., Sawka-Dobrowolska W., Bator G., Sobczyk L., Grech E., Nowicka-Scheibe J.X-ray diffraction, inelastic neutron scattering (INS) and infrared (IR) studies on 2:1 hexamethylbenzene(HMB)-tetracyanoethylene (TCNE) complex.Chemical Physics, 327, 311-318 (2006).

71. Peimel-Stuglik Z., Fabisiak S.Solid state “self-calibrated” EPR-dosimeters – advantageous and shortcomings.Spectrochimica Acta Part A, 63, 855-860 (2006).

72. Podrez-Radziszewska M., Bąkowski D., Lachowicz M., Głuszewski W., Dudziński W.Charakterystyka twardości i właściwości wytrzymałościowych UHMWPE po napromieniowaniu wiązkąelektronów (Characterization of hardness and strength properties UHMWPE after irradiation with anelectron beam).Inżynieria Materiałowa, 2, 75-78 (2006).

73. Polkowska-Motrenko H., Chajduk E., Dybczyński R.Selective separation of trace amounts of selenium using extraction chromatography and its determina-tion by neutron activation analysis in biological samples.Chemia Analityczna, 51, 581-591 (2006).

74. Polkowska-Motrenko H., Dybczyński R.Activities of the INCT, Warsaw, in the domain of quality assurance for inorganic analysis.Journal of Radioanalytical and Nuclear Chemistry, 269, 2, 339-345 (2006).

75. Prager M., Pietraszko A., Sobczyk L., Pawlukojć A., Grech E., Seydel T., Wischnewski A.,Zamponi M.X-ray diffraction and inelastic neutron scattering study of 1:1 tetramethylpyrazine chloranilic acid com-plex: temperature, isotope, and pressure effects.The Journal of Chemical Physics, 125, 194525-1-11 (2006).

76. Premkumar T., Govindarajan S., Starosta W., Leciejewicz J.Diaquatetrakis(pyrazine-2-carboxylato-κ2O,N)-thorium(IV) trihydrate.Acta Crystallographica E, 62, m98-m100 (2006).

77. Pruszyński M., Bilewicz A.211At-Rh(16-S4-diol) complex as a precursor for astatine radiopharmaceuticals.The Quarterly Journal of Nuclear Medicine and Molecular Imaging, 50, Suppl. 1 to issue 1, 44 (2006).

78. Pruszyński M., Bilewicz A., Wąs B., Petelenz B.Formation and stability of astatide-mercury complexes.Journal of Radioanalytical and Nuclear Chemistry, 268, 1, 91-94 (2006).

79. Przybytniak G., Kornacka E., Ryszkowska J., Bil M., Rafalski A., Woźniak P., Lewandowska-Szu-mieł M.Influence of radiation sterilization on poly(ester urethanes) designed for medical applications.Nukleonika, 51, Suppl. 1, s121-s128 (2006).

80. Sadlej-Sosnowska N., Ocios A., Fuks L.Selectivity of similar compounds’ identification using IR spectrometry: β-Lactam antibiotics.Journal of Molecular Structure, 792-793, 110-114 (2006).

81. Sadło J., Michalik J., Kevan L.EPR and ESEEM study of silver clusters in ZK-4 molecular sieves.Nukleonika, 51, Suppl. 1, s49-s54 (2006).


82. Sadło J., Michalik J., Stachowicz W., Strzelczak G., Dziedzic-Gocławska A., Ostrowski K.EPR study on biominerals as materials for retrospective dosimetry.Nukleonika, 51, Suppl. 1, s95-s100 (2006).

83. Samczyński Z.Ion exchange behavior of selected elements on Chelex 100 resin.Solvent Extraction and Ion Exchange, 24, 781-794 (2006).

84. Sartowska B., Piekoszewski J., Waliś L., Stanisławski J., Nowicki L., Ratajczak R.Characterization of the near-surface layers of carbon steels modified by interaction with intense pulsedplasma beams: scanning electron microscopy investigations.Journal of Microscopy, 224, 114-116 (2006).

85. Sastry M.D., Gustafsson H., Danilczuk M., Lund A.Dynamical effects and ergodicity in the dipolar glass phase: evidence from time-domain EPR andphase memory time studies of AsO4

4– in Rb1-x(NH4)xH2PO4 (x = 0, 0.5, 1).Journal of Physics: Condensed Matter, 18, 4265-4284 (2006).

86. Sawka-Dobrowolska W., Bator G., Czarnik-Matusewicz B., Sobczyk L., Pawlukojć A., Grech E.,Nowicka-Scheibe J., Rundlöf H.X-ray and neutron diffraction, IR and INS spectroscopic and DFT theoretical studies on the tetra-methylpyrazine-1,2,4,5-tetracyanobenzene complex.Chemical Physics, 327, 237-246 (2006).

87. Schlick S., Bosnjakovic A., Danilczuk M.Direct ESR and spin trapping methods for the study of radicals in PEMS and model compounds ex-posed to oxygen radicals.Abstracts of Papers of the American Chemical Society, Division of Fuel Chemistry, 51, 2, 688-689 (2006).

88. Sommer S., Deperas-Kamińska M., Wójcik A., Szumiel I.Indywidualna promieniowrażliwość chromosomów i odcisk palca promieniowania. Otwarte pytania wdziedzinie dozymetrii biologicznej (Individual radiosensitiveness of chromosomes and fingerprint ofradiation. Open questions in the field of biological dosimetry).Postępy Techniki Jądrowej, 49, 1, 16-21 (2006).

89. Starosta W., Buczkowski M., Sartowska B., Wawszczak D.Studies on template-synthesized polypyrrole nanostructures.Nukleonika, 51, Suppl. 1, s35-s39 (2006).

90. Starosta W., Leciejewicz J.catena-Poly[[aquacalcium(II)]bis(μ-1H-imidazole-4-carboxylato)-κ4N,O:O,O’; κ3O,O’:O’].Acta Crystallographica E, 62, m2648-m2650 (2006).

91. Starosta W., Leciejewicz J., Premkumar T., Govindarajan S.Crystal structures of two Ca(II) complexes with imidazole-4,5-dicarboxylate and water ligands.Journal of Coordination Chemistry, 59, 5, 557-564 (2006).

92. Stupińska H., Iller E., Zimek Z., Kopania E., Palenik J., Milczarek S.Otrzymywanie mikrokrystalicznej celulozy z zastosowaniem ekologicznych metod depolimeryzacjicelulozy. Część I. Degradacja radiacyjna (Obtaining of microrystalline cellulose with the ecologicalmethod of cellulose depolymerization. Part I. The radiational degradation).Przegląd Papierniczy, 8, 475-481 (2006).

93. Sun Y., Chmielewski A.G., Bułka S., Zimek Z.Influence of base gas mixture on decomposition of 1,4-dichlorobenzene in an electron beam generatedplasma reactor.Plasma Chemistry and Plasma Processing, 26, 347-359 (2006).

94. Szumiel I.Epidermal growth factor receptor and DNA double strand break repair: the cell’s self-defence.Cellular Signalling, 18, 1537-1548 (2006).

95. Trojanowicz M.Analytical applications of carbon nanotubes: a review.Trends in Analytical Chemistry, 25, 5, 480-489 (2006).


96. Trojanowicz M., Wójcik L., Szostek B., Korczak K., Bojanowska-Czajka A., Drzewicz P., Ma-sar M., Kaniansky D.Application of capillary electrophoresis in analysis of perfluorinated carboxylic acids.Organohalogen Compounds, 68, 2531-2534 (2006).

97. Trybuła Z., Kempiński W., Andrzejewski B., Piekara-Sady L., Kaszyński J., Trybuła M., Pieko-szewski J., Stanisławski J., Barlak M., Richter E.Superconducting regions and Kondo effect of MgB2 formed by implantation of magnesium ions intoboron substrate.Acta Physica Polonica A, 109, 4-5, 657-660 (2006).

98. Tymiński B., Zwoliński K., Jurczyk R.Badania w skali wielkolaboratoryjnej rozkładu odpadów poliolefin na produkty ciekłe (Research onwaste polyolefine degradation into liquid products).Prace Naukowe Instytutu Inżynierii Ochrony Środowiska Politechniki Wrocławskiej z. 81, Seria:Konferencje z. 12, 263-267 (2006).

99. Tymiński B., Zwoliński K., Jurczyk R.Degradation of polyolefine wastes into liquid fuels.Nukleonika, 51, Suppl. 1, s95-s100 (2006).

100. Urbański P., Bartak J., Jakowiuk A., Świstowski E., Machaj B., Kowalska E., Pieńkos J.Nowe urządzenia do promieniowania jonizującego (New instruments for measurements of ionizingradiation).Ekopartner, 11, 24-25 (2006).

101. Urbański P., Bartak J., Jakowiuk A., Świstowski E., Machaj B., Kowalska E., Pieńkos J.Urządzenia promieniowania jonizującego (Instruments of ionizing radiation).Ekologia, 6, 42-43 (2006).

102. Wierzchnicki R.Izotopy stabilne w kontroli pochodzenia żywności (Stable isotopes in the control of food authencity).Postępy Techniki Jądrowej, 49, 1, 22-25 (2006).

103. Wojewódzka M., Buraczewska I., Szumiel I., Grądzka I.DNA double-strand break rejoining in radioadapted human lymphocytes: evaluation by neutral cometassay and pulse-field gel electrophoresis.Nukleonika, 51, 4, 185-191 (2006).

104. Wojewódzka M., Kruszewski M., Ołdak T., Bartłomiejczyk T., Goździk A., Szumiel I.Inhibition of poly(ADP-ribose)polymerase does not affect the recombination events in CHO xrs6 andwild type cells.Radiation and Environmental Biophysics, 45, 277-287 (2006).

105. Wojewódzka M., Szumiel I.Ogniska histonu γ-H2AX. Marker pęknięć podwójnoniciowych DNA (γ-H2AX histone foci – markerof DNA double strand breaks).Postępy Techniki Jądrowej, 49, 3, 15-18 (2006).

106. Wójcik A., Bochenek A., Lankoff A., Lisowska H., Padjas A., Szumiel I., von Sonntag C., Obe G.DNA interstrand crosslinks are induced in cells prelabelled with 5-bromo-2’-deoxyuridine and exposedto UVC radiation.Journal of Photochemistry and Photobiology B: Biology, 84, 15-20 (2006).

107. Wójcik A., Szumiel I., Liniecki J.Hormeza czy to zjawisko powszechne i powszechnie nieznane? (Hormesis, a common phenomenonand commonly unknown?)Postępy Techniki Jądrowej, 49, 2, 34-39 (2006).

108. Yordanov N.D., Fabisiak S., Lagunov O.Effect of the shape and size of dosimeters on the response of solid state/EPR dosimetry.Radiation Measurements, 41, 257-263 (2006).

109. Zagórski Z.P.Radiation chemistry of radioactive waste to be stored in the salt mine repository.Nukleonika, 51, Suppl. 2, s87-s92 (2006).


110. Zagórski Z.P.Radiation induced dehydrogenation of organics: from amino acids, to synthetic polymers, to bacterialspores.Indian Journal of Radiation Research, 3, 2-3, 89-93 (2006).

111. Zakrzewska-Trznadel G.Membrane processes for environmental protection: application in nuclear technology.Nukleonika, 51, Suppl. 1, s101-s111 (2006).

112. Zakrzewska-Trznadel G.Tritium removal from water solutions.Desalination, 200, 737-738 (2006).

113. Zhydachevskii Ya., Suchocki A., Sugak D., Luchechko A., Berkowski M., Warchoł S., Jakieła R.Optical observation of the recharging processes of manganese ions in YalO3:Mn crystals under radia-tion and thermal treatment.Journal of Physics: Condensed Matter, 18, 5389-5403 (2006).

114. Zimek Z.Chemia i technika radiacyjna (Radiation chemistry and technology).Postępy Techniki Jądrowej, 50, 4, 14-20 (2006).

115. Zimek Z., Przybytniak G., Kałuska I.Radiation processing of polymers and semiconductors at the Institute of Nuclear Chemistry and Tech-nology.Nukleonika, 51, Suppl. 1, s129-s132 (2006).

116. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K.Zastosowanie techniki radiacyjnej do otrzymywania napełniaczy bentonitowych i ich mieszanek z poli-propylenem (Application of radiation technique to obtain bentonite fillers and their mixtures with polypro-pylene).Inżynieria Materiałowa, 6, 1333-1336 (2006).

BOOKS

1. Chmielewski A.G., Kang C.M., Kang C.S., Vujic J.L.Radiation technology. Introduction to industrial and environmental applications.Seoul National University Press, Seoul 2006, 274 p.

CHAPTERS IN BOOKS

1. Chiarizia R., Jensen M.P., Borkowski M., Nash K.L.A new interpretation of third-phase formation in the solvent extraction of actinides by TBP.In: Separation for the nuclear fuel cycle in the 21st century. G.L. Lumetta, K.L. Nash, S.B. Clark, J.I. Friese(eds). ACS Symposium Series no. 933. American Chemical Society, Washington, DC 2006, pp. 135-150.

2. Chmielewski A.G., Sun Y.Air emission and off-gas treatment technologies – overview.In: Ochrona powietrza w teorii i praktyce. Tom 1. Red. J. Konieczyński. Instytut Podstaw Inżynierii PAN,Zabrze 2006, pp. 9-16.

3. Deptuła A., Goretta K.C., Olczak T., Łada W., Chmielewski A.G., Jakubaszek U., Sartowska B.,Alvani C., Casadio S., Contini V.Preparation of titanium oxide and metal titanates as powders, thin films, and microspheres by novel inor-ganic sol-gel process.In: Nanoparticles and nanostructures in sensors and catalysis. Chuan-Jian Zhong, N.A. Kotov, W. Daniell,F.P. Zamborini (eds). Materials Research Society Symposium Proceedings vol. 900E. MRS, Warrendale2006, pp. 0900-O09-10.1-10.6.

4. Jakowiuk A., Świstowski E., Urbański P., Pieńkos J., Machaj B., Salwa J.System monitoringu zapylenia powietrza (Wireless system for air dust concentration monitoring).


In: Ochrona powietrza w teorii i praktyce. Tom 2. Red. J. Konieczyński. Instytut Podstaw Inżynierii PAN,Zabrze 2006, pp. 119-127.

5. Pruszyński M., Bilewicz A.Binding of 131I to rhodium(III) complexes: model studies on attaching 211At to metal complexes.In: Application of radiotracers in chemical, environmental and biological sciences. S. Lahiri, D. Layak, A.Mukhopadhyay (eds). Saha Institute of Nuclear Physics, Kolkata 2006. Vol. 2, pp. 20-22.

6. Sun Y., Chmielewski A.G., Bułka S., Zimek Z.Organic pollutants treatment from air using electron beam technology.In: Ochrona powietrza w teorii i praktyce. Tom 1. Red. J. Konieczyński. Instytut Podstaw Inżynierii PAN,Zabrze 2006, pp. 253-257.

7. Zimek Z.Economic benefits of radiation processing applied in Poland.In: A study on economical benefits of industrial applications of radiation and radioisotopes. Report ofConsultants Meeting, Vienna 6-9 December 2004. IAEA, Vienna 2006, pp. 56-63.

THE INCT REPORTS

1. INCT Annual Report 2005.Institute of Nuclear Chemistry and Technology, Warszawa 2006, 235 p.

2. Zakrzewska Trznadel G.Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 1/2006, 191 p.

3. Zakrzewska Trznadel G.Procesy membranowe w technologiach jądrowych – wybrane zagadnienia modelowania transportu masyoraz projektowania systemów rozdzielania (Membrane processes in nuclear technologies – selected issuesof mass tansport modeling and separation systems design).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 2/2006, 80 p.

4. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu-ła M., Szopa Z.Polish reference material: Corn Flour (INCT-CF-3) for inorganic trace analysis – preparation and certi-fication.Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria A nr 3/2006, 47 p.

5. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu-ła M., Szopa Z.Polish reference material: Soya Bean Flour (INCT-CBF-4) for inorganic trace analysis – preparationand certification.Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria A nr 4/2006, 51 p.

6. Herdzik I.ICP-MS jako metoda oznaczania stosunków izotopowych galu, indu i talu w badaniach efektów izotopo-wych w układach chromatograficznych (ICP-MS as the method of the determination of gallium, indiumand tallium isotope ratios in the studies of isotope effects in the chromatography systems).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 5/2006, 19 p.

7. Pawlukojć A.Badania widm oscylacyjnych, w obszarze niskich częstości, wybranych kompleksów molekularnych z prze-niesieniem ładunku oraz ich składników metodą nieelastycznego rozpraszania neutronów termicznych(The investigations of low frequency oscillation spectra of selected charge transfer molecular complexesand their compounds by inelastic thermal neutron spectroscopy).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 6/2006, 100 p.

8. Chmielewski A.G.Packaging for food irradiation.Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria B nr 1/2006, 26 p.


9. Polkowska-Motrenko H., Dudek J., Chajduk E., Sypuła M., Sadowska-Bratek M.Badania biegłości ROŚLINY 6 – oznaczanie zawartości As, Cd, Cu, Hg, Pb, Se i Zn w grzybach suszonych(maślak sitarz) (Proficiency test PLANT 6 – determination of As, Cd, Cu, Hg, Pb, Se and Zn in drymushroom powder (Suillus bovinus)).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 2/2006, 22 p.

10. Zimek Z., Dźwigalski Z., Warchoł S., Roman K., Bułka S.Modernizacja Stacji Sterylizacji Radiacyjnej wyposażonej w akcelerator elektronów ELEKTRONIKA10/10. Część I (Upgrading of Radiation Sterilization Facility equipped with electron acceleratorELEKTRONIKA 10/10. Part I).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 3/2006, 28 p.

11. Malec-Czechowska K., Laubsztejn M., Strzelczak G., Stachowicz W.Wykrywanie napromieniowania farmaceutyków zawierających składniki pochodzenia roślinnego metodąpomiaru termoluminescencji oraz metodą spektroskopii elektronowego rezonansu paramagnetycznego(Detection of irradiation in herbal pharmaceuticals with the use of thermoluminescence and electronparamagnetic resonance spectroscopy).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 4/2006, 18 p.

12. Mehta K., Bułka S.Dosimetry for combustion flue gas treatment with electron beam.Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria B nr 5/2006, 26 p.

13. Lewandowska-Siwkiewicz H., Kruszewski M.Dinitrozylowe kompleksy żelaza w układach biologicznych (Dinitrosyl iron complexes in biological sys-tems).Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 6/2006, 36 p.

CONFERENCE PROCEEDINGS

1. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M., Nałęcz-Jawecki G., Sawicki J., Zimek Z.,Nichipor H.Analityczne badania radiolitycznej degradacji wybranych pestycydów (Analytical control of radiolyticaldecomposition of selected pesticides).Dla miasta i środowiska – IV konferencja: Problemy unieszkodliwiania odpadów, Warszawa, Poland,27.11.2006, pp. 23-26.

2. Chmielewski A.G.Practical applications of radiation chemistry.Physical chemistry. Proceedings of the 8th international conference on fundamental and applied aspectsof physical chemistry, Belgrade, Serbia, 26-29.09.2006. Vol. 1, pp. 38-46.

3. Chmielewski A.G., Pawelec A., Tymiński B., Zimek Z.Parametric analysis of the electron beam process for SO2 and NOx removal.V European meeting on chemical industry and environment, 3-5.05.2006, Vienna, Austria. W. Höflinger(ed.). Vienna University of Technology, Vienna. Vol. I, pp. 598-606.

4. Chmielewski A.G., Sun Y., Bułka S., Zimek Z.Chlorinated organic compounds decomposition in air in an electron beam generated plasma reactor.The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Pro-ceedings, [3] p.

5. Dybczyński R.The position of NAA among the methods of inorganic trace analysis in the past and now.Proceedings of the enlargement workshop on neutron measurement, evaluations and applicationsNEMEA-2, Bucharest, Romania, 20-23.10.2004. A.J.M. Plompen (ed.). Report EUR 22136 EN. Insti-tute for Reference Materials and Measurements, Luxemburg [2006], pp. 85-88.

6. Harasimowicz M., Orluk P., Zakrzewska-Trznadel G., Chmielewski A.G.Application of polyimide membranes for biogas purification and enrichment.V European meeting on chemical industry and environment, 3-5.05.2006, Vienna, Austria. W. Höflinger(ed.). Vienna University of Technology, Vienna. Vol. I, pp. 617-625.


7. Harasimowicz M., Ziółkowska W., Zakrzewska-Trznadel G., Chmielewski A.G.Economical comparison of absorption and membrane methods applied for enrichment of methane in biogas.“Ars Separatoria 2006”: Proceedings of the XXI International Symposium on Physico-Chemical Methodsof Separation, Toruń, Poland, 2-5.07.2006. J. Ceynowa, R. Wódzki (eds.). Nicolaus Copernicus University,Toruń 2006, pp. 52-54.

8. Łyczko M., Schibli R., Narbutt J.Substitution of imidazole and bombesin for water in aquatricarbonyl(n-methyl-2-piridenecarbothioamide)technetium(I) cation. [2+1] approach.Technetium, rhenium and other metals in chemistry and nuclear medicine. Proceedings of the 7th Inter-national symposium on technetium in chemistry and nuclear medicine, Italy, 6-9.09.2006. U. Mazzi (ed.)SGE Editoriali, Padova 2006, pp. 335-336.

9. Owczarczyk A., Palige J., Dobrowolski A., Chmielewski A.G., Ptaszek S.CFD and RTD methods for industrial wastewater treatment plants settler investigation.V European meeting on chemical industry and environment, 3-5.05.2006, Vienna, Austria. W. Höflinger(ed.). Vienna University of Technology, Vienna. Vol. I, pp. 96-103.

10. Polkowska-Motrenko H., Dobkowski Z.Rola porównań międzylaboratoryjnych w procesie doskonalenia systemu zarządzania (Role of ILC inthe advancement of management system).XII Sympozjum: Doskonalenie systemu zarządzania w laboratorium, Gdańsk-Sobieszowa, Poland,21-23.05.2006. (I tura). Materiały sympozjum, pp. 73-78.

11. Polkowska-Motrenko H., Dobkowski Z.Rola porównań międzylaboratoryjnych w procesie doskonalenia systemu zarządzania (Role of ILC inthe advancement of management system).XII Sympozjum: Doskonalenie systemu zarządzania w laboratorium, Ustroń, Poland, 10-12.09.2006. (IItura), pp. 85-90.

12. Samczyński Z., Łyczko M., Dybczyński R., Narbutt J.Ion exchange studies on the organometallic aqua-ion fac-[99mTc(CO)3(H2O)3]+ in acidic aqueous solutions.Technetium, rhenium and other metals in chemistry and nuclear medicine. Proceedings of the 7th Inter-national symposium on technetium in chemistry and nuclear medicine, Italy, 6-9.09.2006. U. Mazzi (ed.).SGE Editoriali, Padova 2006, pp. 125-126.

13. Zagórski Z.P.Radiation induced dehydrogenation of organics: from amino acids, to synthetic polymers, to bacterialspores.Proceedings of Trombay Symposium on Radiation and Photochemistry, Mumbai, India, 5-9.01.2006.Vol. I: Invited talks, pp. 97-99.

14. Zakrzewska-Trznadel G., Harasimowicz M., Miśkiewicz A., Chmielewski A.G., Dłuska E., Wroń-ski S., Jaworska A.Reducing the fouling and boundary layer phenomena in membrane processes for radioactive wastestreatment.“Ars Separatoria 2006”: Proceedings of the XXI International Symposium on Physico-Chemical Methodsof Separation, Toruń, Poland, 2-5.07.2006. J. Ceynowa, R. Wódzki (eds.). Nicolaus Copernicus University,Toruń 2006, pp. 140-141.

15. Zimnicki R., Owczarczyk A., Chmielewski A.G.Obserwacja zmian parametrów hydrochemicznych wód podziemnych w rejonie powstającej kopalniodkrywkowej węgla brunatnego (Investigations of groundwater composition and hydrological conditionchanges in area of formation of an open-cast lignite mine).Postęp w inżynierii środowiska. IV Ogólnopolska konferencja naukowo-techniczna, Rzeszów-Bystre k.Baligrodu, Poland, 21-23.09.2006. Pod red. J.A. Tomaszka, pp. 521-529.

CONFERENCE ABSTRACTS

1. Bobrowski K., Hug G.L., Hörner G., Marciniak B., Pogocki D., Schöneich C.Sulfide radical cation chemistry in cyclic dipeptides.20th International Symposium on Radical Ion Reactivity: ISRIR 2006, Rome, Italy, 2-6.07.2006, IL14,[1] p.


2. Bobrowski K., Hug G.L., Pogocki D., Hörner G., Marciniak B., Schöneich C.Stabilization of sulfide cations: mechanisms relevant to oxidation of peptides and proteins containingmethionine.The 1st Asian-Pacific Symposium on Radiation Chemistry, Shanghai, China, 17-21.09.2006. Conferenceabstract book, pp. 58-59.

3. Bobrowski K., Hug G.L., Pogocki D., Marciniak B., Schöneich C.Stabilization of sulfide radical cations through complexation with the peptide bond.RADAM’06: Radiation Damage in Biomolecular Systems, Groningen, The Netherlands, 6-9.06.2006,[1] p.

4. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M.Analityczne badania radiolitycznej degradacji karbendazymu (Analytical control of carbendazim de-composition by gamma irradiation).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 21.

5. Brzóska K., Kruszewski M., Szumiel I.Defect in double-stranded DNA breaks repair in L5178Y-S cells is not associated with alterations inthe autophosphorylation sites of DNA-dependent protein kinase.The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 37.

6. Celuch M., Enache M., Pogocki D.Acid-base catalysis of singlet oxygen-induced oxidation of alkylthiocarboxylic acids.12th International Conference on Physical Chemistry - Romphyschem-12, Bucharest, Romania, 6-8.09.2006.Abstract book, p. 60.

7. Celuch M., Enache M., Pogocki D.Reakcje jednoelektronowego utleniania kwasów alkilotiokarboksylowych (Reactions of one-electronoxidation of alkylthiocarboxylic acids).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 24.

8. Chajduk E., Dybczyński R.Nowa metoda oznaczania śladowych ilości As w materiałach biologicznych za pomocą radiochemicznejneutronowej analizy aktywacyjnej (Determination of trace amounts of arsenic in biological samples byRNAA).XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S8-P20, p.200.

9. Chajduk E., Polkowska-Motrenko H., Dybczyński R.Konstruowanie metod o najwyższej randze metrologicznej dla oznaczania Se w materiałach biologicznychza pomocą RNAA (A new, high accuracy RNAA method for selenium determination in biologicalmaterials).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 25.

10. Chajduk E., Polkowska-Motrenko H., Dybczyński R.Metoda definitywna oznaczania selenu w matrycach biologicznych (Definitive method for seleniumdetermination in biological materials).VI Sesja przeglądowa analityki żywności, Warszawa, Poland, 17.11.2006. Materiały sesji, p. 17.

11. Chmielewski A.G.Industrial scale processing of flue gases from electric and heat power plants.Workshop on the Plasma-Assisted Combustion and Plasma-Aftertreatment of Combustion Flue Gasesfor Power Industry, Gdańsk, Poland, 28-31.05.2006. Book of abstracts, p. 13.

12. Chmielewski A.G.Industrial applications of electron beam flue gas treatment – from laboratory to the practice.11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts,p. 50.

13. Chmielewski A.G.Technologiczne aspekty chemii radiacyjnej (Technological aspects of radiation chemistry).XLIX Zjazd PTChem i SIPChem, Gdańsk, Poland, 18-21.09.2006. Materiały zjazdowe, S12, W-1, p.283.


14. Chmielewski A.G.Water pollutants degradation by electron beam.The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Bookof abstracts, p. 17.

15. Chmielewski A.G., Chmielewska D.K., Sampa M.H.Prospects and challenges in application of gamma and electron beam processing of nanomaterials.IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey,23-28.09.2006. Book of abstracts, p. 44.

16. Chmielewski A.G., Haji-Saeid M., Ramamoorthy N.Fostering new developments in radiation processing and IAEA’s role.14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Con-ference abstracts book, [1] p.

17. Chmielewski A.G., Migdał W., Świętosławski J., Jakubaszek U., Tarnowski T.Chemical-radiation degradation of natural oligo-aminopolysaccharides and product agricultural appli-cations.14th International Meeting on Radiation Processing (IMRP), Kuala Lumpur, Malaysia, 26.02.-3.03.2006.Conference abstracts book, p. 198.

18. Chmielewski A.G., Sun Y., Bułka S., Zimek Z.Chlorinated organic compounds decomposition in air in an electron beam generated plasma reactor.The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Bookof abstracts, p. 55.

19. Chmielewski A.G., Sun Y., Bułka S., Zimek Z.Dosimetric methods for laboratory scale VOC treatment.The Workshop on dosimetry for radiation applications in technologies for environment pollution con-trol, Warszawa, Poland, 5.04.2006, p. 4.

20. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L.Oznaczanie kadmu, ołowiu, miedzi i bizmutu w wodach mineralnych metodą GF-AAS po wydzieleniuza pomocą ekstrakcji do fazy stałej (Determination of cadmium, lead, copper and bismuth in mineralwaters by GF-AAS after preconcentration on dithizone sorbent).Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVPoznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 115.

21. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L.Sorbent chelatujący z ditizonem, własności analityczne i możliwości zastosowania (Chelating sorbentwith dithizon – analytical property and possibility of use).Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVPoznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 114.

22. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L.Własności analityczne i możliwości zastosowania sorbentu chelatującego z ditizonem (Analytical prop-erties and applications of dithizone sorbent).XI Konferencja: Zastosowanie metod AAS, ICP-AES, ICP-MS w analizie środowiskowej – ThermoElectron, Warszawa, Poland, 9-10.11.2006, PO-03, p. 22.

23. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L.Zastosowanie ekstrakcji do fazy stałej przy oznaczaniu metali ciężkich metodą GF-AAS (Applicationof solid-phase extraction for determination of heavy metals by GF-AAS).XI Konferencja: Zastosowanie metod AAS, ICP-AES, ICP-MS w analizie środowiskowej – ThermoElectron, Warszawa, Poland, 9-10.11.2006, PO-04, p. 23.

24. Cieśla K., Eliasson A.-C.DSC studies of retrogradation and amylose-lipid complex transition taking place in gamma irradiatedwheat starch.IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey,23-28.09.2006. Book of abstracts, p. 45.

25. Cieśla K., Lundqvist H., Eliasson A.-C.Surface tension and WAXS diffraction studies of binding cetyltrimethyl-ammonium bromide to gammairradiated and nonirradiated potato starch.XIV International Starch Convention Cracow-Moscow, Cracow, Poland, 20-24.06.2006, pp. 66-67.


26. Cieśla K., Rahier H.Gamma irradiation effect on interaction of potato starch with lipids and surfactants studied by DSC.ESTAC 9: 9th European Symposium on Thermal Analysis and Calorimetry, Kraków, Poland, 27-31.08.2006,p. 26.

27. Cieśla K., Sartowska B., Królak E.Gamma irradiation influence on structure of potato starch gels studied by SEM.XIV International Starch Convention Cracow-Moscow, Cracow, Poland, 20-24.06.2006, pp. 106-107.

28. Cieśla K., Vansant E.F.Physico-chemical changes taking place in gamma irradiated bovine globulins studied by thermal analysis.ESTAC 9: 9th European Symposium on Thermal Analysis and Calorimetry, Kraków, Poland, 27-31.08.2006,p. 37.

29. Danko B., Dybczyński R., Kulisa K., Samczyński Z.Oznaczanie lantanowców w próbkach biologicznych za pomocą neutronowej analizy aktywacyjne i chro-matografii jonów (Determination of the lanthanides in biological samples by NAA and IC).XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S8-P23, p.200.

30. Danko B., Dybczyński R., Kulisa K., Samczyński Z.Schemat wydzielania frakcji lantanowców z materiałów pochodzenia roślinnego oraz środowiskowego(A scheme for the separation of lanthanide fraction from materials of biological and environmentalorigin).Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVPoznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 136.

31. Dybczyński R.Contribution of NAA to the certification of reference materials for inorganic trace analysis.NEMEA-3: 3rd Workshop on Neutron Measurements, Evaluations and Applications, Borovets, Bul-garia, 25-28.10.2006. Book of abstracts, p. 19.

32. Dybczyński R.Neutronowa analiza aktywacyjna i jej znaczenie dla zapewnienia jakości wyników analitycznych w nie-organicznej analizie śladowej (Neutron activation and its significance for the assurance of the qualityof analytical results in inorganic trace analysis).XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S12-W2, p.283.

33. Dybczyński R.Zarys historii, zastosowania i znaczenie materiałów odniesienia w nieorganicznej analizie śladowej(Historical outline of the application and significance of reference materials in inorganic trace analysis).Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVPoznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 147.

34. Dybczyński R., Danko B., Polkowska-Motrenko H., Samczyński Z.Metody definitywne oparte na radiochemicznej neutronowej analizie aktywacyjnej i ich miejsce w metro-logii chemicznej (Definitive methods based on radiochemical neutron activation and their position inchemical metrology).Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 23-24.11.2006,[1] p.

35. Dybczyński R., Danko B., Polkowska-Motrenko H., Samczyński Z.The place of highly accurate methods by RNAA in metrology.15th Radiochemical Conference, Mariánské Lázne, Czech Republic, 23-28.04.2006. Booklet of ab-stracts, p. 84.

36. Dybczyński R., Kulisa K.Wpływ temperatury na proces rozdzielania w chromatografii jonowymiennej i chromatografii pasmachromatograficznego (Influence of temperature on the separation process in ion exchange chromatog-raphy and ion chromatography and the mechanism of band spreading).VII Konferencja chromatograficzna: chromatografia i techniki pokrewne a zdrowie człowieka, Białystok,Poland, 10-13.10.2006, pp. 19-20.

37. Filipczak K., Ulanski P., Przybytniak G., Olah L., Rosiak J.M.Some observations on the effect of ionizing radiation on poly(ε-caprolactone).


11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts,p. 91.

38. Filipczak K., Ulanski P., Przybytniak G., Rosiak J.M.Studies on the free radical chemistry of poly(ε-caprolactone).IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey,23-28.09.2006. Book of abstracts, p. 125.

39. Fuente J. De la, Sobarzo-Sánchez E., Bobrowski K.Spectroscopic characterization of radicals species from 2,3-dihydro-oxoisoaporphines generated by flashphotolysis and pulse radiolysis.XVIII International Conference on Physical Organic Chemistry, Warsaw, Poland, 20-25.08.2006, p. 57.

40. Fuks L.Pt(II) chloride complexed by tetrahydrofurylthiourea or tetrahydrotiophenylthiourea: structural andbiological features.3rd Central European Conference: Chemistry towards biology – CHTB 2006, Kraków, Poland, 8-12.09.2006,P-8, [1] p.

41. Giglio J., León E., Rey A., Künstler J.-U., Gniazdowska E., Decristoforo C., Pietzsch H.-J.99mTc-labelled RGD-peptides using the „4+1” mixed-ligand approach.Technetium, rhenium and other metals in chemistry and nuclear medicine. 7th International Sympo-sium, Italy, 6-9.09.2006. U. Mazzi, A. Nadali (eds). Abstracts, 3AP12, p. 46.

42. Głuszewski W., Zagórski Z.P.Chemia radiacyjna mieszanin polimerowych PP/PS (Radiation chemistry of PP/PS polymer mixtures).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 34.

43. Głuszewski W., Zagórski Z.P.Radiation effects on PP/PS blends as a model of protection effects by aromatics.IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey,23-28.09.2006. Book of abstracts, p. 128.

44. Głuszewski W., Zagórski Z.P.Zjawiska ochronne w chemii radiacyjnej polimerów (Protective phenomena in the radiation chemistryof polymers).9. Spotkanie Inspektorów Ochrony Radiologicznej, Dymaczewo Nowe, Poland, 20.05.-2.06.2006.Materiały konferencyjne, pp. 15-16.

45. Grądzka I., Sochanowicz B., Buraczewska I., Szumiel I.Participation of the EGF receptor in the response to X-irradiation in human glioma M059 K and J cells.The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 42.

46. Grodkowski J., Kocia R., Mirkowski J.Radioliza impulsowa przejściowych widm absorpcyjnych p-terfenylu w cieczy jonowej bis[(trifluoro-metylo)sulfonylo] imidzie metylotributyloamoniowym (R4NNTF2) (Pulse radiolysis of intermediateabsorption spectra of p-terphenyl in ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfo-nyl]imide).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 56.

47. Gryz M., Starosta W., Leciejewicz J.Crystal structure of zinc(II) pyrazolate trihydrate.48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów,A-22, p. 71.

48. Gryz M., Starosta W., Leciejewicz J.Monomeric molecules in the crystal structures of magnesium(II) and zinc(II) structures with imida-zole-4-carboxylate and water ligands.48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów,A-23, pp. 72-73.

49. Herdzik I.Separacja izotopów galu i indu z wykorzystaniem chromatografii jonowymiennej (Separation of gal-lium and indium isotopes using ion-exchange chromatography).


ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 40.

50. Kałuska I., Lazurnik V.T., Lazurnik V.M., Popov G.F., Rogov Y.V., Zimek Z.The features of electron dose distribution in circular objects: comparison of Monte Carlo simulationpredictions with dosimetry.14th International Meeting on Radiation Processing (IMRP), Kuala Lumpur, Malaysia, 26.02.-3.03.2006.Conference abstracts book, p. 206.

51. Kciuk G., Hug G., Mirkowski J., Bobrowski K.Intramolecular electron transfer in dipeptides containing tyrosine.11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts,p. 10.

52. Kciuk G., Hug G., Mirkowski J., Bobrowski K.Radiation-induced oxidation of dipeptides containing tyrosine and methionine: influence of aminoacid sequence, pH and conformation.12th International Conference on Physical Chemistry – Romphyschem-12, Bucharest, Romania, 6-8.09.2006.Abstract book, p. 61.

53. Kciuk G., Hug G., Mirkowski J., Bobrowski K.Utlenianie dipeptydów zawierających reszty tyrozyny i metioniny: badania metodą radiolizy impulsowej(Oxidation of dipeptides containing tyrosine and methionine; studies by pulse radiolysis).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 52.

54. Kocia R., Grodkowski J., Mirkowski J.Pulse radiolysis study of the formation the p-terphenyl radical anion in the ionic liquid methyltributyl-ammonium bis[(trifluoromethyl)sulfonyl]imide (R4NNTf2).12th International Conference on Physical Chemistry - Romphyschem-12, Bucharest, Romania, 6-8.09.2006.Abstract book, p. 116.

55. Kornacka E.M., Przybytniak G., Rafalski A., Kozakiewicz J.Radiation induced effects in segmented poly(siloxaneurethane) ureas based on aliphatic and aromaticdiisocyanates.11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts,p. 77.

56. Kornacka E.M., Przybytniak G., Święszkowski W.Influence of crystallinity on radiation stability of PE.Workshop on Biotribology, COST 533, Warszawa, Poland, 6.10.2006, pp. 8-9.

57. Krejzler J., Narbutt J., Foreman M.R.St J., Hudson M.J., Casensky B., Madic C.Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of n-triden-tate heterocycles and chlorinated cobalt dicarbollide.15th Radiochemical Conference, Mariánské Lázne, Czech Republic, 23-28.04.2006. Booklet of ab-stracts, p. 212.

58. Kruszewski M., Iwaneńko T., Woliński J., Wojewódzka M.Differential action of human metabolism and energy regulators on the lymphocyte susceptibility toionizing radiation.III International and VI Cuban Mutagenesis, Teratogenesis and Carcinogenesis Workshop, Havana,Cuba, 25-27.09.2006, p. 8.

59. Kruszewski M., Iwaneńko T., Woliński J., Wojewódzka M.Ghrelin, a natural ligand for the GHS receptor, sensitizes blood mononuclear cells to oxidative stress.III International and VI Cuban Mutagenesis, Teratogenesis and Carcinogenesis Workshop, Havana,Cuba, 25-27.09.2006, p. 30.

60. Kruszewski M., Iwaneńko T., Woliński J., Zabielski R., Wojewódzka M.Ghrelin, a natural ligand for the growth hormone secretagogue receptor, sensitizes blood mononuclearcells to oxidative stress.The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 45.


61. Kruszewski M., Lewandowska H., Męczyńska S., Sochanowicz B., Sadło J.Differential action of permeable and non-permeable iron chelators on formation on dinitrosyl ironcomplexes in vivo.16th International Conference on Chelators (ICOC), Limassol, Cyprus, 25-31.10.2006, p. 32.

62. Kulisa K., Dybczyński R., Danko B., Samczyński Z.Wstępne wydzielanie grupy lantanowców z materiałów biologicznych i środowiskowych i ich oznaczanieza pomocą chromatografii jonów (Preliminary separation of the lanthanides as a group from biologicaland environmental materials and their determination by ion chromatography).VII Konferencja chromatograficzna: chromatografia i techniki pokrewne a zdrowie człowieka, Białystok,Poland, 10-13.10.2006, p. 97.

63. Łyczko K., Starosta W.The structures of lead(II) complexes with tropolone.ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 67.

64. Łyczko M.Trikarbonylkowe kompleksy technetu(I) z lipofilowymi ligandami bidentnymi (Tricarbonyl complexesof technetium(I) with bidentate lyophylic ligands).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 68.

65. Łyczko M., Schibli R., Narbutt J.Substitution of imidazole and bombesin for water in aquatricarbonyl(n-methyl-2-piridenecarbothio-amide) technetium(I) cation. 2+1 approach.Technetium, rhenium and other metals in chemistry and nuclear medicine. 7th International Sympo-sium, Italy, 6-9.09.2006. U. Mazzi, A. Nadali (eds). Abstracts, 3AP14, p. 47.

66. Maddukuri L., Christiansen M., Dudzińska D., Zaim J., Obutulowicz T., Komisarski M., WójcikA., Kusmierek J., Stevnsner T., Bohr A., Tudek B.Cockayane syndrome group B protein in involved in repairing of DNA adducts induced by trans-4-hy-droxy-2-nonenal.The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 47.

67. Majkowska A., Bilewicz A.Formation kinetics and stability of some TRI and tetraaza derivative complexes of scandium.ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 72.

68. Marciniak B., Hug G.L., Hörner G., Bobrowski K.Reactive intermediates in the photo-oxidation of sulfur-containing organic compounds.20th International Symposium on Radical Ion Reactivity: ISRIR 2006, Rome, Italy, 2-6.07.2006, IL3,[1] p.

69. Męczyńska S., Lewandowska H., Kruszewski M.The role of lysosomal iron in ·NO signaling.ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 77.

70. Męczyńska S., Lewandowska-Siwkiewicz H., Kruszewski M.Interaction of dinitrosyl iron complexes with DNA.The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 49.

71. Narbutt J., Krejzler J.Heteroleptic complexes of Am(III) and Eu(III) with a triazinylbipyridine derivative. Multiple regres-sion analysis of solvent extraction data.37th International Conference on Coordination Chemistry (ICCC), Cape Town, South Africa, 13-18.08.2006.D.J. Robinson, I.M. Robinson (eds.). Oral abstracts, p. 222.

72. Narbutt J., Krejzler J.Oddzielanie trójwartościowych aktynowców od lantanowców w odpadach promieniotwórczych z prze-robu wypalonych paliw jądrowych (Separation of trivalent actinides from lanthanides in radioactivewastes from reprocessing of spent nuclear fuels).XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S12-W4, p.284.


73. Ostapczuk A.Electron beam application for volatile organic compounds removal.The Workshop on dosimetry for radiation applications in technologies for environment pollution con-trol, Warszawa, Poland, 5.04.2006, p. 5.

74. Pawlukojć A., Starosta W., Leciejewicz J., Natkaniec I., Nowak D.The molecular structure and dynamics of 2-aminopyridine-3-carboxylic acid by X-ray diffraction, in-elastic neutron scattering, infrared, Raman spectroscopy and from first principles calculations.V Workshop on investigations at the IBR-2 pulsed reactor, Dubna, Russia, 14-17.06.2006. Programmeand abstracts, p. 58.

75. Polkowska-Motrenko H.Badania biegłości laboratoriów oznaczających pierwiastki toksyczne w żywności (Proficiency testing oflaboratories determining toxic elements in food).XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, p. 221.

76. Polkowska-Motrenko H., Chajduk E., Dybczyński R.Oznaczanie selenu w materiałach biologicznych za pomocą metody definitywnej opartej na radio-chemicznej neutronowej analizie aktywacyjnej (Determination of selenium in biological samples bydefinitive method based on RNAA).Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVPoznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 90.

77. Polkowska-Motrenko H., Dybczyński R.Działalność Instytutu Chemii i Techniki Jądrowej w dziedzinie zapewnienia jakości w nieorganicznejanalizie śladowej (Activities of the Institute of Nuclear Chemistry and Technology in the domain ofquality assurance for inorganic trace analysis).VI Sesja przeglądowa analityki żywności, Warszawa, Poland, 17.11.2006. Materiały sesji, p. 13.

78. Polkowska-Motrenko H., Dybczyński R.Program badań biegłości ROŚLINY – oznaczanie zawartości As, Cd, Cu, Hg, Se, Pb i Zn w żywnościpochodzenia roślinnego (PT scheme: PLANTS – determination of As, Cd, Cu, Hg, Se, Pb and Zn infood of plant origin).Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 23-24.11.2006,[1] p.

79. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu-ła M., Szopa Z.Nowe polskie atestowane materiały odniesienia: Mąka Kukurydziana INCT-CF-3 i Mąka SojowaINCT-SBF-4 dla potrzeb nieorganicznej analizy śladowej – przygotowanie i atestacja (New Polish CRMs:Corn Flour INCT-CF-3 and Soya Bean Flour INCT-SBF-4 for the purpose of inorganic trace analysis– preparation and certification).Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 23-24.11.2006,[1] p.

80. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu-ła M., Szopa Z.Nowe polskie certyfikowane materiały odniesienia dla potrzeb nieorganicznej analizy śladowej: MąkaKukurydziana INCT-CF-3 i Mąka Sojowa INCT-SBF-4 (New Polish certified reference materials: CornFlour INCT-CF-3 and Soya Beam Flour INCT-SBF-4 for inorganic trace analysis).XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006, S8-K40, p. 194.

81. Polkowska-Motrenko H., Fuks L., Sypuła M.Badania biegłości laboratoriów monitorujących skażenia promieniotwórcze kraju (Proficiency testingof laboratories monitoring country radionuclide contamination).XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, p. 289.

82. Polkowska-Motrenko H., Sadowska-Bratek M.Badanie trwałości materiałów odniesienia metodą NAA (Studies of the stability of reference materialsby the NAA method).Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVPoznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 92.

83. Przybytniak G., Kornacka E.M., Kozakiewicz J.Radical processes in segmented poly(siloxaneurethaneureas) induced by ionizing radiation.


IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey,23-28.09.2006. Book of abstracts, p. 160.

84. Przybytniak G., Kornacka E., Mirkowski K., Nowicki A., Rafalski A.Radiation degradation of blends polypropylene/poly(ethylene-co-vinyl acetate).11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts,p. 16.

85. Rafalski A., Przybytniak G., Kornacka E., Mirkowski K., Nowicki A.Influence of copolymers on radiation resistance of polypropylene blends.XVII International Conference on Physical Organic Chemistry, Warszawa, Poland, 20-25.08.2006, p.80.

86. Ramamoorthy N., Haji-Saeid M., Chmielewski A.G., Chupov A.IAEA’s support to radiation processing technology practices in developing countries.14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Con-ference abstracts book, [1] p.

87. Sadło J., Michalik J., Danilczuk M., Turek J.Silver clusters in molecular sieves.E-MRS 2006 Fall Meeting, Warszawa, Poland, 4-8.09.2006. Book of abstracts, p. 71.

88. Samczyński Z., Łyczko M., Dybczyński R., Narbutt J.Badania trikarbonylkowych kompleksów technetu(I) metodą chromatografii jonowymiennej i elektro-forezy bibułowej (Investigations of tricarbonyl complexes of technetium(I) by ion exchange chroma-tography and paper electrophoresis).VII Konferencja chromatograficzna: chromatografia i techniki pokrewne a zdrowie człowieka, Białystok,Poland, 10-13.10.2006, pp. 72-74.

89. Samczyński Z., Łyczko M., Dybczyński R., Narbutt J.Ion exchange studies on the organometallic aqua-ion fac-[99mTc(CO)3(H2O)3]+ in acidic aqueous solu-tions.Technetium, rhenium and other metals in chemistry and nuclear medicine. 7th International Sympo-sium, Italy, 6-9.09.2006. U. Mazzi, A. Nadali (eds). Abstracts, 3AP26, p. 18.

90. Starosta W., Leciejewicz J.The crystal structure of a calcium(II) complex with pyridazine-3-carboxylate and water ligands.48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów,B-27, p. 161.

91. Starosta W., Leciejewicz J.Three-dimensional polymeric molecular pattern in the crystal structure of a Ca(II) complex with pyra-zine-2,3,5,6-tetracarboxylate and water ligands.48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów,B-28, pp. 162-163.

92. Trojanowicz M., Drzewicz P., Bojanowska-Czajka A., Nałęcz-Jawecki G., Sawicki J.Radiolytic removal of selected pesticides from industrial wastes.SETAC Asia/Pacific 2006. Growth with a limit: the integration of ecosystem protection for humanhealth benefits, Peking, China, 18-20.09.2006. Abstracts, [1] p.

93. Trojanowicz M., Szydłowska D., Campas M., Marty J.-L.Determination of microcystins in surface waters using amperometric screen-printed biosensor withimmobilized protein phosphatase and high-performance liquid chromatography.SETAC Asia/Pacific 2006. Growth with a limit: the integration of ecosystem protection for humanhealth benefits, Peking, China, 18-20.09.2006. Abstracts, [1] p.

94. Turek J., Michalik J.Rodniki srebroorganiczne (Organosilver radicals).ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006.Streszczenia, p. 108.

95. Wierzchnicki R., Derda M.Stable isotopes composition in milk origin control.3rd Central European Congress on Food, Sofia, Bulgaria, 22-24.05.2006. Book of abstracts, p. 209.


96. Wojewódzka M., Kruszewski M., Buraczewska I., Xu W., Massuda E., Zhang J., Szumiel I.Sirtuin inhibition increases the rate of DNA-PK-independent double-strand break repair.III International and VI Cuban Mutagenesis, Teratogenesis and Carcinogenesis Workshop, Havana,Cuba, 25-27.09.2006, p. 31.

97. Wojewódzka M., Kruszewski M., Buraczewska I., Xu W., Massuda E., Zhang J., Szumiel I.Type III histone deacetylases inhibition increases the rate of DNA-PK-independent DSB repair.The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 61.

98. Zagórski Z.P.Prebiotic chemical raw material for life.4th International School on Complexity: Basic questions about the origin of life, Cerice, Italy, 2-5.10.2006,p. 26.

99. Zagórski Z.P.Pulse radiolysis of solids.Pune University Workshop on Radiation and Photochemistry (PUWORP-2006), Pune, India, 10-11.01.2006,[1] p.

100. Zagórski Z.P.Role of ionizing in contribution to homochirality as the signature of life.4th International School on Complexity: Basic questions about the origin of life, Cerice, Italy, 2-5.10.2006,p. 51.

101. Zimek Z.Characteristics and capabilities of X-ray converters applied in radiation processing.11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts,p. 35.

102. Zimek Z.Dosimetric method for industrial scale flue gas treatment.The Workshop on dosimetry for radiation applications in technologies for environment pollution con-trol, Warszawa, Poland, 5.04.2006, p. 6.

103. Zimek Z., Chmielewski A.G.Implementation of high power electron accelerators for environmental protection.RuPAC 2006: XXth Russian Conference on Charged Particle Accelerators, Novosibirsk, Russia,10-14.09.2006. Abstracts brochure, p. 109.

104. Zimek Z., Dźwigalski Z., Warchoł S., Bułka S., Roman K.Upgrading of accelerator facility for radiation sterilization.RuPAC 2006: XXth Russian Conference on Charged Particle Accelerators, Novosibirsk, Russia,10-14.09.2006. Abstracts brochure, p. 108.

105. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K.Modification of bentonite fillers using ionizing radiation.E-MRS 2006 Fall Meeting, Warszawa, Poland, 4-8.09.2006. Book of abstracts, p. 113.

SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 2005

CHAPTERS IN BOOKS

1. Dalivelya O., Savina N., Buraczewska I., Grądzka I., Szumiel I.Effects of an antimutagen of 1,4-dihydropyridine series on cell survival in X-irradiated murine L5178Ysublines.In: Molekularnaya i prikladnaya genetika. Institut Genetiki i Citologii Nacional’noj Akademii NaukBelarusi, Minsk 2005. Naucnye trudy, Tom 1, p. 292.

NUKLEONIKA186

NUKLEONIKATHE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH

EDITORIAL BOARD

Andrzej G. Chmielewski (Editor-in-Chief, Poland), Krzysztof Andrzejewski (Poland), Janusz Z. Beer(USA), Jacqueline Belloni (France), Grażyna Bystrzejewska-Piotrowska (Poland), Gregory R.Choppin (USA), Władysław Dąbrowski (Poland), Hilmar Förstel (Germany), Andrei Gagarinsky(Russia), Andrzej Gałkowski (Poland), Evgeni A. Krasavin (Russia), Stanisław Latek (Poland),Robert L. Long (USA), Sueo Machi (Japan), Dan Meisel (USA), Jacek Michalik (Poland), JamesD. Navratil (USA), Robert H. Schuler (USA), Christian Streffer (Germany), Irena Szumiel(Poland), Piotr Urbański (Poland), Alexander Van Hook (USA)

CONTENTS OF No. 1/2006

Proceedings of the 2nd IAEA Research Co-ordination Meeting of the Co-ordinated Research Project onDense Magnetized Plasma, 1-3 June 2005, Kudowa Zdrój, Poland 1. Foreword

A. Malaquias 2. Dense magnetized plasma and its applications: a view of the 3-year activity of the IAEA Co-ordinated

Research ProgrammeV.A. Gribkov, A. Malaquias

3. Development of diagnostic tools for Plasma Focus derived X-ray sourceE. Angeli, C. Bonifazzi, A. Da Re, M. Marziani, A. Tartari, M. Frignani, S. Mannucci, D. Mostacci, F. Rocchi,M. Sumini

4. Dense Plasma Focus as a powerful source of monochromatic X-ray radiationA.V. Dubrovsky, V.A. Gribkov, Yu.P. Ivanov, L. Karpiński, M.A. Orlova, V.M. Romanova, M. Scholz,I.V. Volobuev

5. Production of negative hydrogen ions using a low-pressure reflex discharge sourceE.I. Toader

6. Development of a large beam facilityB.H. Oh, S.R. In, K.W. Lee, S.H. Jeong, C.S. Seo, D.H. Chang

7. Experimental study of a small gas-puff Z-pinch deviceC.M. Luo, X.X. Wang, X.B. Zou

8. D(3He,p)4He and D(d,p)3H fusion in a small plasma focus operated in a deuterium helium-3 gas mix-tureS.V. Springham, T.H. Sim, R.S. Rawat, P. Lee, A. Patran, P.M.E. Shutler, T.L. Tan, S. Lee

9. PF-6 – an effective plasma focus as a source of ionizng radiation and plasma streams for application inmaterial technology, biology and medicineV.A. Gribkov, A.V. Dubrovsky, M. Scholz, S. Jednorog, L. Karpiński, K. Tomaszewski, M. Paduch,R. Miklaszewski, V.N. Pimenov, L.I. Ivanov, E.V. Dyomina, S.A. Maslyaev, M.A. Orlova

10. Colored-noise-induced anomalous transport in periodic structuresT. Laas, A. Sauga, R. Mankin, A. Ainsaar, Ü. Ugaste, A. Rekker

11. Surface and bulk processes in materials induced by pulsed ion and plasma beams at Dense Plasma FocusdevicesV.N. Pimenov, S.A. Maslyaev, L.I. Ivanov, E.V. Dyomina, V.A. Gribkov, A.V. Dubrovsky, M. Scholz,R. Miklaszewski, Ü.E. Ugaste, B. Kolman

12. Status of a mega-joule scale Plasma-Focus experimentsM. Scholz, B. Bieńkowska, M. Borowiecki, I. Ivanova-Stanik, L. Karpiński, W. Stępniewski, M. Paduch,K. Tomaszewski, M. Sadowski, A. Szydłowski, P. Kubeš, J. Kravárik

13. High kinetic energy dense plasma jetA.V. Voronin, V.K. Gusev, Yu.V. Petrov, N.V. Sakharov, K.B. Abramova, K.G. Hellblom

NUKLEONIKA 187


1. The quantum diffusion of carbon in α-iron in low temperatureL. Dąbrowski, A. Andreev, M. Georgiev

2. Investigation of low temperature diffusion of carbon in martensite by Mössbauer spectroscopy and X-raydiffractionA. Jabłońska, L. Dąbrowski, J. Suwalski, S. Neov

3. Surface structure changes of InP and GaAs single crystals irradiated with high energy electrons and swiftheavy ionsA.Yu. Didyk, F.F. Komarov, L.A. Vlasukova, V.N. Yuvchenko, A. Hofman

4. Preparation of [61Cu]DTPA complex as a possible PET tracerA.R. Jalilian, P. Rowshanfarzad, M. Sabet, M. Kamalidehghan

5. Production of [103Pd]Bleomycin complex for targeted therapyA.R. Jalilian, Y. Yari-Kamrani, M. Sadeghi

6. Gamma-ray beam attenuation to assess the influence of soil texture on structure deformationL.F. Pires, O.O.S. Bacchi, N.M.P. Dias

7. A radiographic facility at the Sołtan Institute for Nuclear Studies (SINS) at Świerk, PolandJ. Bigolas, W. Drabik, E. Pławski, A. Wysocka-Rabin

8. Air aerosol sampling station AZA-1000 at Polish Polar Station in Hornsund, SpitsbergenB. Mysłek-Laurikainen, M. Matul, S. Mikołajewski, H. Trzaskowska, Z. Preibisz, I. Garanty, M. Kubicki,P. Rakowski, T. Krynicki, M. Stefański


1. Effects of an antimutagen of 1,4-dihydropyridine series on cell survival and DNA damage in L5178Ymurine sublinesO. Dalivelya, N. Savina, T. Kuzhir, I. Buraczewska, M. Wojewódzka, I. Szumiel

2. Production and quality control of 66Ga radionuclideM. Sabet, P. Rowshanfarzad, A.R. Jalilian, M.R. Ensaf, A.A. Rajamand

3. Development of [66Ga]oxine complex; a possible PET tracerA.R. Jalilian, P. Rowshanfarzad, M. Sabet, A. Rahiminejad-Kisomi, A.A. Rajamand

4. Computation of concentration changes of heavy metals in the fuel assemblies with 1.6% enrichment byORIGEN code for VVER-1000M. Rahgoshay

5. Monte-Carlo simulation of a neutron source generated with electron linear acceleratorA. Wasilewski, S. Wronka

6. Investigation of high-dose irradiation effects on polystyrene calorimeter responseF. Ziaie, A. Noori

7. Influence of temperature on breakdown voltage of 10 MeV electron beam irradiated LDPE and HDPEM. Borhani, F. Ziaie, M.A. Bolorizadeh, G. Mirjalili


1. ObituaryProfessor Barbara Hołyńska (1930-2006)

2. DNA double-strand break rejoining in radioadapted human lymphocytes: evaluation by neutral cometassay and pulse-field gel electrophoresisM. Wojewódzka, I. Buraczewska, I. Szumiel, I. Grądzka

3. Influence of 137Cs and 90Sr on vegetative and generative organs of Lepidium sativum L. and Tradescantiaclone 02D. Marèiulionienë, B. Lukšienë, D. Kiponas, D. Montvydienë, G. Maksimov, J. Darginavièienë, V.Gavelienë

4. Preparation and biodistribution of [201Tl](III)vancomycin complex in normal ratsA.R. Jalilian, M.A. Hosseini, A. Karimian, F. Saddadi, M. Sadeghi

5. Production, quality control and initial imaging studies of [82mRb]RbCl for PET studiesP. Rowshanfarzad, A.R. Jalilian, M. Kiyomarsi, M. Sabet, A.R. Karimian, S. Moradkhani, M. Mirzaii

6. Isotope effects of gallium and indium in cation exchange chromatographyW. Dembiński, I. Herdzik, W. Skwara, E. Bulska, A.I. Wysocka

NUKLEONIKA188

7. Production and separation of manganese-54 from alpha-irradiated V2O5 targetM. Kłos, M. Bartyzel, B. Petelenz

8. Design, construction and performance of a pressure chamber for water retention curve determinationthrough traditional and nuclear methodsL.F. Pires, O.O.S. Bacchi

SUPPLEMENT No. 1/2006

Proceedings of the 2nd Polish-Japanese Workshop on Materials Science “Materials for SustainableDevelopment in the 21st Century”, 12-15 October 2005, Warsaw, Poland 1. Foreword

J. Michalik, K. Halada 2. Worldwide developments in the field of radiation processing of materials in the down of 21st century

A.G. Chmielewski 3. Design of high quality doped CeO2 solid electrolytes with nanohetero structure

T. Mori, J. Drennan, D.R. Ou, F. Ye 4. Structure and properties of nanomaterials produced by severe plastic deformation

Z. Pakieła, H. Garbacz, M. Lewandowska, A. Drużycka-Wiencek, M. Suś-Ryszkowska, W. Zieliński,K.J. Kurzydłowski

5. Synthesis of nanostructured tetragonal ZrO2 of enhanced thermal stabilityA. Adamski, P. Jakubus, Z. Sojka

6. Studies on template-synthesized polypyrrole nanostructuresW. Starosta, M. Buczkowski, B. Sartowska, D. Wawszczak

7. Structural characterization of room-temperature synthesized fullerene nanowhiskersK. Miyazawa, J. Minato, T. Mashino, S. Nakamura, M. Fujino, T. Suga

8. EPR and ESEEM study of silver clusters in ZK-4 molecular sievesJ. Sadło, J. Michalik, L. Kevan

9. Properties of novel silicon nitride-based materialsK. Itatani

10. Development of environmental purification materials with smart functionsH. Yamada, Y. Watanabe, K. Tamura

11. Silica materials with biocidal activityD.K. Chmielewska, A. Łukasiewicz, J. Michalik, B. Sartowska

12. High pressures studies on hydrides of selected manganese alloysH. Sugiura, S.M. Filipek, V. Paul-Boncour, I. Marchuk, R.-S. Liu, S.I. Pyun

13. Application of Pt/Al2O3 catalysts produced by sol-gel process to uranyl ion reductionA. Deptuła, W. Łada, T. Olczak, A.G. Chmielewski

14. Hybrid atomization method suitable for production of fine spherical lead-free solder powderK. Minagawa, H. Kakisawa, S. Takamori, Y. Osawa, K. Halada

15. Degradation of polyolefine wastes into liquid fuelsB. Tymiński, K. Zwoliński, R. Jurczyk

16. EPR study on biominerals as materials for retrospective dosimetryJ. Sadło, J. Michalik, W. Stachowicz, G. Strzelczak, A. Dziedzic-Gocławska, K. Ostrowski

17. Membrane processes for environmental protection: applications in nuclear technologyG. Zakrzewska-Trznadel

18. Advanced processing for recycling of iron scrap with impuritiesY. Osawa, S. Takamori, K. Minagawa, H. Kakisawa, K. Halada

19. Influence of radiation sterilization on poly(ester urethanes) designed for medical applicationsG. Przybytniak, E. Kornacka, J. Ryszkowska, M. Bil, A. Rafalski, P. Woźniak, M. Lewandowska-Szumieł

20. Radiation processing of polymers and semiconductors at the Institute of Nuclear Chemistry and Tech-nologyZ. Zimek, G. Przybytniak, I. Kałuska


Proceedings of the IV All-Polish Conference on Radiochemistry and Nuclear Chemistry, 9-11 May 2005,Kraków-Przegorzały, Poland

NUKLEONIKA 189

1. PrefaceL. Fuks

2. Thermochromatographic separation of 206,208Po from a bismuth target bombarded with protonsB. Wąs, R. Misiak, M. Bartyzel, B. Petelenz

3. Carbon isotope effects in the studies of the mechanism of action of tyrosine phenol-lyaseW. Augustyniak, R. Kański, M. Kańska

4. Synthesis of ring labeled [1’-14C]-L-tyrosineR. Kański, W. Augustyniak, M. Kańska

5. Tritium kinetic isotope effects on enzymatic decomposition of L-tryptophanE. Boroda, R. Kański, M. Kańska

6. Self-absorption correction in gamma-ray spectrometry of environmental samples – an overview ofmethods and correction values obtained for the selected geometriesP. Jodłowski

7. Interlaboratory comparison of the determination of 137Cs and 90Sr in water, food and soil: preparationand characterization of test materialsL. Fuks, H. Polkowska-Motrenko

8. Studies on concentration of some heavy metals and strontium 90Sr and cesium 137Cs isotopes in bottomsediments of selected lakes of Łęczyńsko-Włodawskie PojezierzeJ. Solecki, M. Reszka, S. Chibowski

9. Determination of the sediment deposition rates in the Kuwait Bay using 137Cs and 210PbA.Z. Al-Zamel, F. Bou-Rabee, M.A. Al-Sarawi, M. Olszewski, H. Bem

10. Radionuclides of iron (55Fe), nickel (63Ni), polonium (210Po), uranium (234U, 235U, 238U) and plutonium(238Pu, 239-240Pu, 241Pu) in Poland and Baltic Sea environmentB. Skwarzec, D.I. Strumińska, A. Boryło

11. Investigation of the influence of high humidity and exposure duration on the measurement results ofradon concentration by means of PicoRad system in the CLOR calibration chamberO. Stawarz, M. Karpińska, K. Mamont-Cieśla

12. Accumulation properties of Norway spruce (Picea abies) for different radionuclidesE. Tomankiewicz, J.W. Mietelski, P. Gaca, S. Błażej

13. Spatial 137Cs distribution in forest soilA. Dołhańczuk-Śródka, T. Majcherczyk, M. Smuda, Z. Ziembik, M. Wacławek

14. Isotope effects on selected physicochemical properties of nitromethane and 1-pentanolA. Makowska, J. Szydłowski

15. Radiation chemistry of radioactive waste to be stored in the salt mine repositoryZ.P. Zagórski


Proceedings of the 18th International Conference on Nucleus-Nucleus Collisions, 4-9 August 2005, Budapest,Hungary 1. Preface

J. Pluta 2. Freeze-out and anisotropic flow in microscopic models

L.V. Bravina, K. Tywoniuk, E.E. Zabrodin, G. Burau, J. Bleibel, C. Fuchs, A. Faessler 3. Can thermal model explain Λ

–/p– puzzle?

L.V. Bravina, M.S. Nilsson, K. Tywoniuk, E.E. Zabrodin 4. Rapidity distributions of strange particles in Pb-Pb at 158 A GeV

G.E. Bruno on behalf of the NA57 Collaboration 5. Elliptic flow at RHIC with NeXSPheRIO

R.P.G. Andrade, F. Grassi, Y. Hama, T. Kodama, O. Socolowski Jr., B. Tavares 6. Effect of hadronic rescattering on the elliptic flow after the hydrodynamics model

G.L. Ma, Y.G. Ma, B.H. Sa, X.Z. Cai, Z.J. He, H.Z. Huang, J.L. Long, W.Q. Shen, C. Zhong, J.H. Chen,J.X. Zuo, S. Zhang, X.H. Shi

7. Systematic study of directed flow at RHIC energiesA.C. Mignerey for the PHOBOS Collaboration

NUKLEONIKA190

8. The azimuthal anisotropy of electrons from heavy flavor decays in = 200 GeV Au-Au collisionsby PHENIXS. Sakai for the PHENIX Collaboration

9. Influence of the non-flow effects and fluctuations on the v2 measurements at RHICX. Zhu, M. Bleicher

10. Freeze-out process with in-medium nucleon massS. Zschocke, L.P. Csernai, E. Molnár, J. Manninen, A. Nyiri

11. Non-identical particle correlations in central Pb+Au collisions at 158 A GeVD. Antończyk for the CERES Collaboration

12. Charge balance functions and the transverse flowP. Bożek

13. Preliminary results on direct photon-photon HBT measurements in = 62.4 GeV and 200 GeVAu+Au collisions at RHICD. Das, G. Lin, S. Chattopadhyay, A. Chikanian, E. Finch, T.K. Nayak, S.Y. Panitkin, J. Sandweiss,A.A. Suaide, H. Zhang for the STAR Collaboration

14. Baryon-baryon correlations in Au+Au collisions at = 62 GeV and = 200 GeV, measured inthe STAR experiment at RHICH.P. Gos for the STAR Collaboration

15. Charge transfer fluctuations as a QGP signalS. Jeon, L. Shi, M. Bleicher

16. Strangeness conservation and pair correlations of neutral kaons with close momenta in inclusive pro-cessesV.L. Lyuboshitz, V.V. Lyuboshitz

17. Obtaining the specific heat of hadronic matter from CERN/RHIC experimentsA. Mekjian

18. The evolution of correlation functions from low to high pT in PHENIX: from HBT to jetsJ.T. Mitchell for the PHENIX Collaboration

19. Effect of hard processes on momentum correlations in pp and pp– collisionsG. Paić, P.K. Skowroński

20. A survey of multiplicity fluctuations in PHENIXJ.T. Mitchell for the PHENIX Collaboration

21. How to measure specific heat using event-by-event average pT fluctuationsM.J. Tannenbaum for the PHEHIX Collaboration

22. A statistical model analysis of yields and fluctuations in 200 GeV Au-Au collisionsG. Torrieri, S. Jeon, J. Rafelski

23. Proposition of numerical modelling of BECO.V. Utyuzh, G. Wilk, Z. Włodarczyk

24. Transverse momentum distributions and string percolation study in p+p, d+Au and Au+Au collisionsat = 200 GeVB.K. Srivastava, R.P. Scharenberg, T.J. Tarnowsky for the STAR Collaboration

InformationINSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

NUKLEONIKADorodna 16, 03-195 Warszawa, Poland

phone: (+4822) 504-11-32; fax: (+4822) 811-15-32; e-mail: [email protected] and full texts are available on-line at http://www.ichtj.waw.pl/ichtj/general/nukleon.htm

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191INTERVIEWS IN 2006

INTERVIEWS IN 2006

1. Chmielewski Andrzej G.Niedzicki W.: Sylwetki uczonych (Profiles of scientistis). TVP, Program 1, 20.09.2006.

2. Chmielewski Andrzej G.Truszczak D.: Osiągnięcia nauki (Achievements of science). Polskie Radio, Program 1, 20.09.2006.

3. Chmielewski Andrzej G.Giurla S.: A tecnologia avança e a humanidade agradece (High-tech serving the people). Brasil Nuclear,11, 29, 20-22 (2006).

4. Chmielewski Andrzej G.Łoś P.: Akceleratory elektronów w ochronie środowiska (Application of electron accelerators in environ-mental protection). Radio dla Ciebie, 30.10.2006.

192

THE INCT PATENTS AND PATENT APPLICATIONS IN 2006

THE INCT PATENTS AND PATENT APPLICATIONS IN 2006

PATENTS

1. Sposób otrzymywania paliw ciekłych z odpadów tworzyw sztucznych, zwłaszcza odpadów poliolefinowychi urządzenie do realizacji tego sposobu (Method for obtaining liquid fuels from wastes of plastics, particu-larly of polyolefines, and a facility to realize the method)A.G. Chmielewski, J. Jerzy, T. Siekierski, B. Tymiński, K. ZwolińskiPolish Patent No. 191891

2. Sposób usuwania lotnych zanieczyszczeń organicznych gazowych takich jak wielopierścieniowe węglowodoryaromatyczne z przemysłowych gazów odlotowych (Method for elimination of gaseous organic impuritiessuch as polycyclic aromatic hydrocarbons from industrial flue gases)A.G. Chmielewski, A. Ostapczuk, K. Kubica, J. LickiPolish Patent No. 192519

3. Sposób zwiększenia efektywności oczyszczania promieniotwórczych ścieków nisko i średnio aktywnychzatężanych metodą odwróconej osmozy (Method for enhancement of purification effectiveness of lowand medium level radioactive wastes concentrated by reverse osmosis)A.G. Chmielewski, M. Harasimowicz, B. Tymiński, G. Zakrzewska-TrznadelPolish Patent No. 193649

PATENT APPLICATIONS

1. Detektor do pomiaru stężenia produktów rozpadu radonu w powietrzu (Detector for measuring the con-centration of radon decay products in air)B. Machaj, J. BartakP 378974

2. Sposób otrzymywania dwuwolframianu itrowo-potasowego oraz nanokompozytu tego dwuwolframianudotowanego iterbem (Method for obtaining ittrium-potassium ditungstate and a nanocomposite of thiscompound doped with ytterbium)A. Deptuła, W. Łada, T. Olczak, D. Wawszczak, M. Borowiec, H. Szymczak, W. Diakonow, M. BarańskiP 379537 (with the Institute of Physics, Polish Academy of Sciences)

3. Sposób otrzymywania napełniaczy o strukturze montmorylonitu (Method for obtaining fillers of mont-morillonite structure)Z. Zimek, I. Legocka, K. Mirkowski, A. Nowicki, G. PrzybytniakP 379779

4. Sposób otrzymywania terapeutycznych ilości radionuklidu 177Lu (Method for obtaining therapeutic quan-tities of the 177Lu radionuclide)A. Bilewicz, E. IllerP 379829

5. Sposób wytwarzania mikrokrystalicznej celulozy (Method for obtaining microcrystalline cellulose)H. Stupińska, J. Palenik, E. Kopania, D. Wawro, D . Ciechańska, G. Krzyżanowska, E. Iller, Z. ZimekP 380328 (with the Institute of Biopolymers and Chemical Fibres, and the Pulp and Paper ResearchInstitute)


CONFERENCES ORGANIZED AND CO-ORGANIZEDBY THE INCT IN 2006

1. REGIONAL TRAINING COURSE “APPLICATION OF MONTE CARLO MODELINGMETHODS FOR DOSIMETRY CALCULATION IN RADIATION PROCESSING” IN THEFRAME OF THE TECHNICAL COOPERATION PROJECT RER/8/010 “QUALITYCONTROL METHODS AND PROCEDURES FOR RADIATION TECHNOLOGY”, 3-7APRIL 2006, WARSZAWA, POLAND

Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy AgencyOrganizing Committee: I. Kałuska, M.Sc., Z. Zimek, Ph.D., Prof. A.G. Chmielewski, Ph.D., D.Sc.

OPENINGJ. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)A. Chupov (International Atomic Energy Agency, Vienna, Austria)H. Sampa (International Atomic Energy Agency, Vienna, Austria)

LECTURES• New development in constuction and operation of radiation processing plants

A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw Uni-versity of Technology, Poland)

• The use of dosimetry in process validation and facility qualificationA. Kovacs (Institute of Isotopes and Surface Chemistry, Budapest, Hungary)

• The role of Monte Carlo methods in industrial radiation applicationJ. Mittendorfer (MEDISCAN, Austria)

• Physical and mathematical methods for simulation of radiation processingV. Lazurik (Kharkov State University, Ukraine)

• Models of an irradiation process for EB technologies (numerical code RT-Office)G. Popov (Kharkov State University, Ukraine)

• Software for EB processing: ModeRTL, ModeDF, ModeCEBG. Popov (Kharkov State University, Ukraine)

• Architecture of RT-Office softwareV. Lazurik (Kharkov State University, Ukraine)

• The use of dosimetry and interpretation of dosimetry dataK. Mehta (International Atomic Energy Agency, Vienna, Austria)

• Calorimeters and alanine, CTA, PVC foil dosimetersZ. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Dosimetry system for EB irradiationA. Kovacs (Institute of Isotopes and Surface Chemistry, Budapest, Hungary)

• Introduction to intercomparison experimentsZ. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Uncertainty in dose measurementsK. Mehta (International Atomic Energy Agency, Vienna, Austria)

• Uncertainty evaluation of computer programs based on Monte Carlo method for dose calculationsJ. Mittendorfer (MEDISCAN, Austria)

• Validation of radiation sterilization processI. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• X-ray application for radiation processingZ. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Radiation processing of polymersA.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw Uni-versity of Technology, Poland)

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006194

• Simulation of irradiation process on radiation-technological lines (RTL) with scanned beam; softwareModeRTLV. Lazurik, G. Popov (Kharkov State University, Ukraine)

• Evaluation of intercomparison experimentsK. Mehta (International Atomic Energy Agency, Vienna, Austria), A. Kovacs (Institute of Isotopes andSurface Chemistry, Budapest, Hungary)

• Comparison of the experimental results with simulation predictionsV. Lazurik (Kharkov State University, Ukraine), G. Popov (Kharkov State University, Ukraine), Z. Zimek(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), I. Kałuska (Institute of NuclearChemistry and Technology, Warszawa, Poland)

• Simulation of irradiation process of multi-layer circular objects such as wire, cables, tubing, pipes withscanned beamG. Popov (Kharkov State University, Ukraine)

• Examples of some actual problems solutions in radiation processingV. Lazurik (Kharkov State University, Ukraine), G. Popov (Kharkov State University, Ukraine)

SPECIAL LECTURES – technical visit to the Institute of Nuclear Chemistry and Technology• Film Dose Reader CD-02

B. Machaj (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)• Radiation facilities at the Institute of Nuclear Chemistry and Technology]

Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Sadło (Institute ofNuclear Chemistry and Technology, Warszawa, Poland), I. Kałuska (Institute of Nuclear Chemistry andTechnology, Warszawa, Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa,Poland)

• The experimental validation of simulation predictions for dose mapping in heterogeneous targets irra-diation with scanned EBI. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Bułka (Institute ofNuclear Chemistry and Technology, Warszawa, Poland), Z. Stuglik (Institute of Nuclear Chemistry andTechnology, Warszawa, Poland), G. Popov (Kharkov State University, Ukraine)

• Biological dosimetry in human biomonitoringM. Kruszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Brzozowska(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), T. Bartłomiejczyk (Institute ofNuclear Chemistry and Technology, Warszawa, Poland), A. Wójcik (Institute of Nuclear Chemistry andTechnology, Warszawa, Poland)

2. THE WORKSHOP “DOSIMETRY FOR RADIATION APPLICATION IN TECHNOLOGIESFOR ENVIRONMENT POLLUTION CONTROL” IN THE FRAME OF THE MARIECURIE HOST FELLOWSHIPS FOR THE TRANSFER OF KNOWLEDGE: ADVANCEDMETHODS FOR ENVIRONMENT RESEARCH AND CONTROL (AMERAC), 5 APRIL2006, WARSZAWA, POLAND

Organized by the Institute of Nuclear Chemistry and Technology

LECTURES• Overview of dosimetry methods for radiation technologies for environment preservation

K. Mehta (International Atomic Energy Agency, Vienna, Austria)• Application of dosimetry for wastewater treatment – Brazilian experience

M.H.O Sampa (International Atomic Energy Agency, Vienna, Austria), P.R. Rela (Instituto de PesquisasEnergéticas e Nucleares (IPEN), São Paulo, Brazil), C.L. Duarte (Instituto de Pesquisas Energéticas eNucleares (IPEN), São Paulo, Brazil), C.S. Rela (Instituto de Pesquisas Energéticas e Nucleares (IPEN),São Paulo, Brazil), F.E. Costa (Instituto de Pesquisas Energéticas e Nucleares (IPEN), São Paulo, Brazil)

• Dosimetry for wastewater treatment tests – Italian experienceM. Lavalle (Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council(CNR), Bologna, Italy)

• Dosimetric methods for industrial scale flue gas treatmentZ. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Dosimetric methods for laboratory scale VOC treatmentA.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw Uni-versity of Technology, Poland), Y. Sun (Institute of Nuclear Chemistry and Technology, Warszawa,


3. THE WORKSHOP “METHODS OF ENVIRONMENTAL RESEARCH” IN THE FRAMEOF THE MARIE CURIE HOST FELLOWSHIPS FOR THE TRANSFER OF KNOWLEDGE:ADVANCED METHODS FOR ENVIRONMENT RESEARCH AND CONTROL (AMERAC),10 AUGUST 2006, WARSZAWA, POLAND


LECTURES• The use of stable isotopes of carbon to study the sources and sinks of some greenhouse gases (CO2, CH4)

in airS.M. Cuna (National Institute for Research and Development of Isotopic and Molecular Technologies,Cluj-Napoca, Romania)

• Design of novel membranes and their application for desalination by membrane distillationM. Khayet Souhaimi (University Complutense of Madrid, Spain)

• Modelling and optimization of experimental processes in environmental engineering using ResponseSurface Methodology (RSM)C. Cojocaru (”Gh.Asachi” Technical University of Iaºi, Romania)

DISCUSSION: conclusions, recommendationsModerator: A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; WarsawUniversity of Technology, Poland)

4. SYMPOZJUM „CHEMIA I TECHNIKA RADIACYJNA: WYZWANIA I MOŻLIWOŚCI –JUBILEUSZ 80-LECIA PROF. DR HAB. ZBIGNIEWA P. ZAGÓRSKIEGO” (SYMPOSIUMON CHEMISTRY AND RADIATION TECHNIQUES: CHALLENGE AND POSSIBILITIES– JUBILEE OF THE 80th ANNIVERSARY OF Prof. ZBIGNIEW P. ZAGÓRSKI, Ph.D.,D.Sc. (17 OCTOBER 2006, WARSZAWA, POLAND)


LECTURES• Laudation

L. Waliś (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Mayer (Institute ofApplied Radiation Chemistry, Łódź, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technol-ogy, Warszawa, Poland)

• Przyszłość chemii radiacyjnej, jak ją widziano w roku 1946 (Future of radiation chemistry as was seen in1946)Z.P. Zagórski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Znane i nieznane aspekty pierwszych etapów działania promieniowania jonizującego w biopolimerachi polimerach syntetycznych (Known and unknown aspects of primary stages of ionizing radiation treat-ment of biopolymers and synthetic polymers)G. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Pomiary odległości metodą EPR (Distance measurements by the EPR method)J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Wolne rodniki w związkach o znaczeniu biologicznym (Free radicals in biological important compounds)K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Ciecze jonowe – rozpuszczalniki przyszłości? (Ionic liquids – solvents of future?)J. Grodkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Relaksacja elektronów pułapkowanych w etanolu oraz mieszaninach etanol-woda i etanol-metanol w tem-peraturze 10-77 (100) K (Relaxation of trapped electrons in ethanol and ethanol-methanol mixtures at atemperature of 10-77 (100) K)J.P. Suwalski (Institute of Applied Radiation Chemistry, Łódź, Poland)

• Obecne i przyszłe zastosowania technik radiacyjnych w przetwórstwie polimerów (Present and futureapplications of radiation processing in polymer modification)A. Rafalski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Zimek (Insti-tute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Electron beam application for volatile organic compounds removalA. Ostapczuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006196

5. IV KONFERENCJA „PROBLEMY UNIESZKODLIWIANIA ODPADÓW” (IV CONFERENCEON PROBLEMS OF WASTE DISPOSAL), 27 NOVEMBER 2006, WARSZAWA, POLAND

Organized by the Warsaw University of Technology, Plant for Utilization of Solid Municipal Wastes(Warszawa), Institute of Nuclear Chemistry and Technology, Gdańsk University of TechnologyOrganizing Committee: M. Obrębska, Ph.D., A. Polak, M.Sc.

OPENINGJerzy Bałdyga (Warsaw University of Technology, Poland)

Session IA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY)Chairman: A. Biń (Warsaw University of Technology, Poland)• Przemysłowe testy współspalania komunalnych osadów ściekowych z węglem w kotle pyłowym (Com-

bustion of municipal sludge with coal in a dust boiler – industrial tests)R. Wasilewski (Institute for Chemical Processing of Coal, Zabrze, Poland), S. Stelmach (Institute forChemical Processing of Coal, Zabrze, Poland), J. Zuwała (Institute for Chemical Processing of Coal,Zabrze, Poland)

• Współspalanie odpadów, biomasy i paliw kopalnych w kotłach energetycznych (Combustion of wastes,biomass and fossil fuels in energetic boilers)H. Karcz (Wrocław University of Technology, Poland), M. Krzysztof (ZBUS Combustion, Głowno,Poland), K. Folga (ZBUS Combustion, Głowno, Poland)

• Wykorzystanie odpadowej biomasy do oczyszczania roztworów wodnych (Application of waste biomassfor purification of water solutions)K. Bratek (Wrocław University of Technology, Poland), W. Bratek (Wrocław University of Technology,Poland)

Session IB. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL-ECONOMIC-LAWFUL)Chairman: P. Grzybowski (Warsaw University of Technology, Poland)• EUROVIX – biotechnologie dla życia (EUROVIX – Biotechnologies for life)

K. Łuczak (EUROVIX S.r.l., Italy)• Dlaczego powinniśmy spalać odpady? (Why we should incinerate the wastes?)

G. Wielgosiński (Technical University of Łódź, Poland)

Session IIA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY)Chairman: R. Zarzycki (Technical University of Łódź, Poland)• Analityczne badania radiolitycznej degradacji wybranych pestycydów (Radiolytical degradation of se-

lected pesticides – analytical investigations)A. Bojanowska-Czajka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Drzewicz(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Trojanowicz (Institute of NuclearChemistry and Technology, Warszawa; Warsaw University of Technology, Poland), G. Nałęcz-Jawecki(Medical University of Warsaw, Poland), J. Sawicki (Medical University of Warsaw, Poland), Z. Zimek(Institute of Nuclear Chemistry and Technology, Warszawa, Poland), H. Nichipor (Institute of Radia-tion Physical-Chemical Problems, National Academy of Sciences of Belarus, Minsk, Belarus)

• Unieszkodliwianie odpadów drobiarskich poprzez fermentacje metanową (Disposal of poultry wastesby methane fermentation)A. Zawadzka (Technical University of Łódź, Poland), K. Sikora-Łępicka (Technical University of Łódź,Poland)

• Opracowanie sposobu zmniejszenia zrzutu azotu amonowego w ścieku technologicznym (A method forthe reduction of ammonia in technological wastewater)J. Zieliński (Institute of Industrial Organic Chemistry, Warszawa, Poland), K. Zwierzyński (Institute ofIndustrial Organic Chemistry, Warszawa, Poland), M. Lewandowska (Institute of Industrial OrganicChemistry, Warszawa, Poland)

• Antologia dozymetrii radiacyjnej dużych dawek (Antology of high dose radiation dosimetry)P. Panta (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers)W. Głuszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Chemia i technika radiacyjna - i co dalej? (Radiation chemistry and radiation processing – what the nextthing?)Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)


Session IIB. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL-ECONOMIC-LAWFUL)Chairman: G. Wielgosiński (Technical University of Łódź, Poland)• Spalać czy składować? (To incinerate or to storage on landfill sites)

J. Kaznowski (SPEC S.A., Warszawa, Poland)• Eliminacja przykrych zapachów w oczyszczalniach ścieków (Elimination of stench in wastewater treat-

ment)M. Szatkowski (Westrand Polska, Warszawa, Poland)

Session IIIA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY)Chairman: M. Obrębska (Warsaw University of Technology, Poland)• Przetwarzanie poużytkowych opakowań z poli(tereftalanu etylenu) na węgiel aktywny (Processing of

used PET packaging into active carbon)A. Świątkowski (WAT Military University of Technology, Warszawa, Poland), A. Padée (Warsaw Agri-cultural University, Poland)

• Analiza własności ciekłych produktów termicznej depolimeryzacji polipropylenu (Properties of liquidproducts of polypropylene degradation)P. Grzybowski (Warsaw University of Technology, Poland)

• Problemy związane z upłynnianiem odpadów poliolefin (Problems of liquefaction of polyolefine wastes)B. Tymiński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Jurczyk (Instituteof Nuclear Chemistry and Technology, Warszawa, Poland)

198

Ph.D./D.Sc. THESES IN 2006

Ph.D./D.Sc. THESES IN 2006

Ph.D. THESES

1. Hanna Lewandowska-Siwkiewicz, M.Sc.Powstanie, struktura i przemiany dinitrozylowych kompleksów żelaza w modelowych układach biolo-gicznych (Formation, structure and interactions of dinitrosyl iron complexes in model biological sys-tems)supervisor: Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 23.02.2006

D.Sc. THESES

1. Grażyna Zakrzewska-Trznadel, Ph.D.Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies)Technical University of Łódź

199

EDUCATION

EDUCATION

Ph.D. PROGRAMME IN CHEMISTRY

The Institute of Nuclear Chemistry and Technology holds a four-year Ph.D. degree programme for grad-uates of chemical, physical and biological departments of universities, for graduates of medical univer-sities and to engineers in chemical technology and material science.

The main areas of the programme are:• radiation chemistry and biochemistry,• chemistry of radioelements,• isotopic effects,• radiopharmaceutical chemistry,• analytical methods,• chemistry of radicals,• application of nuclear methods in chemical and environmental research, material science and pro-

tection of historical heritage.The candidates accepted for the mentioned programme can be employed in the Institute. The can-

didates can apply for a doctorial scholarship. The INCT offers accommodation in 10 rooms in theguesthouse for Ph.D. students not living in Warsaw.

During the four-year Ph.D. programme the students participate in lectures given by senior staff fromthe INCT, Warsaw University and the Polish Academy of Sciences. In the second year, the Ph.D. studentshave teaching practice in the Chemistry Department of Warsaw University. Each year the Ph.D. studentsare obliged to deliver a lecture on topic of his/her dissertation at a seminar. The final requirements for thePh.D. programme graduates, consistent with the regulation of the Ministry of Education and Science,are:• submission of a formal dissertation, summarizing original research contributions suitable for publi-

cation;• final examination and public defense of the dissertation thesis.

In 2006, the following lecture series were organized:• “Fundalmentals of coordination chemistry” – Prof. Jerzy Narbutt, Ph.D., D.Sc. (Institute of Nuclear

Chemistry and Technology, Warszawa, Poland);• “Spectrometry mass techniques (ICP MS, electrospray MS, MALDI MS) in analytical chemistry” –

Prof. Ryszard Łobiński, Ph.D. (Centre National de la Recherche Scientifique – CNRS, Pau, France);• “Radiation technologies and nuclear techniques in environmental protection” – Prof. Andrzej G. Chmie-

lewski, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa; Warsaw Universityof Technology, Poland).The qualification interview for the Ph.D. programme takes place in the mid of October. Detailed

information can be obtained from:• Head: Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc.

(phone: (+4822) 504 13 57, e-mail: [email protected]);• Secretary: Dr. Ewa Gniazdowska

(phone: (+4822) 504 10 74 or 504 11 78, e-mail: [email protected]).

TRAINING OF STUDENTS

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200 EDUCATION

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201RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTEDBY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION

IN 2006 AND IN CONTINUATION

1. Neutron activation analysis and ion chromatography as a tool for reliable lanthanides determina-tion in biological and environmental samples.supervisor: Bożena Danko, Ph.D.

2. The chemical isotope effects of gallium, indium and thallium in ligand exchange and red-ox reac-tions.supervisor: Wojciech Dembiński, Ph.D.

3. Comparative analysis of telomere length, chromosomal aberration frequency and DNA repair kineticsin peripheral blood lymphocytes of healthy donors and cancer patients.supervisor: Prof. Andrzej Wójcik, Ph.D., D.Sc.

4. Oxidation of thioether by organic complexes of copper. Processes of potential importance for patho-genesis of some neurodegenerative diseases.supervisor: Assoc. Prof. Dariusz Pogocki, Ph.D., D.Sc.

5. New methods of the study and reduction of fouling in processes of micro- and ultrafiltration of liquidradioactive waste.supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc.

6. Modelling of the dispersion of pollutants and studying their transport in natural water receiversusing stable isotopes as tracers.supervisor: Andrzej Owczarczyk, Ph.D./Jacek Palige, Ph.D.

7. Influence of gamma irradiation on starch properties: starch interaction with water and lipids,starch-lipid films.supervisor: Krystyna Cieśla, Ph.D.

8. Changes of sulphur isotope ratio in the products of coal combustion and flue gas desulphurizationprocesses.supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

9. Process of nanostructure formation of small-molecule organic gels using synchrotron methods.supervisor: Assoc. Prof. Helena Grigoriew, Ph.D., D.Sc.

10. Analytical studies of products of degradation of selected chlorophenols and pesticides caused byionizing radiation.supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc.

11. Studies of coordination of magnesium and zinc ions in their complexes with the azine dicarboxylateligands.supervisor: Prof. Janusz Leciejewicz, Ph.D., D.Sc.

12. Stable isotope applications to quality and origin control of milk and milk products.supervisor: Ryszard Wierzchnicki, Ph.D.

13. Protection phenomena in radiation chemistry of polypropylene.supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc.

14. Modification of the near surface layer of carbon steels with intense argon and nitrogen plasma pulses.supervisor: Prof. Jerzy Piekoszewski, Ph.D., D.Sc.

15. Pilot plant for thermocatalytic degradation of polyolefine and polystyrene wastes into liquid fuels.supervisor: Bogdan Tymiński, Ph.D.

202 RESEARCH PROJECTS AND CONTRACTS

16. Cheap and non-toxic dosimeter for measurement of absorbed dose in radiation processing of fluidizedbeds and fluid streams.supervisor: Zofia Stuglik, Ph.D.

17. Analytical studies of decomposition of selected pesticides using ionizing radiation.supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc.

18. Complexes of astatine-211 with metals as potential precursors of radiopharmaceuticals.supervisor: Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc.

19. The role of pirin in regulation of NF-κκκκκB signalling in response to oxidative stress.supervisor: Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc.

20. Examination of the antimutagenic effects of 1,4-dihydropyridine on mammalian cells after exposureto X-rays.supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.

RESEARCH PROJECTS ORDEREDBY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION

IN 2006

1. Radiation processing application to form nanofillers with different structure including hybrid andfunctionalized.PBZ-KBN-095/T08/2003supervisor: Zbigniew Zimek, Ph.D.

2. Mutual interactions between nutritional components in steering of development of the intestinal im-munological system.PBZ-KBN-093/P06/2003supervisor: Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc.

IAEA RESEARCH CONTRACTS IN 2006

1. Application of ionizing radiation for removal of pesticides from ground waters and wastes.12016/ROprincipal investigator: Prof. Marek Trojanowicz, Ph.D., D.Sc.

2. Radiation resistant polypropylene for medical applications and as a component of structural engineer-ing materials.12703/ROprincipal investigator: Zbigniew Zimek, Ph.D.

3. Electron beam for VOCs treatment emitted from oil combustion process.13136/ROprincipal investigator: Anna Ostapczuk, M.Sc.

IAEA TECHNICAL CONTRACTS IN 2006

1. Methyl bromide generator type ABC with accesories for transportation and labeling with radioactivegaseous methyl bromide.RAF4016-92242C

EUROPEAN COMMISSION RESEARCH PROJECTS IN 2006

1. FP6 Integrated Project European research program for the partitioning of actinides from high activewastes issuing the reprocessing of spent nuclear fuels (EUROPART).FP6-508854

203RESEARCH PROJECTS AND CONTRACTS

2. FP5 Research Training Network: Sulfur radical chemistry of biological significance: the protective anddamaging roles of thiol and thioether radicals (SULFRAD).principal investigator: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.RTN-2001-00096 under FP5

3. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Advanced methods for environmentresearch and control (AMERAC).principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc.MTKD-CT-2004-509226

4. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Chemical studies for design and pro-duction of new radiopharmaceuticals (POL-RAD-PHARM).principal investigator: Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.MTKD-CT-2004-509224

5. European cooperation in the field of scientific and technical research. COST D27 – Prebiotic chemistry andearly evolution. Role of radiation chemistry in the origin of life on Earth.supervisor: Prof. Zbigniew Zagórski, Ph.D., D.Sc.

6. European cooperation in the field of scientific and technical research. COST P9 – Radiation damage inbiomolecular systems (RADAM). Mechanisms of radiation damage transfer in polypeptide molecules.supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.

OTHER FOREIGN CONTRACTS IN 2006

1. Laboratory scale experimental analysis of electron beam treatment of flue gases from combustion ofliquid petroleum oils.Contract with King Abdulaziz City for Science and Technology, Atomic Energy Research Institute, SaudiArabia

2. Feasibility study for electron beam flue gas treatment at oil fired boiler.Contract with King Abdulaziz City for Science and Technology, Atomic Energy Research Institute, SaudiArabia

3. The realization and delivery of nickel electrodes coated with magnesium doped lithium cobaltite.Research contract with ENEA, the Italian Agency for New Technologies, Energy and Environment

204 LIST OF VISITORS TO THE INCT IN 2006

LIST OF VISITORS TO THE INCT IN 2006

1. Agorastos Nikos, University of Zurich, Switzerland, 21-26.05.

2. Ajji Zaki, Atomic Energy Commission of Syria, Damascus, Syria, 07-12.05.

3. Araya Ramiro, Universidad de Chile, Chile, 19-27.08.

4. Bekmuratov Timur, Institute of Nuclear Physics, National Nuclear Centre of the Republic of Kazakhstan,Almaty, Kazakhstan, 05.04.

5. Belchior Ana, Instituto Nacional de Engenharia e Technologia Industrial (INETI), Sacavém, Portugal, 05.04.

6. Belgaya Tamas, Institute of Isotope and Surface Chemistry, Budapest, Hungary, 16-20.10.

7. Botelho Maria Luisa, Nuclear and Technological Institute (ITN), Sacavém, Portugal, 05.04.

8. Bznuni Surik, Nuclear and Radiation Safety Center of Armenian Nuclear Regulatory Authority,Yerevan, Armenia, 05.04.

9. Cabalka Martin, Nuclear Research Institute, Øež, Czech Republik, 05.04.

10. Chorniy Anton, Kharkov State University, Ukraine, 05.04.

11. Chukalov Sergey, Institute of Nuclear Physics, National Nuclear Center of the Republic of Kazakhstan,Almaty, Kazakhstan, 28-29.06.

12. Cojocaru Corneliu, “Gh. Asachi” Technical University of Iaºi, Romania, 04.07.-04.10.

13. Cuna Stela, National Institute for Research and Development of Isotopic and Molecular Technologies,Cluj-Napoca, Romania, 18.07.-18.09.

14. Dalivelya Olga, Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk,Belarus, 03-21.07.

15. Demski Mikhail, The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus(NIIEFA), St. Petersburg, Russia, 01-06.10.

16. Drapkin Valery, St. Petersburg Instruments Ltd., Russia, 22-29.04.

17. Duc Ho Minh, Institute for Nuclear Science and Techniques, Vietnam Atomic Energy Commission(VAEC), Hanoi, Vietnam, 02-14.10.

18. Enache Mirela, Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest,Romania, 01.01.-31.03.

19. Fuente Julio de la, Universidad de Chile, Chile, 08-27.08.

20. Fulop Marko, Institute of Preventive and Clinical Medicine, Bratislava, Slovakia, 05.04, 26-27.10.

21. Georgescu Rodica-Maria, Horia Hulubei National Institute of Physics and Nuclear Engineering,Bucharest, Romania, 05.04.

22. Gryzlov Anatolij, NPO “Toriy”, Moscow, Russia, 20.06.-05.07, 18-24.09.

23. Gürtler Sylvia, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09.

24. Houeé-Levin Chantal, Université Paris-Sud, France, 17-18.02.

25. Hug Gordon L., University of Notre Dame Radiation Laboratory, USA, 03-06.01, 17-18.02, 28.09.-01.10.

26. Hustuc Aleksandru, National Scientific Center of Applied Preventive Medicine, Chisinau, Moldavia, 05.04.

27. Ivanov A., The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St.Petersburg, Russia, 22-28.10.

28. Jafarov Yadigar, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Baku,Azerbaijan, 05.04.

29. Kasztovszky Zsolt, Institute of Isotope and Surface Chemistry, Budapest, Hungary, 16-20.10.

30. Khalil Luai Ahmad, Jordan Atomic Energy Commission, Amman, Jordan, 08.10.-09.11.

31. Khayet Souhaimi Mohamad, University Complutense of Madrid, Spain, 03.07.-29.08.

32. Kim Jinkyu, EB-Tech Co., Ltd., Daejeon, Korea, 19-24.08.

33. Kovacs Andras, Institute of Isotope Research, Hungarian Academy of Sciences, Budapest, Hungary, 05.04.

205LIST OF VISITORS TO THE INCT IN 2006

34. Knyazev Mikhail, St. Petersburg Instruments Ltd., Russia, 22-29.04, 07-12.08, 07-12.11.

35. Krpan Katarina, Rudjer Boskovic Institute, Zagreb, Croatia, 05.04.

36. Kuenstler Jens-Uwe, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany,26.06.-26.07.

37. Lazurik Valentina, Kharkiv National University, Ukraine, 02-07.04.

38. Lavalle Marco, Institute for the Organic Synthesis and Photoreactivity, National Research Council ofItaly (ISOF-CNR), Bologna, Italy, 02-09.04.

39. Le Minh Tuan, Research and Development Center for Radiation Technology, Vietnam Atomic EnergyCommission (VINA GAMMA), Ho Chi Minh City, Vietnam, 07.05.-08.08.

40. Lebeda Ondrei, Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Øež, CzechRepublic, 18.03-18.05.

41. Lebedev Vjacheslav, Joint Institute for Nuclear Research, Dubna, Russia, 13-20.08.

42. Letournel Eric, VIVIRAD SA, France, 12-13.12.

43. Lyssukin Sergey, Institute of Nuclear Physics, Almaty, Kazakhstan, 28-29.06.

44. Łobiński Ryszard, Centre National de la Recherche Scientifique – CNRS, France, 05.04.-05.06.

45. März Peter, EPR Division, Bruker Biospin GmbH, Silberstreifen, Germany, 20-25.11.

46. Mehta Kishor, International Atomic Energy Agency, United Nations, 28.02.-28.04.

47. Mozziconazzi Olivier, France, 01.01.-28.02.

48. Neves Maria, Instituto Tecnologico e Nuclear, Sacavém, Portugal, 04.09.-04.11.

49. Nichipor Henrietta, Institute of Radiation Physical-Chemical Problems, National Academy of Sciencesof Belarus, Minsk, Belarus, 17-28.07, 01-04.10.

50. Novikova Galina, National Research Restoration Centre of Ukraine, Kiev, Ukraine, 01-07.08.

51. Pawlukojć Andrzej, Joint Institute for Nuclear Research, Dubna, Russia, 17-19.09.

52. Pietzsch Juergen Hans, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany,05-10.04.

53. Politkovskij Fiodor, NPO “Toriy”, Moscow, Russia, 20.06-05.07.

54. Popov Genadiv, Kharkiv State University, Ukraine, 05.04, 06-08.11.

55. Ramirez Trajano, National Technological University, Quito, Ecuador, 11-12.09.

56. Romanova Irina, Institute of Genetics, Academy of Sciences of Moldavia, Chisinau, Moldavia, 05.04.

57. Redaelli Renato, Universita degli Studi di Milano, Italy, 31.10.-02.11.

58. Rieck Stefanie, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09.

59. Ritter Alina, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09.

60. Said Amr El-Hag Ali, National Center for Radiation Research and Technology, Cairo, Egypt, 04.04.-29.06.

61. Saidi Mouldi, National Center for Nuclear Sciences and Technologies, Tunis, Tunisia, 16.05.-16.07.

62. Sampa Maria Helena, International Atomic Energy Agency, United Nations, 05.04.

63. Savina Natalya, Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk,Belarus, 03-21.07.

64. Sheyno Igor, Institute of Biophysics, State Scientific Center, Moscow, Russia, 05.04.

65. Skarnemark Gunnar, Chalmers University of Technology, Göteborg, Sweden, 06.08.-05.09.

66. Smolko Edvardo, Irradiation Processing Laboratory, Centro Atomico Buenos Aires, Argentina, 07-11.09.

67. Spies Hartmut, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany,18.03.-18.04.

68. Svinin Mikhail, The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA),St. Petersburg, Russia, 22-28.10.

69. Taroyan Sargis, Yerevan Physics Institute, Yerevan Armenia, 05.04.

70. Tereshatov Evgeny, Joint Institute for Nuclear Research, Dubna, Russia, 13-20.08.

71. Tsrunchev Tsvetelin, National Centre of Radiobiology and Radiation Protection (NCRRP), Sofia,Bulgaria, 05.04.

72. Weissabel Robert, Slovak Office of Standards, Metrology and Testing, Bratislava, Slovakia, 26-27.10.

206 THE INCT SEMINARS IN 2006

THE INCT SEMINARS IN 2006

1. Ewelina Chajduk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Prace nad konstruowaniem metod o najwyższej randze metrologicznej do oznaczania Se i As w materiałachbiologicznych za pomocą RNAA (High-accuracy RNAA methods for the determination of Se i As inbiological samples)

2. Prof. Zbigniew Florjańczyk (Warsaw University of Technology, Poland)Polimery hybrydowe (Hybrid polymers)

3. Michał Gryz, M.Sc. (Office for Registration of Medicinal Products, Medical Devices and Biocides, War-szawa, Poland)Cynk i magnez w procesach biologicznych (Zinc and magnesium in biological processes)

4. Gabriel Kciuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Wpływ grup funkcyjnych aminokwasów na mechanizmy reakcji rodnikowych w peptydach zawierającychtyrozynę (The influence of the amino acid functional groups on the mechanism of radical reactions inpeptides containing tyrosine)

5. Monika Łyczko, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Trikarbonylkowe kompleksy technetu(I) z amidowymi pochodnymi kwasu pikolinowego i tiopikolinowegojako prekursory radiofarmaceutyków (Tricarbonyl technetium(I) complexes with amide derivatives ofpicolinic and thiopicolinic acid as potential radiopharmaceuticals)

6. Prof. Józef Mayer (Technical University of Łódź, Poland)Reakcje jonowe w poli(chlorku winylu) (Ionic reactions in polyvinyl chloride)

7. Sylwia Męczyńska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Wpływ ·OH i ONOO– na konformację i aktywność białek zawierających żelazo (The influence of nitricoxide and peroxynitrite on conformation and activity of the iron proteins)

8. Dr. Maria Neves (Instituto Tecnologico e Nuclear, Sacavém, Portugal)Radiation in medicine and biology

9. Sławomir Ostrowski, M.Sc. (Industrial Chemistry Research Institute, Warszawa, Poland)Mechanizm reakcji wydłużania łańcucha i właściwości fizykochemiczne związków alkiloaromatycznych.Badania metodami chemii obliczniowej (Mechanism of chain elongation reactions and physicochemicalproperties of alkylaromatic compounds. Studies using calculation chemistry methods)

10. Wojciech Ozimiński, M.Sc. (National Institute of Public Health, Warszawa, Poland)Tautometria pięcioczłonowych pierścieni heterocyklicznych zawierających trzy heteroatomy. Badaniaobliczeniowe (Tautomerism of five-membered heterocyclic rings containing three heteroatoms. Calcu-lation studies)

11. Sylwia Ptaszek, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Zastosowanie znaczników i CFD do badania dynamiki przepływu w oczyszczalni ścieków (Applicationof tracers and CFD for the study of flow dynamics in wastewater treatment plant)

12. Dr. Tomasz Szreder (Institute of Dyes and Organic Products, Zgierz, Poland)Indywidua przejściowe generowane radiacyjnie w cieczach jonowych: badania wykorzystujące piko-sekundowy akcelerator elektronów w Narodowym Laboratorium w Brookhaven (USA) (Radiationallygenerated transients in ionic liquids: investigations using picosecond electron accelerator in the Brook-haven National Laboratory (USA))

13. Dr. Daniel Tedder (Georgia Institute of Technology, USA)Efficient strategies for partitioning actinides from alkaline wastes

14. Jerzy Turek, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Budowa i oddziaływania rodników srebroorganicznych. Badania EPR i DFT (Structure and interactionof organosilver radicals. EPR and DFT study)

15. Dr. Grażyna Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies)

207LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006

LECTURES AND SEMINARS DELIVERED OUT OF THE INCTIN 2006

LECTURES

1. Bilewicz A.Influence of relativistic effect on hydrolysis of heavy cations.First International Symposium on Hydration and Hydroxo Complexation of Cations, Minsk, Belarus,05-06.10.2006.

2. Bobrowski K.Protection of tyrosine in Met-enkephalin against oxidation by blocking the amine function.CNR Conference “Free Radicals in Chemical Biology”, Bologna, Italy, 30.06.2006.

3. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M.Analityczne badania radiolitycznej degradacji karbendazymu (Analytical control of carbendazim decom-position by gamma irradiation).III Warszawskie Seminarium Doktorantów Chemików ChemSession’06, Warszawa, Poland, 19.05.2006.

4. Brzozowska K.Wypadek radiacyjny w Białostockim Ośrodku Onkologicznym (The radiological accident in the BiałystokOncological Center).II Krakowsko-Poznańskie Studenckie Seminarium Fizyki Biomolekularnej i Medycznej, Poznań, Poland,22-25.02.2006.

5. Brzozowska K., Wójcik A.Wpływ temperatury na poziom mikrojąder indukowanych promieniowaniem jonizującym w ludzkich limfo-cytach krwi obwodowej (Influence of temperature on radiation-induced micronuclei in human peripheralblood lymphocytes).II Krakowsko-Poznańskie Studenckie Seminarium Fizyki Biomolekularnej i Medycznej, Poznań, Poland,22-25.02.2006.

6. Brzóska K.Piryna: nowy element regulacji sygnalizacji szlaku NFκB (Piryn: a new regulatory element of the NFκBsignaling pathway).Sympozjum “Rola żelaza w organizmie”, Warszawa, Poland, 25.11.2006.

7. Chmielewski A.G.Techniki i technologie jądrowe w zastosowaniach przemysłowych (Application of radiation and nucleartechnologies in industry).Seminarium Naukowe “Technika jądrowa w służbie społeczeństwa”, Warszawa, Poland, 30.11.2006.

8. Chmielewski A.G., Kałuska I., Zimek Z., Migdał W., Bułka S.Radiolytic decomposition of pesticide MCPA in various conditions – comparison of experimental dataand calculated kinetic model.14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-03.03.2006.

9. Chmielewski A.G., Migdał W., Zimek Z., Kałuska I., Bułka S.Commercial application of an electrom beam accelerator at the R&D and service center.14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-03.03.2006.

10. Dembiński W.Chemia materiałów paliwowych dla reaktorów jądrowych w “Nukleonice” (Chemistry of fuel materialsfor nuclear reactors in “Nukleonika”).Seminarium z okazji 50-lecia “Nukleoniki”, Warszawa, Poland, 30.06.2006.

11. Kałuska I.Legislation and standardization concerning radiation sterilization process.

208 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006

IAEA Course “Economical and Social Benefits of Radiation Processing; Standardization and LegislationIssues Regarding Radiation Processing Implementation in Europe”, Eger, Hungary, 26.08.-02.09.2006.

12. Kałuska I.Dose setting procedures for radiation deactivation and sterilization.IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006.

13. Kałuska I.Physical, chemical and biological dose modifying factors.IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006.

14. Kałuska I.Dosimetry systems for radiation processing.IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006.

15. Kałuska I.Quality assurance in radiation processing.IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006.

16. Kruszewski M.Białka żelazowo-siarkowe, nowe funkcje starych klastrów (Iron-sulphur cluster proteins, old pals withnew functions).Sympozjum “Rola żelaza w organizmie”, Warszawa, Poland, 25.11.2006.

17. Męczyńska S.Dinitrozylowe kompleksy żelaza: powstawanie i rola w organizmie (Dinitrosyl iron complexes: forma-tion and the role in organisms).Sympozjum “Rola żelaza w organizmie”, Warszawa, Poland, 25.11.2006.

18. Narbutt J.Thermodynamics of solvent extraction of metal ions: fundamentals.Fifth Half-yearly Meeting of EUROPART, Roma, Italy, 26-29.06.2006.

19. Narbutt J.50 lat radiochemii w “Nukleonice” (50 years of radiochemistry in “Nukleonika”).Seminarium z okazji 50-lecia “Nukleoniki”, Warszawa, Poland, 30.06.2006.

20. Sauerwein W., Malago M., Moss R., Wójcik A., Altieri S., Hampel G., Wittig A., Nievaart V.,Collette L., Mauri P., Huiskamp R., Michel J., Daquino G., Gerken G., Bornfeld N., Broelsch C.E.Boron neutron capture therapy (BNCT) for treating disseminated, non-resectable liver metastases.International Workshop on Fast Neutron Therapy, Essen, Germany, 14-16.09.2006.

21. Wójcik A.Aberacje chomosomowe i mikrojądra (Chromosomal aberrations and micronuclei).Kurs Radiobiologii, Kielce, Poland, 20-23.03.2006.

22. Wójcik A.Odczyny popromienne (Post-radiation early and late tissue injuries).Kurs Radiobiologii, Kielce, Poland, 20-23.03.2006.

23. Wójcik A.Hipoksja i jej rola w promieniowrażliwości guzów (Hypoxia and its role in tumor radiosensitivity).Kurs Radiobiologii, Kielce, Poland, 20-23.03.2006.

24. Wójcik A.Percepcja ryzyka dla zdrowia promieniowania jonizującego (Perception of ionizing radiation).Letnia Szkoła Energetyki Jądrowej „Dunaj’06”, Warszawa, Poland, 06.04.2006.

25. Wójcik A., Bochenek A., Lankoff A., Lisowska A., Padjas A., von Sonntag C., Szumiel I., Obe G.DNA interstrand crosslinks are induced in cells prelabelled with BrdU and exposed to UVC radiation.35th Annual Meeting of European Radiation Research Society – European Radiation Research 2006,Kiev, Ukraine, 22-25.08.2006.

26. Wójcik A., Sommer S., Deperas-Kaminska M., Moss R., Sauerwein W.Effects of high LET (C-12) and low LET (Co-60) irradiation on chromosomal aberrations in peripheralblood lymphocytes.International Workshop on Fast Neutron Therapy, Essen, Germany, 14-16.09.2006.

209LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006

27. Wójcik A., Wittig A., Sauerwein W.What is the tolerance dose of the liver?International Conference “Innovative Treatment Concepts for Liver Metastases”, Essen, Germany,07-09.12.2006.

28. Zagórski Z.P.Panspermia revisited?Gordon Research Conference “Origin of Life”, Lewiston, Maine, USA, 23-28.07.2006.

29. Zakrzewska-Trznadel G.Conditioning of biogas from biomass fermentation by membrane method.7th Framework Programme in Poland, Warszawa, Poland, 16-17.11.2006.

30. Zimnicki R.Sulphur isotopes ratio as a marker of pollutant migration in the ecosystem – opencast mine landfil.2nd International Workshop “Pathways of pollutants from landfills to air and water-soil systems andmitigation strategies of their impact on the ecosystems”, Kazimierz Dolny, Poland, 17-20.09.2006.

SEMINARS

1. Bilewicz A.Radiofarmaceutyki (Radiopharmaceuticals).Warsaw University, Poland, 16.05.2006.

2. Krzysztof BobrowskiStabilization of sulfide radical cations in linear and cyclic peptides containing methionine.National Research Council (CNR), Institute for Organic Synthesis and Photoreactivity (ISOF), Bologna,Italy, 24.02.2006.

3. Krzysztof BobrowskiStabilization of sulfide radical cations: mechanisms relevant to oxidation of peptides and proteins con-taining methionine.Swiss Federal Institute of Technology – ETH, Zurich, Switzerland, 23.03.2006.

4. Krzysztof BobrowskiStabilization of sulfide radical cations: mechanisms relevant to oxidation of peptides and proteins con-taining methionine.University Paris XI, Orsay, France, 12.05.2006.

5. Krzysztof BobrowskiFree radicals in chemistry, biology and medicine: contribution of radiation chemistry.Universidad de Chile, Santiago de Chile, Chile, 13.11.2006.

6. Krzysztof BobrowskiOxidation of methionine containing peptides: mechanism relevant to biological conditions of oxidative stress.Universidad de Valparaiso, Chile, 20.11.2006.

7. Krzysztof BobrowskiOxidation of methionine containing peptides: mechanism relevant to biological conditions of oxidative stress.Universidad de Chile, Santiago de Chile, Chile, 22.11.2006.

8. Andrzej G. ChmielewskiElectron beam flue gas treatment – the basics.University of Pavia, Italy, 08.05.2006.

9. Andrzej G. ChmielewskiElectron beam flue gas treatment – VOC and industrial applications.University of Pavia, Italy, 08.05.2006.

10. Andrzej G. ChmielewskiEnvironmental protection - worldwide developments.University of Pavia, Italy, 08.05.2006.

210 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006

11. Adrian JakowiukBezprzewodowe sieci monitoringu z radioizotopowymi czujnikami zapylenia powietrza AMIZ-2004 (Wire-less dust concentration monitoring network based on the radioisotope gauge AMIZ-2004).International Ecological Fair POLEKO, Poznań, Poland, 23.11.2006.

12. Iwona KałuskaDozymetria procesów radiacyjnych (Dosimetry of radiation processes)Poznań University of Medical Sciences, Poland, 15.03.2006.

13. Andrzej WójcikPopromienne aberracje chromosomowe: mechanizmy powstawania i biofizyczne modele, czyli badaniana pograniczu biologii i fizyki (Radiation induced chromosomal aberrations, on studies on the border ofbiology and physics).Warsaw University, Poland, 24.02.2006.

14. Andrzej WójcikAwaria reaktora w Czarnobylu: przyczyny i skutki (Accident of the Chernobyl reactor: causes and results).Polskie Sieci Energetyczne, Warszawa, Poland, 24.04.2006.

15. Andrzej WójcikCzarnobyl 20 lat po: co wiemy o skutkach dla zdrowia? (Chernobyl 20 years after: what do we know aboutthe health effects?)Świętokrzyska Academy, Kielce, Poland, 26.04.2006.

16. Andrzej Wójcik20 lat po awarii w Czarnobylu: co dziś wiemy o skutkach zdrowotnych? (20 years after the Czernobylaccident: what do we know today on the health effects?)Świętokrzyska Academy, Kielce, Poland, 26.06.2006.

17. Andrzej WójcikCytogenetic markers of individual radiation sensitivity.Gesellschaft für Schwerionenforschung (GSI), Darmstadt, Germany, 25.10.2006.

18. Zbigniew ZimekElectron beam flue gas treatment process.Saudi Aramco, Dhahran, Saudi Arabia, 19.02.2006.

19. Zbigniew ZimekHigh power electron accelerators for flue gas treatment.Institute of Atomic Energy Research, King Abdulaziz City of Science and Technology, Riyadh, SaudiArabia, 20.02.2006.

20. Zbigniew ZimekAkceleratory dla techniki jądrowej (Accelerators for nuclear power generation).Polish Nuclear Society, Warszawa, Poland, 30.11.2006.

21. Zbigniew ZimekElectron accelerators for radiation processing.Office of Normalization and Metrology, Bratislava, Slovakia, 13.12.2006.

211AWARDS IN 2006

AWARDS IN 2006

1. Down-regulation of iron regulatory protein 1 activities and expression in superoxide dismutase 1 knock-outmice is not associated with alterations in iron metabolismSecond degree group award of the Polish Genetic Society for the best work carried out in Polishlaboratories and published in 2005R.R. Starzyński, P. Lipiński, J.-C. Drapier, A. Diet, E. Smuda, T. Bartłomiejczyk, M.A. Gralak,M. Kruszewski

2. Method for obtaining the Ni/NiO cathodesBronze medal at the 34th International Exhibition of Inventions, New Techniques and Products of Geneva,Switzerland, 05-09.04.2006W. Łada, A. Deptuła, T. Olczak, A.G. Chmielewski, A. Moreno

3. Method for obtaining the Ni/NiO cathodesGold medal at the 55th World Exhibition of Innovation, Research and New Technology “Brussels Eureka2006”, Belgium, 23-27.11.2006W. Łada, A. Deptuła, T. Olczak, A.G. Chmielewski, A. Moreno

4. Diploma of the Ministry of Education and Science for the project “Method for obtaining hollow sphericalparticles from ceramic and metallic materials reduced by hydrogen”A. Deptuła, A.G. Chmielewski, W. Łada, T. Olczak

5. Congratulatory letter of the Ministry of Education and Science for the project “Method for obtainingcalcium phosphate layers, especially hydroxyapatite”A. Deptuła, W. Łada, T. Olczak, R.Z. LeGeros, J.P. LeGeros

6. Method for removal of nitrogen oxides from industrial gases. A facility for mixing gases reacting chemi-cally. Method for removal volatile organic impurities such as polycyclic aromatic hydrocarbons fromindustrial flue gasesGold medal at the 55th World Exhibition of Innovation, Research and New Technology “Brussels Eureka2006”, Belgium, 23-27.11.2006A.G. Chmielewski

7. Method for removal of nitrogen oxides from industrial gases. A facility for mixing gases reacting chemi-cally. Method for removal volatile organic impurities such as polycyclic aromatic hydrocarbons fromindustrial flue gasesSpecial award from the Russian Federal Agency for Science and InventionA.G. Chmielewski

8. First place for the meritorious poster “Application of extraction to the solid phase in the determinationof heavy metals by GF-AAS” presented at the XI Conference “Application of AAS, ICP-AES, ICP-MSmethods in the environmental analysis”, Warszawa, Poland, 09-10.11.2006J. Chwastowska, W. Skwara, E. Sterlińska, J. Dudek, L. Pszonicki

9. First degree group award of Director of the Institute of Nuclear Chemistry and Technology for two publi-cations in “Talanta” presenting methods for the determination of platinum, palladium and chromium intrace quantities in environmental samples and speciation analysis of Cr(VI) in the presence of Cr(III)L. Pszonicki, J. Chwastowska, W. Skwara, E. Sterlińska

10. Second degree group award of Director of the Institute of Nuclear Chemistry and Technology for publica-tions in the journals “Biochemical and Biophysical Research Communications”, “Journal of BiologicalChemistry” and “Acta Biochimica Polonica” devoted to studies of relations between the metabolism ofiron on a cell level and DNA oxidative damageM. Kruszewski, H. Lewandowska, T. Bartłomiejczyk, T. Iwaneńko, B. Sochanowicz

11. Third degree group award of Director of the Institute of Nuclear Chemistry and Technology for theessential contribution to the work on basic studies of secondary periodicity of elements of the block p(group 13) published in “European Journal of Inorganic Chemistry”S. Siekierski, K. Frąckiewicz

212 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

INSTRUMENTAL LABORATORIES AND TECHNOLOGICALPILOT PLANTS

I. DEPARTMENT OF NUCLEAR METHODS OF MATERIALS ENGINEERING

1. Laboratory of Materials ResearchActivity profile: Studies of the structure and properties of materials and historical art objects. Modi-fication of surface properties of materials by means of intense plasma pulses and ions beams. Syn-thesis and studies of new type of materials with predetermined properties (biocidal, fungicidal,sorptional). Characterization of structural properties of materials using SEM (scanning electronmicroscopy), X-ray fiffraction (powder and single crystal). Determination of elemental content ofenvironmental and geological samples, industrial waste materials, historic glass objects and othermaterials by energy dispersive X-ray fluorescence spectrometry using a radioisotope excitation sourceas well as a low power X-ray tube and using a 2 kW X-ray tube in total reflection geometry. Deter-mination of radioactive isotope content in environmental samples and historical glass objects bygamma spectrometry.• Scanning electron microscopeDSM 942, LEO-Zeiss (Germany)Technical data: spatial resolution – 4 nm at 30 kV, and 25 nm at 1 kV; acceleration voltage – up to 30 kV;chamber capacity – 250x150 mm.Application: SEM observation of various materials such as metals, polymers, ceramics and glasses.Determination of characteristic parameters such as molecule and grain size.• Scanning electron microscope equipped with the attachment for fluorescent microanalysisBS-340 and NL-2001, TESLA (Czech Republic)Application: Observation of surface morphology and elemental analysis of various materials.• Vacuum evaporatorJEE-4X, JEOL (Japan)Application: Preparation of thin film coatings of metals or carbon.• Gamma radiation spectrometerHP-Ge, model GS 6020; Canberra-Packard (USA)Technical data: detection efficiency for gamma radiation – 60.2%, polarization voltage – 4000 V,energy resolution (for Co-60) – 1.9 keV, analytical program “GENIE 2000”.Application: Neutron activation analysis, measurements of natural radiation of materials.• Gamma spectrometer in low-background laboratoryEGG ORTECTechnical data: HPGe detector with passive shield; FWHM – 1.9 keV at 1333 keV, relative effi-ciency – 92%.• Total reflection X-ray spectrometerPico TAX, Institute for Environmental Technologies (Berlin, Germany)Technical data: Mo X-ray tube, 2000 W; Si(Li) detector with FHWM 180 eV for 5.9 keV line;analysed elements – from sulphur to uranium; detection limits – 10 ppb for optimal range of analysedelements, 100 ppb for the others.Application: XRF analysis in total reflection geometry. Analysis of minor elements in water (tap, river,waste and rain water); analysis of soil, metals, raw materials, fly ash, pigments, biological samples.• X-ray spectrometerSLP-10180-S, ORTEC (USA)Technical data: FWHM – 175 eV for 5.9 keV line, diameter of active part – 10 mm, thickness of activepart of detector – 5.67 mm.Application: X-ray fluorescence analysis.• Coulter Porometer IICoulter Electronics Ltd (Great Britain)Application: Pore size analysis in porous media.• Vacuum chamber for plasma researchPOLVAC Technika Próżniowa

213INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

Technical data: dimensions – 300x300 mm; high voltage and current connectors, diagnostic windows.Application: Studies on plasma discharge influence on physicochemical surface properties of polymerfilms, particularly TEM (track-etched membranes).

2. Laboratory of Diffractional Structural Research

Activity profile: X-ray diffraction structural studies on metal-organic compounds originating as degra-dation products of substances naturally occurring in the environment. Röntgenostructural phaseanalysis of materials. Studies on interactions in a penetrant-polymer membrane system using smallangle scattering of X-rays, synchrotron and neutron radiation. Studies of structural changes occur-ring in natural and synthetic polymers under influence of ionising radiation applying X-ray diffrac-tion and differential scanning calorimetry.• KM-4 X-ray diffractometerKUMA DIFFRACTION (Poland)Application: 4-cycle diffractometer for monocrystal studies.

• CRYOJET - Liquid Nitrogen Cooling SystemOxford InstrumentsApplication: Liquid nitrogen cooling system for KM-4 single crystal diffractometer.

• HZG4 X-ray diffractometerFreiberger Präzisionsmechanik (Germany)Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphousmaterials.

• URD 6 X-ray diffractometerFreiberger Präzisionsmechanik (Germany)Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphousmaterials.

3. Sol-Gel Laboratory of Modern Materials

Activity profile: The research and production of advanced ceramic materials in the shape of powders,monoliths, fibres and coatings by classic sol-gel methods with modifications – IChTJ Process or byCSGP (Complex Sol-Gel Method) are conducted. Materials obtained by this method are the fol-lowing powders: alumina and its homogeneous mixtures with Cr2O3, TiO3, Fe2O3, MgO+Y2O3, MoO3,Fe, Mo, Ni and CaO, CeO2, Y2O3 stabilized zirconia, β and β’’ aluminas, ferrites, SrZrO3, ceramicsuperconductors, type YBCO (phases 123, 124), BSCCO (phases 2212, 2223), NdBa2Cu3Ox, theirnanocomposites, Li-Ni-Co-O spinels as cathodic materials for Li rechargeable batteries and fuelcells MCFC, BaTiO3, LiPO4, Li titanates: spherical for fusion technology, irregularly shaped assuperconductors and cathodic materials, Pt/WO3 catalyst. Many of the mentioned above systems, aswell as sensors, type SnO2, were prepared as coatings on metallic substrates. Bioceramic materialsbased on calcium phosphates (e.g. hydroxyapatite) were synthesized in the form of powders, mono-liths and fibres.• DTA and TGA thermal analyserOD-102 Paulik-Paulik-Erdey, MOM (Hungary)Technical data: balance fundamental sensitivity – 20-0.2 mg/100 scale divisions, weight range – 0-9.990 g,galvanometer sensitivity – 1x10–10 A/mm/m, maximum temperature – 1050oC.Application: Thermogravimetric studies of materials up to 1050oC.

• DTA and TGA thermal analyser 1500MOM (Hungary)Technical data: temperature range – 20-1500oC; power requirements – 220 V, 50 Hz.Application: Thermal analysis of solids in the temperature range 20-1500oC.

• Research general-purpose microscopeCarl Zeiss Jena (Germany)Technical data: General purpose microscope, magnification from 25 to 2500 times, illumination ofsample from top or bottom side.

• Metallographic microscopeEPITYP-2, Carl-Zeiss Jena (Germany)Technical data: magnification from 40 to 1250 times.Application: Metallographic microscope for studies in polarized light illumination and hardnessmeasurements.

• Laboratory furnaceCSF 12/13, CARBOLITE (Great Britain)Application: Temperature treatment of samples in controlled atmosphere up to 1500oC with auto-matic adjustment of final temperature, heating and cooling rate.


II. DEPARTMENT OF RADIOISOTOPE INSTRUMENTS AND METHODS

Laboratory of Industrial RadiometryActivity profile: Research and development of non-destructive methods and measuring instrumentsutilizing physical phenomena connected with the interaction of radiation with matter: developmentof new methods and industrial instruments for measurement of physical quantities and analysis ofchemical composition; development of measuring instruments for environmental protection (dustmonitors, radon meters); implementation of new methods of calibration and signal processing (multi-variate models, artificial neural networks); designing, construction and manufacturing of measur-ing instruments and systems; testing of industrial and laboratory instruments.• Multichannel analyser board with software for X and γ-ray spectrometryCanberra• Function generatorFG-513, American Reliace INC

III. DEPARTMENT OF RADIOCHEMISTRY

1. Laboratory of Coordination and Radiopharmaceutical ChemistryActivity profile: Preparation of novel technetium(I, III, V) complexes with chelating ligands (mono-and bifunctional), labelled with 99mTc, as potential diagnostic radiopharmaceuticals or their pre-cursors. Studying of their hydrophilic-lipophilic properties, structure and their interactions withpeptides. Also analogous rhenium(I) complexes are synthesised and studied. Novel platinum andpalladium complexes with organic ligands, analogs of cisplatin, are synthesised and studied as po-tential antitumor agents. Solvent extraction separation of trivalent actinides from lanthanides isstudied, directed towards nuclear waste treatment. Studies on chemical isotope effects of metal ions –search of correlations between isotope separation factor and structure of species exchanging theisotopes in two-phase chemical systems. (For the research equipment, common for both Laboratories,see below.)

2. Laboratory of Heavy ElementsActivity profile: Synthesis of novel macrocyclic complexes of 47Sc, 103m,105Rh and 212Bi radionuclides –potential precursors for therapeutic radiopharmaceuticals. Elaboration of new methods forastatination (211At) of biomolecules via metal complexes. Design of new medically important radio-nuclide generators, e.g. 82Sr/82Rb, 103Ru/103mRh, 44Ti/44Sc. Structural studies on the complexes andsolvates of heavy p-block elements in the solid state and in solution.• Spectrometric setORTECMultichannel analyser, type 7150, semiconductor detectorApplication: Measurements and identification of γ- and α-radioactive nuclides.

• Gas chromatograph610, UNICAM (England)Application: Analysis of the composition of mixtures of organic substances in the gas and liquid state.

• High Performance Liquid Chromatography systemGradient HPLC pump L-7100, Merck (Germany) with γ-radiation detector, INCT (Poland)Application: Analytical and preparative separations of radionuclides and/or various chemical formsof radionuclides.

• High Performance Liquid Chromatography systemGradient HPLC pump LC-10ADvp, with a UV-VIS detector SPD-10Avp/10AVvp, Shimadzu (Japan)Application: Analytical and preparative separations of radionuclides and/or various chemical formsof radionuclides.

• Capillary electrophoresis systemPrinCE Technologies with a UV-VIS detector (Bischoff Lambda 1010) and a radiometric detectorActivity Gauge type Tc-99m (INCT, Poland)Application: Analytical separation of various radiochemical and chemical species, in particular charged.

• Gamma isotope TLC analyzerSC-05 (INCT, Poland)Application: Measurements of gamma radioactivity distribution along thin-layer-chromatographyplates and electrophoretic strips.

• UV-VIS spectrophotometerDU 68, Beckman (Austria), modernized and computerizedApplication: Recording of electronic spectra of metal complexes and organic compounds in solu-tion. Analytical determination of the concentration of these compounds.


• FT-IR spectrophotometerEQUINOX 55, Bruker (Germany)Application: Measurements of IR spectra of metal complexes and other species in the solid stateand in solution.

IV. DEPARTMENT OF NUCLEAR METHODS OF PROCESS ENGINEERING

1. Laboratory for Flue Gases AnalysisActivity profile: Experimental research connected with elaboration of removal technology for SO2and NOx and other hazardous pollutants from flue gases.• Ultrasonic generator of aerosolsTYTAN XLG

• Gas chromatographPerkin-Elmer (USA)

• Gas analyser LANDApplication: Determination of SO2, NOx, O2, hydrocarbons, and CO2 concentrations.

• Impactor MARK IIIAndersen (USA)Application: Measurement of aerosol particle diameter and particle diameter distribution.

2. Laboratory of Stable Isotope Ratio Mass Spectrometry

Activity profile: Study of isotope ratios of stable isotopes in hydrogeological, environmental, medi-cal and food samples.• Mass spectrometer DELTAplus

Finnigan MAT (Bremen, Germany)Technical data: DELTAplus can perform gas isotope ratio measurements of H/D, 13C/12C, 15N/14N,18O/16O, 34S/32S.Application: For measurements of hydrogen (H/D) and oxygen (18O/16O) in water samples with twoautomatic systems: H/Device and GasBench II. The system is fully computerized and controlled bythe software ISODAT operating in multiscan mode (realtime). The H/Device is a preparation sys-tem for hydrogen from water and volatile organic compounds determination. Precision of hydrogenisotope ratio determination is about 0.5‰ for water. The GasBench II is a unit for on-line oxygenisotope ratio measurements in water samples by “continuous flow” techniques. With GasBench II,water samples (0.5 ml) can be routinely analyzed with a precision and accuracy of 0.05‰. The totalvolume of water sample for oxygen and hydrogen determination is about 2 ml.

• Elemental Analyzer Flash 1112 NCSThermo Finnigan (Italy)Application: For measurement of carbon, nitrogen and sulfur contents and their isotope composi-tion in organic matter (foodstuff and environmental samples).

• Gas chromatograph mass spectrometerGC MS-QP 5050A, GC-17A, Shimadzu (Japan)Technical data: capillary column – SPB 5, HP-5MS, SUPELCOWAX™-10.

3. Radiotracers Laboratory

Activity profile: Radiotracer research in the field of: environmental protection, hydrology, under-ground water flow, sewage transport and dispersion in rivers and sea, dynamic characteristics ofindustrial installations and waste water treatment stations.• Heavy lead chamber (10 cm Pb wall thickness) for up to 3.7x1010 Bq (1 Ci) radiotracer activity

preparations in liquid or solid forms

• Field radiometers for radioactivity measurements

• Apparatus for liquid sampling

• Turner fluorimeters for dye tracer concentration measurements

• Automatic devices for liquid tracers injection

• Liquid-scintillation counterModel 1414-003 ”Guardian”, Wallac-Oy (Finland)Application: Extra low-level measurements of α and β radionuclide concentrations, especially for H-3,Ra-226, Rn-222 in environmental materials, e.g. underground waters, surface natural waters; inother liquid samples as waste waters, biological materials, mine waters, etc.


4. Membrane LaboratoryActivity profile: Research in the field of application of membranes for radioactive waste processing,separation of isotopes and gas separation.• Membrane distillation plant for concentration of solutionsTechnical data: output ~0.05 m3/h, equipped with spiral-wound PTFE module G-4.0-6-7 (SEPGmbH) with heat recovery in two heat-exchangers.• Ultrafiltration plant equipped with replaceable ceramic multichannel modules• US 150 laboratory stand (Alamo Water) for reverse osmosis testsTechnical data: working pressure – up to 15 bar, flow rate – 200 dm3/h, equipped with two RO modules.• Laboratory stand with different ceramic replaceable tubular UF modules• Laboratory set-up for small capillary and frame-and-plate microfiltration and membrane distil-

lation module examination (capillary EuroSep, pore diameter 0.2 μm and frame-and-plate theINCT modules)

• The system for industrial waste water pretreatmentTechnical data: pressure – up to 0.3 MPa; equipped with ceramic filters, bed Alamo Water filterswith replaceable cartridge (ceramic carbon, polypropylene, porous or fibrous) and frame-and-platemicrofiltration module.• Gas separation system equipped with UBE capillary module• Laboratory stand for pervaporation and vacuum membrane distillation tests• Automatic refractometerJ357, Rudolph Technologies Inc. (USA)Technical data: nD=1.29-1.70 , 0-95 BRIX.

• SpectrophotometerHACH 2000 (Germany)

V. DEPARTMENT OF RADIATION CHEMISTRY AND TECHNOLOGY

1. Laboratory of Radiation Modified PolymersActivity profile: Modification of polymers by ionising radiation. Radiation-induced radicals in poly-mers. Optimization of mechanical and chemical properties of biocompatible materials followingelectron beam and gamma irradiation, biological application of polymers. Nanocomposites andnanofillers modified by ionising radiation.• ExtruderPLV-151, BRABENDER-DUISBURG (Germany)Technical data: Plasti-Corder consists of: driving motor, temperature adjustment panel, thermo-stat, crusher, mixer, extruder with set of extrusion heads (for foils, rods, sleevs, tubes), cooling tank,pelleting machine, collecting device.Application: Preparation of polymer samples.

• Equipment for mechanical testing of polymer samplesINSTRON 5565, Instron Co. (England)Technical data: high performance load frame with computer control device, equipped with DigitalSignal Processing and MERLIN testing software; max. load of frame is 5000 N with accuracy below0.4% in full range; max. speed of testing 1000 mm/min in full range of load; total crosshead travel –1135 mm; space between column – 420 mm; the environmental chamber 319-409 (internal dimen-sions 660x230x240 mm; temperature range – from -70 to 250oC).Application: The unit is designed for testing of polymer materials (extension testing, tension,flexure, peel strength, cyclic test and other with capability to test samples at low and high tem-peratures).

• ViscosimeterCAP 2000+H, Brookfield (USA)Technical data: range of measurements – 0.8-1500 Pa*s, temperature range – 50-235oC, cone rota-tion speed – 5-1000 rpm, sample volume – 30 μl. Computer controlled via Brookfield CALPCALC®

software.Application: Viscosity measurements of liquids and polymer melts.• Differential scanning calorimeterMDSC 2920 CE, TA InstrumentsTechnical data: equipped with liquid nitrogen cooling adapter (LNCA) for 60 l of liquid nitrogenand sample encapsulating press for open or hermetically sealed pans. Module for Modulated DSC™is included. Working temperature – from -150oC with the LNCA to 725oC.


Application: Determines the temperature and heat flow associated with material phase transitionsas a function of time and temperature. It also provides quantitative and qualitative data on endother-mic (heat absorption) and exothermic (heat evolution) processes of materials during physical tran-sitions that are caused by phase changes, melting, oxidation, and other heat-related changes.• Processor tensiometer K100CTechnical data: supplied with the thermostatable sample vessel. Working temperature is from -10to +100oC. The height of the sampler carrier is adjusted with the help of a high-precision motor.The balance system is automatically calibrated by a built-in reference weight with a high precision.Resolutions of measurement is 0.01 mN/m.Application: Surface and interfacial tension measurement of liquids – Du Noüy Ring method andDynamic Wilhelmy method with range 1-1000 mN/m; dynamic contact angle measurements; sur-face energy calculations on solids, powders, pigments, fibers, etc.; sorption measurements with theWashburn method for determining the surface energy of a powder-form solid. Controlled byLabDesk™ software.

• Spectrophotometer UV-VISUNICAM SP 1800 with linear recorder UNICAM AR 25Technical data: Wavelength – 190-850 nm.

• Equipment for gel electrophoresisSystem consists of: horizontal electrophoresis apparatus SUBMINI Electrophoresis Mini-System,transilluminator UV STS-20M JENCONS (United Kingdom), centrifuge EBA 12 Hettich/Zen-trifugen, microwave oven KOR 8167 Daewoo.• Melt flow testerZWICK 4105, Zwick GmbH (Germany)Technical data: temperature of measurements – 150, 190 and 230oC; press load – 2.16 and 5.00 kg;manual operating.Application: Determination of standard values of melt-mass flow rate (MFR) of the thermoplasticmaterials (polymers) under specified conditions of temperature and load (according to standards:PN-EN ISO 1133:2005, ASTM 1328); comparison of rheological properties of polymers, includingfilled materials; comparison of degree of degradation; testing of catalogue data.

2. Radiation Sterilization Pilot Plant of Medical Devices and Tissue Grafts

Activity profile: Research and development studies concerning new materials for manufacturingsingle use medical devices (resistant to radiation up to sterilization doses). Elaboration of monitor-ing systems and dosimetric systems concerning radiation sterilization processing. Introducing spe-cific procedures based on international recommendations of ISO 13485:2003 and ISO 11137:2006standards. Sterilization of medical utensils, approx. 70 million pieces per year.• Electron beam acceleratorUELW-10-10, NPO TORIJ (Moscow, Russia)Technical data: beam energy – 10 MeV, beam power – 10 kW, supply power – 130 kVA.Application: Radiation sterilization of medical devices and tissue grafts.• Spectrophotometer UV-VISModel U-1100, HitachiTechnical data: wavelength range – 200-1100 nm; radiation source – deuterium discharge (D2) lamp,and tungsten-iodine lamp.• Spectrophotometer UV-VISModel SEMCO S/ECTechnical data: wavelength range – 340-1000 nm, radiation source – halogen lamp.Application: Only for measurements of dosimetric foils.• Bacteriological and culture oven with temperature and time control and digital readingIncudigit 80LTechnical data: maximum temperature – 80oC, homogeneity – ±2%, stability – ±0.25%, thermometererror – ±2%, resolution – 0.1oC.

3. Laboratory of Radiation Microwave CryotechniqueActivity profile: Radiation processes in solids of catalytic and biological importance: stabilization ofcationic metal clusters in zeolites, radical reactions in polycrystalline polypeptides, magnetic prop-erties of transition metals in unusual oxidation states; radical intermediates in heterogeneouscatalysis.• Electron spin resonance (ESR) Q-band spectrometerBruker E-500, equipped with continuous flow helium cryostat Oxford Instruments CF935 O andDICE cw ENDOR/TRIPLE unit Bruker E-560 with rf amplifier 10 kHz-220 MHz.


• Electron spin resonance (ESR) X-band spectrometerBruker ESP-300, equipped with: frequency counter Hewlett-Packard 5342A, continuous flow heliumcryostat Oxford Instruments ESR 900, continuous flow nitrogen cryostat Bruker ER 4111VT,ENDOR-TRIPLE unit Bruker ESP-351.Application: Studies of free radicals, paramagnetic cations, atoms and metal nanoclusters as well asstable paramagnetic centers.

• Spectrophotometer UV-VISLAMBDA-9, Perkin-ElmerTechnical data: wavelength range – 185-3200 nm, equipped with 60 nm integrating sphere.

4. Pulse Radiolysis Laboratory

Activity profile: Studies of charge and radical centres transfer processes in thioether model com-pounds of biological relevance in liquid phase by means of time-resolved techniques (pulse radiolysisand laser flash photolysis) and steady-state γ-radiolysis.• Accelerator LAE 10 (nanosecond electron linear accelerator)INCT (Warszawa, Poland)Technical data: beam power – 0.2 kW, electron energy – 10 MeV, pulse duration – 7-10 ns and about 100ns, repetition rate – 1, 12.5, 25 Hz and single pulse, pulse current – 0.5-1 A, year of installation 1999.Application: Research in the field of pulse radiolysis.

• Gas chromatographGC-14B, Shimadzu (Japan)Specifications: two detectors: thermal conductivity detectors (TCD) and flame ionization detector(FID). Column oven enables installation of stainless steel columns, glass columns and capillarycolumns. Range of temperature settings for column oven: room temperature to 399oC (in 1oC steps),rate of temperature rise varies from 0 to 40oC/min (in 0.1oC steps). Dual injection port unit with twolines for simultaneous installation of two columns.Application: Multifunctional instrument for analysis of final products formed during radiolysis ofsulphur and porphyrin compounds and for analysis of gaseous products of catalytic reactions inzeolites.

• Dionex DX500 chromatograph systemDionex CorporationSpecifications: The ED40 electrochemical detector provides three major forms of electrochemi-cal detection: conductivity, DC amperometry and integrated and pulsed amperometry. The AD20absorbance detector is a dual-beam, variable wavelength photometer, full spectral capability isprovided by two light sources: a deuterium lamp for UV detection (from 190 nm) and a tungstenlamp for VIS wavelength operation (up to 800 nm). The GP40 gradient pump with a deliverysystem designed to blend and pump mixtures of up to four different mobile phases at preciselycontrolled flow rates. The system can be adapted to a wide range of analytical needs by choice ofthe chromatography columns: AS11 (anion exchange), CS14 (cation exchange) and AS1 (ion ex-clusion).Application: The state-of-the-art analytical system for ion chromatography (IC) and high-perfor-mance liquid chromatography (HPLC) applications. Analysis of final ionic and light-absorbed prod-ucts formed during radiolysis of sulphur compounds. The system and data acquisition are controlledby a Pentium 100 PC computer.

• Digital storage oscilloscope6051A Wave Runner, LeCroySpecifications: Bandwidth – 500 MHz; rise time – 750 ps; sample rate - up to 5 Gs/s (by combining2 channels); acquisition memory – 16 Mpt with 8 Mpt per channel; sensitivity – 2 mV/div to 10 V/div;fully variable, fully programmable; standard ports – 10/100Base-T Ethernet, Parallel, GPiB –IEEE488.2, USB 2.0 (5), RS-232, SVGA Video Out, Audio in/out; Windows XP Professional operatingsystem.Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulseradiolysis system dedicated to the nanosecond electron linear accelerator (LAE 10). The multipletime scales can be generated by a computer from a single kinetic trace originating from DSO sincethe oscilloscope produces a sufficient number of time points (up to 16 M points record length).

• Digital storage oscilloscope9354AL, LeCroySpecifications: Bandwidth DC to 500 MHz; sample rate – 500 Ms/s up to 2 Gs/s (by combining4 channels); acquisition memory – up to 8 Mpt with 2 Mpt per channel; time/div range – 1 ns/div to1000 s/div; sensitivity – 2 mV/div to 5 V/div; fully variable, fully programmable via GPIB andRS-232C.Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulseradiolysis system dedicated to the nanosecond laser flash photolysis. The multiple time scales can


be generated by a computer from a single kinetic trace originating from DSO since the oscilloscopeproduces a sufficient number of time points (up to 8 M points record length).• Digital storage oscilloscope9304C, LeCroySpecifications: Bandwidth DC to 200 MHz; sample rate – 100 Ms/s up to 2 Gs/s (by combining 4channels); acquisition memory – up to 200 kpt per channel; time/div range – 1 ns/div to 1000 s/div;sensitivity – 2 mV/div to 5 V/div; fully variable.Application: Digital oscilloscope (DO) is used in pulse radiolysis system dedicated to the nano-second electron linear accelerator (LAE 10).

• Nd:YAG laserSurelite II-10, Continuum (USA)Specifications: energy (mJ) at 1064 nm (650), 532 nm (300), 355 nm (160) and 266 nm (80); pulsewidth – 5-7 ns (at 1064 nm) and 4-6 ns (at 532, 355 and 266 nm); energy stability – 2.5-7%; can beoperated either locally or remotely through the RS-232 or TTL interface.Application: A source of excitation in the nanosecond laser flash photolysis system being currentlyunder construction in the Department.

• Potentiostat/Galvanostat VersaStat IIPrinceton Applied Research (USA)Specifications: Power amplifier compliance voltage single channel – ±20 V, maximum current –±200 mA, rise time – 100 μs, slew rate – 1 V/μs; system performance: minimum timebase – 100 μs,minimum potential step – 250 μV, noise and ripple <50 μV rms typically, minimum current range –1 μA (hardware), minimum current range – 100 nA (software), minimum current resolution – 200pA, drift – vs. time <50 μV/°C vs. time: <200 μV/week. iR compensation: current interrupt 12-bitpotential error correction total int. time <50-2000 μs. Accuracy: applied potential – 0.2% of read-ing ±2 mV, applied current – 0.2% of full-scale current. Computer interface: GPIB IEEE-488,RS-232. Differential electrometer: input bias current <50 pA at 25°C, typically <20 pA at 25°C.Max. voltage range – ±2 V, max. input voltage differential – ±10 V. Bandwidth – -3 dB at>4 MHz.Offset voltage <100 μV. Offset temperature stability <5 μV/°C. Common mode rejection >70 dBat 100 Hz and >60 dB at 100 kHz. Input impedance >1010 Ω, typically 1011 Ω in parallel with<50 pF.

5. Research Accelerator LaboratoryActivity profile: Laboratory is equipped with accelerators providing electron beams which makecapable to perform the irradiation of investigated objects within wide range of electron energy from100 keV to 13 MeV and average beam power from 0.1 W do 20 kW, as well as with Co-60 gammasources with activity 1.9x1010 to 1.3x1014 Bq and dose rate from 0.03 to 1.8 kGy/h. The described aboveirradiators are completed in a unique in world scale set of equipment which can be applied in a widerange of electron beam and gamma-ray research and radiation processing.• Accelerator ILU-6INP (Novosibirsk, Russia)Technical data: beam power – 20 kW, electron energy – 0.7-2 MeV.Application: Radiation processing.• Linear electron acceleratorLAE 13/9, Institute of Electro-Physical Equipment (Russia)Technical data: electron energy – 10-13 MeV; electron beam power – 9 kW.Application: Radiation processing.• Cobalt source IIssledovatel (Russia)Technical data: 32 sources with an actual activity of 9.2x1013 Bq.Application: Radiation research.• Cobalt source IIMineyola 1000, INR (Świerk, Poland)Technical data: 8 rods with an initial activity of 2.66x1013 Bq; the actual activity is 1.07x1013 Bq.Application: Radiation research.

• Electron acceleratorAS-2000 (the Netherlands)Technical data: energy – 0.1-2 MeV, max. beam current – 100 μA.Application: Irradiation of materials.

• SpectrometerDLS-82E, SEMITRAP (Hungary)Application: Research in radiation physics of semiconductors.


• Argon laserILA-120, Carl Zeiss (Jena, Germany)Application: Measurements of optical properties.

• SpectrometerDLS-81 (Hungary)Application: Measurements of semiconductor properties.

• Argon laserLGN-503 (Russia)Application: Measurements of optical properties.

VI. DEPARTMENT OF ANALYTICAL CHEMISTRY

1. Laboratory of Spectral Atomic AnalysisActivity profile: atomic absorption and emission spectroscopy, studies on interference mechanisms,interpretation of analytical signals, service analysis.• Atomic absorption spectrometerSH-4000, Thermo Jarrell Ash (USA); equipped with a 188 Controlled Furnace Atomizer (CTF 188),Smith-Heftie background correction system and atomic vapor (AVA-440) accessory.Application: For analyses of samples by flame and furnace AAS.

• Atomic absorption spectrometerSP9-800, Pye Unicam (England); equipped with SP-9 Furnace Power Supply, PU-9095 data graphicssystem, PU-9095 video furnace programmer and SP-9 furnace autosampler.Application: For analyses of samples by flame and furnace AAS.

• Atomic absorption spectrometerSOLAR M6 MK II (Thermo Electron Corporation), equipped with: graphite furnace GF 95 withD2 and Zeeman background correction system, autosampler FS 95 and hydride and cold vapourgenerator.Application: For analyses of samples by flame and furnace AAS.

2. Laboratory of Neutron Activation AnalysisActivity profile: The sole laboratory in Poland engaged for 40 years in theory and practice of neu-tron activation analysis in which the following methods are being developed: reactor neutron acti-vation analysis (the unique analytical method of special importance in inorganic trace analysis),radiochemical separation methods, ion chromatography. The laboratory is also the main Polishproducer of CRMs and the provider for Proficiency Testing exercises.• Laminar boxHV mini 3, Holten (Denmark)Technical data: air flow rate 300 m3/h.Application: Protection of analytical samples against contamination.

• Ion chromatograph2000i/SP, Dionex (USA)Technical data: data evaluating program AI-450, ion exchange columns of type Dionex Ion Pac,conductivity detector, UV/VIS detector.Application: Analyses of water solutions, determination of SO2, SO3 and NOx in flue gases and inair, determination of metals in biological and environmental samples.

• HPGe detector, well-typeCGW-3223, Canberra, coupled with analog line (ORTEC) and multichannel gamma-ray analyzerTUKANApplication: Instrumental and radiochemical activation analysis.

• Coaxial HPGe detectorPOP-TOP, ORTEC (USA), coupled with analog line (ORTEC) and multichannel gamma-ray ana-lyzer TUKAN

• HPGe detector, well-typeCGW-5524, Canberra, coupled with multichannel gamma-ray analyzer (hardware and software)CanberraApplication: Instrumental and radiochemical activation analysis.

• Analytical balanceSartorius BP2 215Application: For weighing sample of mass >10 mg to 220 g.


• Analytical micro-balanceSartorius MC5Application: Preparation of mono- and multi-elemental standards as well as for weighing smallmass samples, less than 10 mg.• BalanceWPX 650, RADWAG (Poland)Application: For weighing sample of mass >10 mg to 650 g.• Liquid Scintillation AnalyzerTRI-CARB 2900TR, Packard BioScience CompanyApplication: α- and β-ray measurements.• Planetary Ball MillPM 100, RetschApplication: Grinding and mixing: soft, medium hard to extremly hard, brittle or fibrous materials.• Balance-drierADS50, AXIS (Poland)Application: Determination of mass and humidity of samples.• Microwave digestion systemUnicleverTMII, PLAZMATRONIKA (Poland)Application: Microwave digestion of samples.• Microwave digestion systemBM-1S/II, PLAZMATRONIKA (Poland)Application: Microwave digestion of samples.• HomogenizerINCT (Poland)Application: Homogenization of the material used for preparation of CRMs.• Peristaltic pumpREGLO ANALOG MS-4/6-100, ISMATEC (Switzerland)Application: Regulation of flow of eluents during elution process.

3. Laboratory of ChromatographyActivity profile: Development of HPLC methods for determination of environmental pollutants,application of HPLC and ion-chromatography monitoring of degradation organic pollutants in watersand wastes using ionizing radiation, development of chromatographic methods, preconcentrationof organic environmental pollutants, development of chromatographic methods of identification ofnatural dyes used for ancient textiles.• Apparatus for biological oxygen demand determination by respirometric method and dissolved

oxygen measurement methodWTW-Wissenschaftlich-Technische Wersttätten (Germany)Application: Analyses of water and waste water samples.• Apparatus for chemical oxygen demand determination by titrimetric methodBehr Labor-Technik (Germany)Application: Analyses of water and waste water samples.• Set-up for solid phase-extraction (vacuum chamber for 12 columns and vacuum pump)Application: Analyses of water and waste water samples.• Shimadzu HPLC system consisting of: gradient pump LC-10AT, phase mixer FCV-10AL, diode-

-array detector SPD-M10A, column thermostat CTO-10ASApplication: Analyses of natural dyes, radiopharmaceuticals, water and waste water samples.• Laboratory ozone generator301.19, Erwin Sander Elektroapparatebau GmbH (Uetze-Eltze, Germany)Application: Ozone production for degradation of pollutants in waste water samples.

4. Laboratory of General AnalysisActivity profile: Preparation and application of new chelating sorbents to the separation of metaltraces from environmental materials for their determination by atomic absorption spectrometry,speciation analysis, service analysis.• SpectrophotometerPU8625 Series UV/Visible, PhilipsTechnical data: wavelength range – 200-1100 nm.Application: Measurements of absorbance in spectrophotometric analysis.


• SpectrophotometerUV-160, Shimadzu (Japan)Technical data: wavelength range – 200-1100 nm, with automatic baseline correction and graphic printer.Application: Routine spectrophotometric analysis and research works.

VII. DEPARTMENT OF RADIOBIOLOGY AND HEALTH PROTECTION

• Equipment for electrophoretic analysis of DNACHEF III, BIO-RAD (Austria)Application: Analysis of DNA fragmentation as a result of damage by various physical and chemical agents.• Microplate readerELISA, ORGANON TEKNICA (Belgium)Application: For measurement of optical density of solutions in microplates.• Hybridisation ovenOS-91, BIOMETRA (Germany)Technical data: work temperatures from 0 to 80oC; exchangeable test tubes for hybridisation.Application: For polymerase chain reaction (PCR).• SpectrofluorimeterRF-5000, Shimadzu (Japan)Application: For fluorimetric determinations.

• Transilluminator for electrophoretic gelsBiodoc, BIOMETRA (Great Britain)Application: For analysis of electrophoretic gels.• Laminar flow cabinetNU-437-400E, Nu Aire (USA)Application: For work under sterile conditions.• Liquid scintillation counterLS 6000LL, BECKMAN (USA)Application: For determinations of radioactivity in solutions.

• Research microscope universalNU, Carl Zeiss Jena (Germany)Application: For examination of cytological preparations.Comments: Universal microscope for transmission and reflected light/polarised light. Magnifica-tion from 25x to 2500x. Possibility to apply phase contrast.• IncubatorT-303 GF, ASSAB (Sweden)Technical data: 220 V, temperature range – 25-75oC.Application: For cell cultures under 5% carbon dioxide.• IncubatorNU 5500E/Nu Aire (USA)Technical data: 220 V, temperature range from 18 to 55oC.Application: For cell cultures under 0-20% carbon dioxide.• Laminar flow cabinetV-4, ASSAB (Sweden)Application: For work under sterile conditions.• Image analysis systemKomet 3.1, Kinetic Imaging (Great Britain)Application: For comet (single cell gel electrophoresis) analysis.• ISIS 3Metasystem (Germany)Application: Microscopic image analysis system for chromosomal aberrations (bright field and fluor-escence microscopy).

VIII. LABORATORY FOR DETECTION OF IRRADIATED FOOD

Activity profile: Detection of irradiated foods. European standards (CEN) adapted as analyticalmethods to be routinely used in the Laboratory, are based on electron paramagnetic resonance(EPR/ESR) spectroscopy, pulsed photostimulated luminescence (PPSL) and thermoluminescencemeasurements (TL). The research work is focused mainly on the development of the above three


methods and the enlargement of their ability of the detection of irradiation in the variety of food-stuffs. Laboratory is capable to examine food samples by the DNA comet assay (decomposition ofsingle cell) and statistical germination study. The quality assurance system was adapted in the Labo-ratory in 1999 and in 2006 was actualised and documented in agreement with the PN-EN 1SO/IEC17025:2005 standard. Actually Laboratory possesses Accreditation Certificate of Testing Labora-tory nr AB 262 issued by the Polish Centre for Accreditation and valid until 24.10.2010.• Thermoluminescence readerTL-DA-15 Automated, Risoe National Laboratory (Denmark)Technical data: turntable for 24 samples, heating range – 50÷500oC, heating speed – 0.5÷10.0oC/s,optical stimulated luminescence (OSL) system.Application: Detection of irradiated foods containing silicate minerals, e.g. spices, vegetables shrimpstc, research work on irradiated foods.• Fluorescence microscopeOPTIPHOT Model X-2, NIKON (Japan)Technical data: halogen lamp 12 V-100 W LL; mercury lamp 100 W/102 DH; lenses (objectives)CF E Plan Achromat 4x, CF E Plan Achromat 40x, CF FLUOR 20x.Application: Detection of irradiated foods by the DNA comet assay method, research work onapoptosis in mammalian cells, biological dosimetry, analysis of DNA damage in mammalian cells.• Compact EPR spectrometerEPR 10-MINI, St. Petersburg Instruments Ltd. (Russia)Technical data: sensitivity – 3x1010, operating frequency (X band) – 9.0-9.6 GHz, max. microwavepower – 80 mW, magnetic field range – 30-500 mT, frequency modulation – 100 kHz.Application: Detection of irradiated foods, bone and alanine dosimetry, research work on irradi-ated foods and bone tissues.• Pulsed photostimulated luminescence systemSURRC (United Kingdom)Technical data: pulsed light source – diodes IR LED; detector – photomultiplier ETL; pulse on andoff periods – 15 μs; sample holder – 50 mm diameter disposable Petri dishes; set up – sample chamberand detector head assembly, contol unit, on line computer, optional.Application: Irradiated food screening system.

IX. EXPERIMENTAL PLANT FOR FOOD IRRADIATION

1. Microbiological LaboratoryActivity profile: optimization of food irradiation process by microbiological analysis.• SterilizerASUE, SMS (Warszawa, Poland)Application: Autoclaving of laboratory glass, equipment, and microbiological cultures.• Fluorescence microscopeBX, Olimpus (Germany)Application: Quantitative and qualitative microbiological analysis.

2. Experimental Plant for Food IrradiationActivity profile: Development of new radiation technologies for the preservation and hygienizationof food products. Development and standarization of the control system for electron beam process-ing of food. Development of analytical methods for the detection of irradiated food. Organization ofconsumer tests with radiation treated food products.• Accelerator ELEKTRONIKA (10 MeV, 10 kW)UELW-10-10, NPO TORIJ (Moscow, Russia)Application: Food irradiation.

224 INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

AAleshkevych Pavlo 151Antunes Ines 67Anuszewska Elżbieta 77

BBarański Marek 151Barcz Adam 141Barlak Marek 141Bartak Jakub 156Bartłomiejczyk Teresa 101Bartoś Barbara 67Basfar Ahmed A. 117Bilewicz Aleksander 67, 69, 70Bobrowski Krzysztof 19, 21, 22Bojanowska-Czajka Anna 52Borowiec Mieczysław T. 151Brykała Marcin 147, 151Brzozowska Kinga 104Brzóska Kamil 99Buczkowski Marek 145Bulska Ewa 81Bułka Sylwester 114, 118, 161Buraczewska Iwona 109

CCeluch Monika 25, 27Chajduk Ewelina 82, 85Chatgilialoglu Chryssostomos 21Chmielewska Dagmara K. 141, 153Chmielewski Andrzej G. 42, 114, 115, 117, 120,125, 126, 161Chwastowska Jadwiga 89, 147Cieśla Krystyna 44, 47, 49Cojocaru Cornel 121Cuna Stela Maria 113

DDanko Bożena 85Dąbrowski Ludwik 141Dembiński Wojciech 81Deperas Joanna 103Deperas-Kaminska Marta 103, 105Deptuła Andrzej 147, 151Derda Małgorzata 113, 123, 126Dłuska Ewa 121Dobrowolski Andrzej 125Domuchowski Wiktor 151Drzewicz Przemysław 52Dudek Jakub 82, 89Dyakonov Vladimir P. 151

Dybczyński Rajmund 73, 85Dziedzic-Gocławska Anna 30Dzierżanowski Piotr 134, 136Dźwigalski Zygmunt 163

EEdwards Alan 103Eliasson Ann-Charlotte 47Enache Mirela 25, 27

FFerreri Carla 21Filipiuk Dorota 79Fuente Julio R. De la 22Fuks Leon 77, 79

GGłuszewski Wojciech 39, 41, 49Gniazdowska Ewa 159Goretta Kenneth C. 147Govindarajan Subbian 93Grądzka Iwona 106Grigoriew Helena 153Grodkowski Jan 23Gruber Bożena 77Gryczka Urszula 42Gryz Michał 91, 92, 96Guzik Grzegorz P. 56, 63

HHarasimowicz Marian 120, 121Herdzik Irena 81Houée-Levin Chantal 19

IIwaneńko Teresa 100, 101, 102

JJaworska Agnieszka 121Jurczyk Renata 119

KKalinowska Justyna 141Kałuska Iwona 161Kamiński Artur 30Kciuk Gabriel 22Kempers Alexander J. 126Kierzek Joachim 134Kocia Rafał 23Kopcewicz Michał 141, 142

225INDEX OF THE AUTHORS

Kornacka Ewa M. 36Kosior Grzegorz 126Kowalska Ewa 67, 159Kozakiewicz Janusz 36Krasavin Eugene A. 105Krejzler Jadwiga 75Królak Edward 49Kruszewska Hanna 77Kruszewski Marcin 99, 100, 101, 102, 107Kulisa Krzysztof 85Kunicki-Goldfinger Jerzy 134, 136

LLaubsztejn Magdalena 60, 63Leciejewicz Janusz 91, 92, 93, 94, 96Lehner Katarzyna 58, 63Lewandowska Hanna 99Licki Janusz 115, 117Lindholm Carita 103Lloyd David 103Lundqvist Henrik 47

ŁŁada Wiesława 147, 151Łukasiewicz Andrzej 141Łyczko Monika 71, 73

MMachaj Bronisław 156, 159Mádl Martin 136Majdan Marek 79Majkowska Agnieszka 67, 70Malec-Czechowska Kazimiera 60, 63Mehta Kishor 118Męczyńska Sylwia 99Michalik Jacek 28, 30Migdał Wojciech 42, 161Mirkowski Jacek 19, 23Mirkowski Krzysztof 33Mirowicz Jan 158Miśkiewicz Agnieszka 121Morand Josselin 103Moss Raymond 103Mozziconacci Olivier 19, 21

NNarbutt Jerzy 71, 73, 75Natkaniec Ireneusz 94Neves Maria 67Nichipor Henrietta 52, 114Nowak Dorota 94Nowicki Andrzej 33, 144Nowicki Lech 142

OOlczak Tadeusz 147, 151Olszewska-Świetlik Justyna 128Orelovitch Oleg 144Ostapczuk Anna 115

PPalige Jacek 124, 125Pańczyk Ewa 128, 130Pawelec Andrzej 117Pawlukojć Andrzej 94Piekoszewski Jerzy 141, 142Pieńkos Jan 158, 159, 160Pogocki Dariusz 25, 27Polkowska-Motrenko Halina 82, 85Premkumar Thatan 93Pruszyński Marek 69Przybylski Jarosław 36Przybytniak Grażyna 33, 36Pszonicki Leon 89Ptaszek Sylwia 125

RRahier Hubert 44Ratajczak Renata 142Romm Horst 103Roy Laurence 103

SSadlej-Sosnowska Nina 77Sadło Jarosław 27, 28, 30, 99Sadowska-Bratek Monika 82Samczyński Zbigniew 73, 85Samecka-Cymerman Aleksandra 126Sartowska Bożena 49, 130, 141, 142, 144, 145, 147Serdiuk Katarzyna 27Skarnemark Gunnar 67Skwara Witold 81, 89Sobarzo-Sanchez Eduardo 22Sochanowicz Barbara 99, 106, 108Sołtyk Wojciech 124Sommer Sylwester 109Stachowicz Wacław 56, 58, 60, 63Stanisławski Jacek 141, 142Starosta Wojciech 42, 91, 92, 93, 94, 96, 145Sterlińska Elżbieta 89, 147Strzelczak Grażyna 30, 60Sun Yongxia 114Sypuła Michał 82, 85Szłuińska Marta 103Szopa Zygmunt 85Szostek Bogdan 52Szumiel Irena 106, 107, 108Szymczak Henryk 151

ŚŚwistowski Edward 158, 159

TTimoshenko Gennady N. 105Trojanowicz Marek 52Turek Janusz 28Tymiński Bogdan 117, 119

UUrbański Piotr 156, 158, 160

226 INDEX OF THE AUTHORS

WWalendziak Jolanta 124Waliś Lech 128, 130, 141, 142Wawszczak Danuta 145, 147, 151Werner Zbigniew 141Wierzchnicki Ryszard 113, 123, 126Wojewódzka Maria 100, 101, 102, 107Woliński Jarosław 100, 101, 102Wójcik Andrzej 103, 104, 105, 109Wroński Stanisław 121Wysocka Agnieszka 81

ZZabielski Roman 101, 102Zagórski Zbigniew P. 31, 39, 41Zakrzewska-Trznadel Grażyna 120, 121Zalutsky Michael R. 69Zayarnyuk Tetyana 151Zimek Zbigniew 33, 52, 114, 117, 161, 163Zimnicki Robert 124Ziółkowska Weronika 120Zwoliński Krzysztof 119

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ANNUAL REPORT 2006 - · PDF fileannual report 2006 institute ... of intermediates in pulse irradiated p-terphenyl solution in the ionic liquid ... in dry mushroom powder