NANOSTRUCTURED MULTIFUNCTIONAL

MATERIALS

“POLITEHNICA” UNIVERSITY OF TIMISOARA

Sinaia, Romania, October 18-20, 2007

BOOK OF ABSTRACTS

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1st Conference NANOSTRUCTURED MULTIFUNCTIONAL MATERIALS

Sinaia, Romania, October 18 – 20, 2007

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WELCOME REMARKS

On behalf of the Organizing Committee I would like to

welcome you to the 1st National Conference ”Nanostructured

Multifunctional Materials” (NMM07), with international participation.

The event is organized by the “Al.I.Cuza” University of

Iasi - Romania, Faculty of Chemistry, Laboratory of Materials

Chemistry, under the auspices of the Research Excellence

Programme CEEX initiated by the Romania's Ministry of Education

and Research.

Also, the 1st Conference”Nanostructured Multifunctional

Materials” is included as an important event in the Programme of

“Al.I.Cuza University Days’-2007”.

The Conference is aimed at promoting the fundamental and

applied studies of nanostructured multifunctional materials. The

scientific program will consist of plenary and keynote lectures, and

oral and poster presentations.

Many of key topics impacting on nanostructured materials

will be addressed by our colleagues over the next two days and we

are sure that all of you will be involved in many discussions to

make this event more productive and having in mind that the

nanostructured multifunctional materials are key for “high tech”

strategic materials.

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The event brings together experts in the field of

nanomaterials to present and discuss their research and

development work and serve as a stimulus for increased

collaborations among the researchers for solving important national

issues associated with multifunctional nanostructured materials.

Another equally important objective is to attract today’s students who

will carry on the task of solving issues into the next period.

The Conference will provide the opportunity for developing

new scientific collaboration and represents an important meeting

for those who are interested to share and disseminate their

experience, knowledge and innovative ideas on nanostructured

materials.

The feedback from YOU is very important for planning the

next conference in 2011, to which You are invited.

Conference Chairman,

Prof.univ.dr.Evelini Popovici

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Honorific Committee

Prof.dr.eng.Ecaterina ANDRONESCU - „Politehnica” University,

Bucharest, Romania

Prof.dr.eng.Corneliu TRISCA-RUSU - Executive Manager,

MATNANTECH, Bucharest, Romania

Prof.dr.Etienne.F. VANSANT - Antwerpen University, Belgium

Prof.dr.Pegie COOL - Antwerpen University, Belgium

Prof.dr.Panagiotis MISAELIDIS - Aristotle University, Thessaloniky,

Greece

Prof.dr.Gheorghe BREZEANU - „Politehnica” University,

Bucharest, Romania

Prof.dr.Alfonso NASTRO - Callabria University, Italy

Prof.dr.Nicolaie NAUM - Manager ANCS, Bucharest, Romania

Dr.eng.Doru PUSCASU - Scientific Manager - CEPROCIM,

Bucharest, Romania

Prof.dr.Vasile PARVULESCU - University of Bucharest, Romania

Prof.dr.eng. Vasile Ababi - “Gh.Asachi” Technical University, Iasi,

Romania

Prof.dr.eng.Mihai Cruceanu - „Al. I. Cuza” University, Iasi,

Romania

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Organizing Committee

Prof.univ.dr.Evelini POPOVICI –Chairman Conference Prof.univ.dr.Aurelia VASILE- Co-Chairman Conference

Prof.univ.dr.Gh. POPA, „Al. I. Cuza” University, Iasi, Romania

Prof.univ.dr. N. BILBA, „Al. I. Cuza” University, Iasi, Romania

Prof.univ.dr. Rodica PODE – „Politehnica” University, Timisoara,

Romania

Prof.univ.dr. N. SULITANU, „Al. I. Cuza” University, Iasi, Romania

Assoc.Prof. dr. Maria ALEXANDROAEI, „Al. I. Cuza” University,

Iasi, Romania

Assoc.Prof. dr. Doina HUMELNICU, „Al. I. Cuza” University, Iasi,

Romania

Lecturer dr.I. ASAFTEI, „Al. I. Cuza” University, Iasi, Romania

Secretariat:

Lecturer dr. I. ASAFTEI PhD Student Emiliana DVININOV PhD Student Maria IGNAT PhD Student Elena SEFTEL PhD Student Gina MIHAI PhD Student Claudia HRISTODOR PhD Student Violeta COPCIA PhD Student Camelia LUCHIAN PhD Student Nicoleta TURTA

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CONFERENCE TOPICS

1. NANOSTRUCTURED POROUS MATERIALS 2. ADVANCED MULTIFUNCTIONAL MATERIALS 3. NATURAL AND SYNTHETIC ZEOLITES 4. MESOSTRUCTURED MATERIALS-SYNTHESIS AND

MODIFICATION 5. CATIONIC AND ANIONIC CLAYS 6. INDUSTRIAL AND ENVIRONMENTAL

APPLICATIONS 7. OTHER ASPECTS OF NANOMATERIALS SCIENCE

AND TECHNOLOGY

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PL- 4. What Does ESR Spectroscopy Tell us about Size Dependent Phenomena in NANO Systems ?

L. M. Giurgiu National Institute for Research and Development of Isotopic and Molecular Technologies, P.O.Box 700, Cluj-Napoca, Romania; giurgiu@s3.itim-cj.ro

Electron Spin Resonance (ESR) spectroscopy is well known to be

a powerful tool for studying microscopic details of nanostructured

materials. In the present contribution, the size dependent phenomena as

seen by ESR in NANO systems are reported.

I will concentrate on the following informations revealed by EPR:

(i) metallic and magnetic nanoparticle’s mean size evaluation (ii)

orientation degree of magnetic nanoparticles and (iii) spin dynamics as

function of the grain size reduction in nanostructured colossal

magnetoresistive (CMR) manganites.

The first nano systems under investigations were the conducting

polymer nanocomposites based on polypyrrole (PPy) and iron oxide

magnetic particles and noble metallic nanoparticles. As far as the spin

dynamics in CMR nanoparticles is concerned, the size dependence of the

polaron activation energy and double exchange coupling is analysed.

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PL - 5. Fundamentals of Synthesis Processes of Microporous Materials

E.F. Vansant, P. Cool Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerpen, Universiteitsplein 1, 2610 Wilrijk, Belgium, etienne.vansant@ua.ac.be

The presentation gives a review on the synthesis and properties

of microporous (zeolites) and combined micro/meso porous layered

structures.

Since their discovery, more than one century ago, many studies

on microporous zeolites have been carried out. However, attempts to

prepare synthetic zeolites succeeded only in the late 1940’s. Adsorption

and ion exchange properties were soon recognized as their specific

characteristics. The latter result from their structural formula:

x/n Mn+

[ (AlO2)x (SiO2)y ] . w H2O

The framework of zeolites is built of AlO4 and SiO4 tetrahedra linked to

each other by sharing all corner oxygen atoms. The structure contains as

many equivalents of exchangeable cations as there are aluminium atoms

in the framework. As these frameworks are so porous, their interstices

hold not only the cations needed to neutralize the anionic framework

charge but also large amounts of water. As zeolites are crystalline solids,

the pores which are of molecular dimensions, are as regular as the

position of the lattice atoms. The possibility of zeolites to adsorb

molecules of relatively small size over molecules of larger size formed the

basis for the introduction of the term molecular sieves.

Following the history of synthetic zeolites, the first generation of

molecular sieves were synthesized between 1940 – 1950, where zeolites

were formed with low silica to alumina ratios (SiO2/Al2O3 ≤ 10) by

crystallizing reactive aluminosilicate gels with alkali and alkaline earth

metalhydroxides. Representative structures are the zeolites A, X, Y

(faujasites) and mordenite. Such zeolites are characterized by a high ion-

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exchange capacity, an extremely hydrophilic surface and many acid sites

with a wide variety of acid strength. Such frameworks show different

thermal and hydrothermal stability, depending on structural and

compositional factors. In the synthesis of the second generation of

molecular sieves (1960 – 1970) all possible quaternary ammonium ions

were used which resulted in new materials with new structure types and

different chemical compositions. In particular, aluminosilicates with

SiO2/AlO3 ≥ 20 were synthesized (silicalite, ZSM-5, etc.). Furthermore, the

isomorphous substitution of many elements was shown to be possible in

such silica polymorphs, and metallosilicates with zeolitic properties were

generated (Ti -, B - substituted silicalites). The extensive use of organic

amines as structure-directing templates or pore filling agents, coupled with

a new gel chemistry resulted in the discovery of a third generation of

molecular sieves (1982 – 1986), containing Al3+

and P5+

as lattice atoms

(ALPO, SAPO, MeAPSO, ElAPO). This class of materials contains

molecular sieves of known zeolitic structures and new tri- and bi

dimensional structures.

In order to improve the performance of zeolites as molecular sieves,

several chemical modification techniques were developed to vary in a

controlled way the zeolitic pore system: pore size engineering.

In practice, pore size engineering can be the result of

a) modification by cation exchange processes

b) modification by pre adsorption of polar molecules

c) modification of the zeolitic framework

A cation exchange process can enlarge or can reduce the zeolitic pore

openings depending on the size of the cations, cation population and or

resiting of cations, which are normally located near these openings.

Another method for altering the molecular sieving effect of zeolites is the

formation of cationic complexes, caused by a pre adsorption of polar

molecules. However, the most efficient and stable way to change the

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microporosity of zeolites can be achieved by a modification of the zeolitic

framework. This porosity change can be result of:

a) crystallographic changes by thermal treatment

b) internal and external structural modification by

implantation of additional atom groups

c) external surface modification of the zeolite crystal

(coating process)

Porous materials with porosity in the large micro- and small

mesoporous regions can be obtained in the pillared interlayered clays

(PILC). The general concept of pillaring consists of two main steps: first,

the interlamellar small cations are exchanged for other bulky ions (organic

cations, organometal complexes or inorganic polyoxycations). A second

or calcination step converts the inorganic polyoxocation precursors into a

rigid, stable metal oxide pillars, tightly bonded to the clay layers.

When the lateral dimensions of the clay layers are small (≤ 0.05 µm) and

the layer morphology is lath-like, the flocculation of smectite clays by

polyoxocations can lead to delaminated aggregates. The delamination

changes the well-ordered F-to F lamellar structures (∼ 2 µm) into F-to-F

and E-to-F structures. Pillaring these mixed lamellar structures give rise to

both micropores (for F-to-F structures) and mesopores (for E-to-F

structures).

Selected bibliography

1. D.W. Breck, Zeolite Molecular Sieves, Wiley, New York, 1974

2. P.A. Jacobs, Carboniogenic Activity of Zeolites, Elsevier, Amsterdam, 1977.

3. R.M. Barrer, Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Academic Press, London, 1978.

4. G. Gottardi and E. Galli, Natural Zeolites, Springer Verlag, Berlin, 1985.

5. E.F. Vansant, Pore Size Engineering in Zeolites, J. Wiley & Sons, 1990.

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6. W.J. Mortier, Compilation of Extra Framework Sites in Zeolites, Butterworth Scientific Ltd., Guilford, 1982.

7. R. Von Ballmoos, Collection of Simulates XRD Patterns for Zeolites, Butterworth Scientific Ltd., Guilford, 1984.

8. W.M. Meier and D.J. Olson, Atlas of Zeolite Structure Types, Butterworth Scientific Ltd., Sevenoaks, 1988.

9. D.W. Breck, W.G. Eversole, R.M. Milton, T.B. Reed and T.L. Thomas, J. Am. Chem. Soc., 1966, 78, 5963.

10. E.F. Vansant, G. Peeters and I. Michelena, J. Chem. Res., 1978, 90, 1165.

11. R.M. Barrer and L.C.V. Rees, Trans. Far. Soc., 1945, 10, 852

12. M. Niva, S. Kato, T. Hattori and Y. Marakumi, J. Chem. Soc. Faraday Trans. I, 1984, 80, 3135.

13. E.F. Vansant, P. De Bièvre, G. Peeters, A. Thijs and I. Verhaert, Eur. Appl. Res. Rep.-Nucl. Sci. Techn., 1982, 4, 983.

14. P. Cool and E.F. Vansant, Pillared Clays: Preparation, Characterization and Applications, Molecular Sieves, 1998, vol. 1, 265 – 288.

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PL- 6. Novel Synthesis and Activation Strategies Leading to the Formation of Tuned Mesostructures

Pegie Cool, E.F. Vansant Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerpen, Universiteitsplein 1, 2610 Wilrijk, Belgium, pegie.cool@ua.ac.be

The presentation gives a review on the synthesis and properties

of mesoporous materials and mesoporous materials with microporous

characteristics.

Most of the synthesis approaches to form inorganic mesoporous

materials in general are based on the use of organic template molecules

in different assembly processes around which the inorganic precursor can

condense. However, also template free synthesis mechanisms like the

nanobuilding block (NBB) mechanism and other approaches are studied.

A large diversity in synthesis approaches are known for the formation of

different materials but also similar materials (e.g. MCM-48) can be made

by different synthesis methods, each of them allowing other parameters to

be altered and controlled. For this reason, knowledge of the synthesis

methods and parameters that influence the final material will allow pore

size engineering and control of the morphology and structure of the

obtained material. Basically, the synthesis of mesoporous materials and

its control can be limited to the altering of the combination of the chosen

surfactant type, the specific synthesis mechanism and the interaction of

the silica source with the template molecules (see Table 1). For example,

M41S is made by a S+I- direct interaction between an ionic, positively

charged molecular based organized systems (MOS) surfactant and

negatively charged silica source in basic environment. Three types of

mechanisms: fluid crystal template and self-assembly and cooperative

self-assembly processes have been suggested for the synthesis of M41S

materials based on the applied synthesis conditions. SBA materials on the

other hand have been made by use of polymeric based organized

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systems (POS) surfactants that interact through an indirect reaction of the

template with the positively charged silica source (S+X

-I-) in acid medium.

A neutral interaction between MOS surfactants and an inorganic source

results in the formation of e.g. HMS materials (S0I0). Moreover, also other

parameters such as pH, additives (e.g. salts, swelling agents, co-solvents,

co-surfactants, etc.), the concentrations, the silica source, the solvent,

temperature, etc. will allow the fine tuning of the final material due to small

changes in the characteristics of the surfactant, the mechanism or the

interaction.

Table 1: Schematic overview of the main synthesis parameters to

generate a diversity of mesoporous materials.

Surfactant Mechanism

MOS LCT Direct ionic

POS Self-assembly non-ionic

Textural templates Cooperative self-assembly Indirect ionic

Nanometric building blocks non-ionic

Interaction

MOS = molecular based organised systems,

POS = polymeric based organised systems,

LCT = liquid crystal template

Combined micro- and mesoporous materials were claimed to

have advantages compared to the exclusively microporous or

mesoporous materials. They provide improved diffusion rates for transport

in catalytic processes (faster reactions), better hydrothermal stability,

multifunctionality to process a large variety of feedstocks, capabilities of

encapsulating waste in the micropores, controlled leaching rates for a

constant and gradual release of active components etc. Different porous

materials that combine micro- and mesopores have been developed in the

last few years such as SBA-15, PHTS (Plugged Hexagonal Templated

Silica), MAS (Mesoporous Aluminium Silicates), MTS (Mesoporous

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Titanium Silicates), UL-ZSM-5, zeotiles etc. Of which the latter 4 are

mesoporous materials build up from zeolite precursors.

A lot of different approaches for the synthesis of this new

generation of bimodal porous materials have been described in literature.

An overview of the most important synthesis routes is given in Table 2.

Table 2: Overview of the different existing synthesis routes for the

formation of mesoporous materials with zeolite character.

Method mesopore formation zeolite formation

steaming/acid leaching dealumina

tion/

desilication alkaline treatment

full-grown zeolite

with template

with carbon recrystalli

sation

mesoporous

amorphous

silica

structures

with carbonised

template

TPAOH

impregnation and

temperature

increase

carbon

based

mesoporous carbon or inversed

carbon replicas zeolite precursors

deposition large pore silica structures zeolite precursors

templating

approach surfactants zeolite precursors

Furthermore, all these nanoporous materials can be catalytically

activated by the Molecular Designed Dispersion (MDD) technique. In this

way, various depositions of dispersed pure and mixed transition

metaloxide layers on the surface of the mesoporous materials can be

obtained.

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References

1. G.J.A.A. Soler-Illia, C. Sanchez, B. Lebeau, J. patarin, Chem. Rev,

2002, 102, 4093. 2. A. Corma, Chem. Rev., 1997, 97, 2373. 3. Cool P., Vansant E.F., Collart O., Ordered siliceous mesostruc-

tured materials: synthesis and morphology control, Inorganic Chemistry in Focus II/ G. Meyer, D. Naumann, L. Weissmann [edit.], Wiley-VCH Verlag GmbH & Co., Weinheim, 2005, p. 319-346.

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PL- 7. Nanocasting – Powerful Strategy for Nanostructured Porous Materials Design

Eveline Popovici ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi Romania, evelinepopovici@yahoo.com

Nanocasting is a powerful method for creating nanostructured

materials that are more difficult to synthesize by conventional processes.

Structure replication on the nanometer length scale allows materials properties

to be manipulated in a controlled manner, such as tunable composition,

controllable structure and morphology, and specific functionality [1].

The nanocasting needs for the precursor and template materials.

The templates that can be used include followed types, namely soft, hard,

complex templates and biotemplates.

The template must have the controllable morphology and

structure and the ability to remove it without affecting the cast. The

templates should be easily and completely removed by chemical

(leaching, combustion) or physical (thermal treatment) methods to obtain

the true replicas.

The soft lyotropic liquid crystal phases resemble a casting mold in

which the chemical synthesis and precipitation of the inorganic material

takes place without altering the self-assembled structure [2,3].

The soft templates, which can be subsequently removed by heat

treatment, are normally organic-based molecules, supra-molecules, and

molecular associations, such as cationic surfactant micelles, non-ionic

surfactants, amines, amphiphilic block copolymers polymers [4], cationic

and anionic polyelectrolyte blocks [5], poly(styrene)–PEO block-

copolymers of low molecular weight [6], large variety of polymers like

poly(ethylene oxide), poly(methyl methacrylate) [7], poly(vinyl alcohols),

poly(vinyl acetate) [8].

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Additionally, vesicles, ionic liquids, self-assembled colloidal

crystals, and air bubbles that can be considered as soft templates have

also been used to prepare various porous materials [1,9].

Such soft templates have been employed in synthesizing microporous

zeolites and ordered mesoporous molecular sieves (Fig.1) [10-20].

In recent synthesis, instead of organic amines or surfactants,

highly ordered mesoporous silicates are employed as templates, which

are considered as hard templates.

The hard template method has recently been employed to

fabricate various novel porous structures, which are difficult to synthesize

using the soft template method.

The nanocasting pathway with hard templates opens the door to

the design of highly porous solids with multifunctional properties and

interesting application perspectives [2].

Fig.1. Schematic representation of the nanocasting concept. using soft template [10].

Microporous zeolites [22], ordered mesoporous silicas (e.g.,

MCM-48 [23], SBA-15 [24], and SBA-16 [25]), ordered mesoporous

carbon,[10] and anodic alumina membranes with micro- and sub-

micrometre pores [16] have been used to fabricate microporous,

mesoporous and macroporous carbons, various porous metals and metal

oxides , metal sulfide and polymer replica mesostructures with unique

catalytic, sensoring, and electronic properties.

The hard template refers to porous solids. One of the most

versatile hard templates is ordered mesoporous silica, since it can be

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prepared in shapes as diverse as spherical, fibrous, rodlike, and even with

chiral morphologies [2].

The pore structures of these parent materials can be transferred

to the solid structure of the generated porous materials, while the walls of

the parent become the voids of the replica.

Upon heat treatment, the precursors are thermally decomposed,

and the nanoparticles derived grow larger and larger by interconnection to

each other combined with a crystallization process. If the loading rate of

the precursors is high enough, during the annealing process, the

nanocrystals may interlink with each other and form continuous

frameworks.

After the templates of the mesoporous silicates are destroyed, the

mesostructures are fully copied by the nanocrystals, and replica materials

are obtained.

Nanocasting strategy with hard template involves two main

steps: provision of a suitable template, and the casting step.

In the first step, the template pores impregnation with a precursor

of the desired compound takes place. The precursors can be incorporated

into the channels of mesoporous silicates by sorption, phase transition,

ion exchange, complex or covalent grafting. The precursor must enter the

template structure; it must either be gaseous, highly soluble, or liquid at

moderate conditions, so that it can be infiltrated into the voids of the

template while achieving sufficiently high loadings.

The casting step starts by a heat treatment under controlled

atmosphere of the impregnated template, by which the infiltrated

precursor is converted into the inorganic material. This step is followed by

the template removal. The template moving off step implies the template

dissolution (when the template mesostructures are fully copied by the

nanocrystals and replica materials are obtained) or heat treatment with

thermally template decomposition (when the derived nanoparticles grow

larger and larger by interconnection to each other combined with a

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crystallization process). Generally, the bioproducts leave the channels in

the gas phase [3].

Fig.2. Nanocasting routes for the preparation of nanoparticles and

nanostructured inorganic materials.

In the casting step, since the synthesis takes place in a confined

nanospace, the sintering of the particles is restricted and the

nanostructures or nanoparticles obtainment is achieved. The structure of

the synthesized compounds can be tailored depending on the pore

characteristics of the selected template.

When the template consists of a fully continuous solid phase and

a continuous porous system (for instance activated carbons, silica gels,

mesostructured silica), the obtained material may retain a 3D structure

containing framework-confined pores. In this case, the product is an

inverse replica of the template structure and may be referred to as a

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nanostructured material. The filling degree of the porosity of the template

by the precursor must be sufficiently high.

When the template porosity is made up of non-connected pores

(anodic aluminum oxide membranes, MCM-41 silica) will produce solid

without framework-confined pores, made up of small particles (<100nm)

and may be referred to as nanoparticulate material.

During the impregnation process, the precursors tend to be

absorbed at the external surface of the templates and the mesopore

channels are fairly difficult to fill completely. Besides, the driving force for

promoting the movement of the precursors into the mesopores is the

capillary effect, and a weak interaction between the silicate walls and the

precursors may decrease the capillary function and cause the precursors

to remain outside the mesopores and/or stick inside the mesopore

channels and/or lock the channels.

The interactions between the silicate walls and the precursors are

determined by several complicated factors: hydrogen bonding;

coordination bonding; Van der Waals forces.

Carbon replicas from microporous materials such as zeolites have

also been synthesized. The first zeolite replica with a well resolved X ray

diffraction pattern was obtained by Patarin and colab [32].

Nanocasting, using highly ordered mesoporous silica as a

template, has brought forward incredible possibilities in preparing novel

mesostructured materials, and has led to a great number of ordered

nanowire arrays with small diameter (<10 nm), large surface areas (up to

2500 m2 g

–1) and uniform mesopores (1.5–10 nm), with tunable 2-D or 3-D

mesostructures and controlled morphology such as spheres, rods, films,

and monoliths; and different components including carbon, metals, metal

oxides and metal sulfides.

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Fig. 3. Some zeolites used as hard template and the representation of the carbon

materials prepared from them [ 31 ].

Fig.4. Schematic illustration of nanocasting preparation of the carbon nanocage [33].

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Fig. 5. Schematic representation of the framework structure of SBA-15 and

replication to platinum nanostructures [27].

The complex template, which combines the soft template with the

hard template, or two hard templates, or two soft templates of different

length scales, has been used to prepare hierarchically bi-modal and tri-

modal porous structures with the primary objectives of minimizing

diffusion resistance and improving the accessibility of various surfaces.

For instance, bimodal mesoporous–macroporous materials with

interconnected pore channels can be prepared by using surfactant template

in combination with a colloidal-crystal template [17]. The surfactant template

can also be combined with polymer foam [18], bio-cellulose [19], emulsion

[20], inorganic salt [21], and ice crystal templates [22].

Fig.6 shows the schematic representation of the structure of a

new type of hierarchically three-length-scaled porous zirconium oxide

material with high BET surface area of > 900 m2 g

–1, having a uniform

macroporous (300–500 nm) structure of a supermicroporous (1.5 nm)

nanoparticle ( 25 nm in size) assembly with irregular mesovoids (20–60

nm) in the macroporous walls [34].

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Fig.6. Schematic representation of the structure of a new type of hierarchically three-length-scaled porous zirconium oxide material [34].

Nanocasting strategies are becoming more and more usual tool

for the preparation of novel porous materials, ranging from

nanomicroporous to nanomacroporous materials, and further to

hierarchically structured porous nanomaterials.

References

1. E.Popovici, E, Dvininov, Materiale nanostructurate avansate-

Prezent si viitor, vol.1.,Casa Editoriala Demiurg, 2007. 2. F. Schüth, Chem. Mater., 2001, 13, 3184. 3. H. Yang and D. Zhao, J. Mater. Chem., 2005, 15, 1217. 4. Smarsly, S. Polarz and M. Antonietti, J. Phys. Chem. B, 2001,

105, 10473. 5. E. Krämer, S. Förster, C. Göltner and M. Antonietti, Langmuir,

1998, 14, 2027. 6. C. G. Göltner, S. Henke, M. C. Weißenberger and M. Antonietti,

Angew. Chem., 1998, 110, 633. 7. E. J. A. Pope, M. Assami and J. D. MacKenzie, J. Mater. Res.,

1989, 4, 1018. 8. D. Grosso, G. Soler-Illia, F. Babonneau, C. Sanchez, P. A. Albouy, A.

Brunet-Bruneau and A. R. Balkenende, Adv. Mater., 2001, 13, 1085. 9. K. K. W. Wong, S. Mann, Adv. Mater., 1996, 8, 928. 10. X. Liu, B. Tian, C. Yu, F. Gao, S. Xie, B. Tu, R. Che, L. M. Peng

and D. Zhao, Angew. Chem. Int. Ed., 2002, 41, 3876. 11. F. Kleitz, S. H. Choi and R. Ryoo, Chem. Commun., 2003, 2136. 12. Y. Sakamoto, T. W. Kim, R. Ryoo and O. Terasaki, Angew.

Chem., Int. Ed., 2004, 43, 5231.

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13. S. Che, A. E. Garcia-Bennett, T. Yokoi, K. Sakamoto, H. Kunieda, O. Terasaki and T. Tatsumi, Nat. Mater., 2003, 2, 801.

14. S. Che, Z. Liu, T. Ohsuna, K. Sakamoto, O. Terasaki and T. Tatsumi, Nature, 2004, 429, 281.

15. P. Yang, D. Zhao, D. I. Margolese, B. F. Chmelka and G. D. Stucky, Nature, 1998, 396, 152.

16. P. Yang, D. Zhao, D. I.. Margolese, B. F. Chmelka and G. D. Stucky, Chem. Mater., 1999, 11, 2813.

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Angew. Chem., Int Ed., 1996, 35, 541. 11. 20. G. S. Attard, P. N. Bartlett, N. R. B. Coleman, J. M. Elliott, J. R.

Owen and J. H. Wang, Science, 1997, 278, 838. 21. G. S. Attard, C. G. Goltner, J. M. Corker, S. Henke and R. H.

Templer, Angew. Chem., Int. Ed. Engl., 1997, 36, 1315. 22. J. L. H. Chau and K. L. Yeung, Chem. Commun., 2002, 960. 23. R. Rockmann

and Grit Kalies, Applied Surface Science, 253,

2007, 5666. 24. E. Delahaye, V. Escax, N. El Hassan, and A. Davidson, J. Mater.

Chem., 2006, 16, 623.

25. T. Tsoncheva, J. Rosenholm, C.V. Teixeira, M. Dimitrov, M. Linden

and C.Minchev, Microporous Mesoporous Mater., 89, 1-3, 2006, 209.

25. B. Tian, X. Liu, B. Tu, C. Yu, J. Fan, L. Wang, S. Xie, G. D. Stucky and D. Zhao, Nat. Mater., 2003, 2, 159.

26. F. Schulth, Chem. Mater., 2001, 13, 3184. 27. Choi, M.; Heo, W.; Kleitz, F.; Ryoo, R. Chem. Commun. 2003,

1340. 28. F. Schuth, Chem. Mater., 2001, 13, 3184. 29. S. H. Joo, S. Jun and R. Ryoo, Microporous Mesoporous Mater.,

2001, 44, 153. 30. R. Ryoo, S. H. Joo and S. Jun, J. Phys. Chem. B., 1999, 103,

7743. 31. Valdes-Solis, A.B.Fuertes, Materials Research Bull. 41, 2006, 2187

32. F. O. M. Gaslain, J. Parmentier, V. P. Valtchev and J.l Patarin, Chem. Commun., 2006, 991.

33. A.Vinu, M. Miyahara, T. Mori, K.Ariga, J Porous. Mater.,2006, 13: 379.

34. A. Vantomme, Z.Y. Yuan and B.L. Su, New J. Chem., 2004,28, 1083.

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PL.9. Nanomaterials for Environmental Applications

N.Bilba “Al.I.Cuza” University of Iasi, Faculty of Chemistry

Environmental pollution and destruction on a global scale, as well

as the lack of sufficient clean and natural energy sources have drawn

much attention and concern to the vital need for ecologically clean

chemical technology, materials and processes.

The increasing ability of scientists to manipulate the matter

virtually atom by atom, to create and use structures, devices and systems

that have unique physical an chemical properties and functions because

of their small size in a nanometer scale can be expected to have a

significant impact on sustainable development and an enormous potential

for industry and technology, social, economic and environmental benefits.

Materials with very small features (particle size or grain size) on

the order of 1-100 nm of at least one dimension are known as

nanomaterials.

The reason the scientific community has such an interest objects

operating at such a small length scale are because, at lengths under ∼

100 nm, materials stop exhibiting bulk, macroscopic characteristics and

start exhibiting unique nanoscopic characteristics.

Two principal factors cause the properties of nanomaterials to

differ significantly from other materials:

- increased relative surface area,

- quantum effects.

These factors can change or enhance properties such as

reactivity, strength, optical, electrical and magnetic characteristics.

As a particle decreases in size, a greater proportion of atoms are

found at the surface compared to those inside (for example, a particle of

size 30 nm has 5% of its atoms on its surface, at 10 nm has 20% and at 3

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Environmental (clean water, air

and soil)

- Healt care (tissue and bone

repairs, drug delivery)

- cosmetics

Clean energy (GTL, H2, Coal,

natural gas, fuel cells, Li-ion

battery, green

nm has 50% of its atoms on its surface). As catalytic chemical reactions

occur at surfaces, this means that a given mass of material in

nanoparticulate form well be much more reactive than the same mass of

bulk material.

Ultrafine microstructures produced by the consolidation or the

assembly of building blocks having an average phase or grain size range

from ∼ 1 (molecular scale) to ∼ 50 nm are classified as nanostructured

materials.

Nanomaterials can be metals & alloys nanoparticles, ceramic

nanoparticles, nanoporous materials, nanopolymes, nanocomposite

materials, carbon based nanomaterials and biological nanomaterials.

Nanostructured materials include: atomic clusters, layered

(lamellar) films, filamentary structures, nanocrystalline materials,

nanocomposites and bulk nanostructured materials.

Areas of nanomaterials applications:

Most environmental applications of nanomaterials and of

nanotechnologies fall into four categories:

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1. Environmental remediation to clean up past environmental

damage:

- nanomaterials and nanotechnologies for water remediation:

nanoporous membranes, nanofibres, nanoparticles,

nanofiltration, sorption, ion exchange;

- nanomaterials and nanotechnologies for air remediation

(POP-s, VOC-s, HAP-s):

nanofibers, nanoporous membranes, adsorbents;

2. Environmental protection to correct present environmental

problems:

- transportation: nanocatalysts;

- pesticide replacements;

- nanotechnologies for recycling.

3. Environmental maintenance to prevent future environmental

impacts:

- nanosensors for air quality;

- nanosensors for water quality;

- nanosensors for radiations.

4. Environmental enhancement to sustain the planet for future

generation:

- green technologies (manufacturing);

- food processing enhancement (package materials, storage

life sensors, additives).

With respect to remediation of environmental contaminants, the

applied nanotechnologies can be adsorptive versus reactive and in situ

versus ex situ.

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PL - 9. Coronands with Multiple Binding Sites

Ionel I. Mangalagiu*, Ana Maria Balan, Ondina Florea “Al. I. Cuza” University of Iasi, Organic and Biochemistry Department, Bd. Carol 11, 700506 Iasi, Romania. e-mail: ionelm@uaic.ro

During the last decades host-guest chemistry has emerged as a

central paradigm within organic chemistry.

The emphasis of this work was to design and to synthesize a new

class of coronands possessing multiple binding sites. This class are

coronands with oniu skeleton and contain two main units: a

dihydroxyacetophenone unit (with aliphatic or aromatic arms) and a

nitrogen heterocycle one (Schema 1, compound III); the obtaining

pathway could be rationalized bellow:

Acknowledgements: to Romanian Ministry of Research and

Education - MATNANTECH program, grant no. 36/2005, for financial

support.

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O - 1. NANOSTRUCTURED POROUS MATERIALS

O-1-01. The Influence of Hydrolysis Parameters on the Synthesis of Zr, Y and Al Nanocrystalline Compounds

Laura M. Popescu*, Cristina F. Rusti, Adrian M. Motoc, Roxana M. Piticescu, Radu R. Piticescu National R&D Institute for Non-Ferrous and Rare Metals, Pantelimon, Ilfov, RO, *roxana@imnr.ro, mpopescu@imnr.ro

Nanomaterials have been studied since the 1990s because of

their specific features. Nowadays, an increasing attention is paid to the

environmental friendly obtaining methods of nanomaterials that could

control the grain size and which are easy to implement at the small and

medium enterprises (SMEs) level. High pressure hydrothermal synthesis

in aqueous solution follows the trend of these new techniques.

In the present paper hydrolysis reactions for the synthesis of ceramic

powders based on Y doped ZrO2 and ZrO2-Al2O3 were investigated. The

preliminary studies revealed the application potential of these

nanomaterials in the field of nanomedicine, sensors, FGMs, high added

value materials. The main objective was the study of precipitation-

dissolving equilibriums of Zr, Y and Al salts which take place in precursor

suspension of metallic oxides in order to obtain powders with small

crystallite sizes. Precursor suspension is introduced in the autoclave

under high pressure. The different solubility of the precipitating species

influences the kinetics of the co-precipitation reaction. This can determine

the formation of heterogeneous precipitate. Solubility and conductivity

measurements of the reaction system were performed to establish the

optimum working conditions (pH, temperature) that will determine the

formation of fine, small sized crystallites.

Hydrolysis degree, q, which determines the hydrated species

composition, can be estimated taking into account the Sanderson

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hypothesis which states that in a chemical compound the participant

atoms tend to equal their electronegativities. Hydrolysis degree increases

with increasing cation valence and electronegativity. Zr hydrolysis degree

is greater than that of Al. Hence, Zr4+

ions precipitate before Al3+

ions at

more acid pH value. Aqueous solutions of zirconium salts showed a

strong hydrolysis tendency due to their great electric charge and small

ionic radius.

Unlike Y doped ZrO2 system where Y and Zr cations have

comparable ionic radii and only one equivalence point is observed, ZrO2-

Al2O3 system showed two equivalence points corresponding to totally

different precipitation pH of Zr4+

and Al3+

.

Based on these preliminary results, further studies are necessary to

elaborate methods that investigate the in situ behaviour of the same

systems under high pressure conditions.

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O-1-02. Characterization of Nanostructured Ni-Al-M (M: Co, Fe) Composites Prepared by TVA Method

A. M. Lungu1, C. P. Lungu1, I. Mustata1, A. Anghel1, C. C. Surdu-Bob, P. Chiru1, O. Pompilian1, E. Dutu1, M. Badulescu1, V. Zaroschi1, C. Iacob1, C. Georgescu1, R. M. Piticescu2, R. Piticescu2, S. Stoleriu3, V. Ciupina4, R. Vladoiu4, G.Prodan4 1 National Institute for Laser, Plasma and Radiation Physics,

Bucharest, Romania Cristian.Lungu@inflpr.ro 2 National R&D Institute for Non-Ferrous and Rare Metals

Bucharest, Romania 3 ”Politehnica” University, Faculty of Applied Chemistry and

Material Science, Bucharest, Romania 4 “Ovidius” University, Constanta, Romania

Ni-Al-M (M: Co, Fe) nanostructured composite films were

prepared using the original thermionic vacuum arc (TVA) method

developed at NILPRP [1]. The method uses three separate electron

beams emitted by three externally heated cathodes (grounded tungsten

filaments) accelerated by three high anodic voltages. The electron beams

evaporate the metals used as anodes as neutral metal atoms. Applying

high voltages (1-5kV) between cathodes and respective anodes, bright

plasmas in pure metal atoms were ignited simultaneously. The plasmas

were controlled independently by the electron beams (thermoelectrons)

emitted by the heated cathodes. The process parameters (discharge

current and plasma potential) were studied and optimized.

The Ni-Al-M films were characterized by transmission electron

microscopy (TEM) as inter-metallic complex of nanocrystals of 5-10 nm

average diameters. The prepared samples were characterized also by

scanning electron microscopy (SEM), electron dispersive spectrometry

(EDS), X-ray diffraction (XRD), atomic force microscopy (AFM), gravimetric

thermal analysis (GTA) and differential thermal analysis (DTA).

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References

1. C. P. Lungu, I. Mustata, G. Musa, A. M. Lungu, V. Zaroschi, K. Iwasaki, R. Tanaka, Y. Matsumura, I. Iwanaga, H. Tanaka, T. Oi, K. Fujita: Surf and Coat. Techn, Vol.200, 399-402,2005

O-1-03. Optical Characterization of Cu/Ni/NiOx Thin Films Used as Selective Surfaces for Flat Plate Collectors

Mihaela Voinea*, Cristina Bogatu, Anca Duta* *The Centre: Product Design for Sustainable Development, Transilvania University of Brasov, Eroilor 29, 500036 e-mail: m.voinea@unitbv.ro Economical and efficient conversion of the solar radiation

into thermal energy requires a low cost spectrally selective solar absorbing surface. These coatings must present a large absorption coefficient and a small reflection coefficient in the spectral range of the solar radiation corresponding to the photon energies E > 0.5 eV, and low emission or high reflection in the IR spectral range at E < 0.5 eV. Black nickel layers Ni/NiOx can be used as selective surfaces due to their good optical properties.

Thin films of NiOx were deposited by spray pyrolysis deposition

technique (SPD) onto a copper substrate previously coated with

electrolytic nickel. Aqueous solutions of nickel chloride were used as

precursors for SPD. The deposition parameters (precursor’s concentration

and temperature) were varied in order to optimize the films properties.

The optical properties of the films (UV-VIS, IR) were correlated with their

chemical composition, crystalline structure (XRD) and morphology (AFM).

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O - 2. ADVANCED MULTIFUNCTIONAL MATERIALS O-2-01. Multifunctional Bio and Chemical Sensors Based on

Wide Band Gap Materials

Anita Lloyd Spetz, Kristina Buchholt, Rodrigo Petoral, Kajsa Uvdal Per-Olov Käll, Doina Lutic*, Mehri Sanati**, Rositza Yakimova.

Div of Applied Physics, Dep. of Physics, Chemistry and Biology, Linköping University, SE-581 83 LINKÖPING, Sweden

* Al. I. Cuza University of Iasi, Faculty of Chemistry, Bd. Carol I 11, 700506 IASI, Romania

** Dep. of Technology and Design, Växjö University, SE-351 95 VÄXJÖ, Sweden spetz@ifm.liu.se

The multifunctional properties of wide band gap, WBG, materials

like SiC, GaN/ GaAlN, AlN, ZnO and Diamond provide the possibility of

multifunctional bio and chemical sensors. Semiconducting and

piezoelectric properties introduce parameters like resistivity, potential,

mass changes and temperature to be measured. Excellent properties like

high melting point, chemical inertness and biocompatibility enable

applications such as in car exhausts, flue gases, oil wells or in the

stomach. For example SiC devices have been operated up to 1000°C.

Using the piezoelectric properties of AlN, resonator devices have been

processed with a frequency of 2 GHz and thereby potentially extremely

high sensitivity. The ZnO material exhibit potential as multisensing

material, since both FET and resonating devices are realized. The

material is a semiconducting oxide, which makes it especially interesting

for bio and chemical sensors. The oxide surface provides both oxygen

sites for the gas response in a FET device and also sites for

functionalization by biomolecules. We have successfully functionalised the

ZnO surface by APTES and MPTMS [1]. Also the SiC surface was

successfully functionalised. Here it was of special interest to investigate

the insulating properties of the biomolecule layer [2]. Also, the use of

nanoparticles as the sensing layers in FET chemical sensor devices has

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been explored. Au nanoparticles show an increased response to NO or

NO2. Pd showed an interesting fractal particle formation and also

increased sensitivity to NO. For devices based on SiC/ZnO, thin film of

ZnO was compared to ZnO nanoparticles and it was shown that the

oxygen sensitivity increased for nanoparticles.

References

1. R. M. Petoral Jr., G. R. Yazdi, A. Lloyd-Spetz, R. Yakimova, K.

Uvdal , Organosilane-functionalized wide bandgap semiconductor surfaces, Appl. Phys. Lett. In press

2. R. Yakimova, R.M.Petoral Jr., G.R. Yazdi, C. Vahlberg, A.Lloyd

Spetz and K. Uvdal Surface functionalization and biomedical applications based on SiC, J. Phys. D., in press

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O – 2-02. Advanced Multifunctional Materials from Maleic Anhydride Copolymers

Gabrielle Charlotte Chitanu, “Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania; e-mail: chita@icmpp.ro

Maleic anhydride copolymers are particularly suitable for

preparation of multi-functional materials. Their chemical structure can be

tailored either by the appropriate choice of the comonomer (hydrophilic or

hydrophobic) or by chemical reaction with suitable low molecular

compounds bearing different functions: charged groups (which cause

them to behave as polyelectrolytes), dyes or chromophores, bioactive

molecules, LC moieties, and other. Moreover they can be obtained from

easily accessible commercial monomers which are relatively cheap, by

convenient radical copolymerization in organic solvents using common

initiators. The co-monomer can be N-vinylpyrrolidone (NVP), vinyl acetate

(VA), methyl methacrylate (MMA), or styrene (St), given in the order of

increasing hydrophobic character.

In this paper will be presented recent results regarding new materials

based on maleic anhydride copolymers:

• layer-by-layer deposition from maleic polyelectrolytes and

different cationic low or high molecular partners;

• supramolecular systems in which one of the partners are

maleic anhydride/acid copolymers. Original results are presented

regarding the interaction of maleic acid copolymers with collagen

hydrolysate or the intermacromolecular complexes formed between

maleic acid copolymers and chitosan.

Acknowledgement: The financial support of Romanian

National Authority for Scientific Research, CEEX projects no. 42/2005

(RO-NANOMED) and 14/2005 (NANOAGMAM), is gratefully

acknowledged. We are thankful for the collaboration with Dr. Gabriela

Aldea and Prof. Jean-Michel Nunzi, University of Angers, France, and

Prof. Heikki Tenhu and Dr. Adina Graziella Anghelescu-Dogaru,

University of Helsinki, Finland.

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O – 2-03. The Use of Oxide-Type Solids in Chemical Sensor

Formulations

Doina Lutic, Mehri Sanati*, Anita Lloyd-Spetz** “ Al. I. Cuza” University of Iasi, Faculty of Chemistry, 11 Bd. Carol

I, 700506 Iasi, Romania, doilub@uaic.ro, oina.lutic@vxu.se * Dep. of Technology and Design, Växjö University, SE-351 95

VÄXJÖ, Sweden ** Div of Applied Physics, Dep. of Physics, Chemistry and Biology,

Linköping University, SE-581 83 LINKÖPING, Sweden

The sensitive layer in a chemical sensor is for example a solid

able to catch the sensed molecules by physical adsorption or by

chemisorption; this is often followed by chemical reactions like

combustion. During this interaction, some properties of the sensitive layer

will change (density of charge carriers, colour, light emission, mass, etc.).

The oxides, characterized by selective uptake for different classes of

molecules from mixtures, are widely used for sensor formulations.

Beside the widely used SnO2 as main compound in resistor-based

sensors, several other oxides as: titania, chromia, silica, alumina, ITO

(indium-tin oxide), rare-earth oxides and even zeolites and mesoporous

materials are reported in the literature. The detection mechanism

comprises mostly resistance changes, but also impedance

measurements, surface polarization (field effect sensors), mass changes

(QMB sensors), light emission (cataluminescence sensors), optical

sensors etc.

The conference will review some recent interesting results from

literature comprising sensors based on nanocrystalline oxides,

microporous oxides (zeolites and aluminophosphates) and mesoporous

oxides.

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References

1. D. Lutic, M. Sanati and A. Lloyd Spetz, “Gas Sensors”: in

“Synthesis, Properties and Applications of Oxide Nanomaterials”, Wiley-Interscicence, J. A. Rodriguez and M. Fernandez-Garcia (editors), 2007, p. 411.

2. X. Xu, J. Wang and Y. Long, “Zeolite-based Materials for Gas Sensors (review)”, Sensors, 6, 2006, p. 1751.

3. G.E.Fryxell, “The synthesis of functional mesoporous materials (mini review)”, Inorganic Chemistry Communications, 9, 2006, p.1141.

4. H. Fan, S. Reed, T. Baer, R. Schunk, G.. Lopez and C.J. Brinker, “Hierarchically structured functional porous silica composite produced by evaporation-induced self assembly”, Microporous and Mesoporous Materials, 44-45, 2001, p. 625.

5. D. Lutic, M. Strand, A. Lloyd-Spetz, K. Buchholt, E. Ieva, P.-O. Käll and M. Sanati, “Catalytic properties of oxide nanoparticles applied in gas sensors”, accepted, “Topics in Catalysis”

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O – 2-04. Magnetic Nanostructures grown in Porous Polymer Structures

N Sulitanu, F. Brinza, V. Tura Solid State and Theoretical Physics Dept., Faculty of Physics, Al.I.Cuza University, 700506 Iasi, Romania

The new concept of magnetic nanoparticles, nanoclusters or

nanowires embedded in matrices of porous polymers are good examples

of functional nanostructures with excellent potential for applications such

as electromagnetic interference shielding, magneto-optical storage,

biomedical sensing, flexible electronics, etc. Possibly, polymer coated

nanostructures are the only starting material to produce macroscopic

parts showing the very special properties of nanomaterials. The very

special properties of nanomaterials often are properties of isolated

particles. By proper selection of the porous polymer it is possible to avoid

grain growth and to properly change of the strength of magnetic

interaction. Therefore, to obtain macroscopic parts exhibiting the

properties of the isolated particles it is necessary to avoid or at least

reduce the interaction of the particles. This can be achieved by coating

each individual particle with a polymer layer or by polymer filling with

nanoparticles. Control over the dispersion of the nanoparticle phase

embedded in a polymer matrix is critical and often challenging. To achieve

excellent dispersion, competition between polymer-polymer and polymer-

particle interactions have to be balanced to avoid clustering of particles in

polymer nanocomposites. This type of materials can be synthesized by a

variety of methods such is: electrodeposition, CVD, chemical co-

precipitation from solution, microwave plasma polymerization, spin-

coating etc.

Moreover, we present here our results upon various magnetic

nanoclusters grown in polyethylenetereftalate, nanoporous nanofibrous

polyurethane, nanofibrous polyvinylchloride and nanoporous polyethylene

membranes. X-ray diffraction-XRD, cross-sectional scanning electron

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microscopy-SEM, transmission electron microscopy-TEM, and magnetic

measurements confirm the excellent dispersion and magnetic response of

nanoclusters embedded in porous polymers.

References

1. F. Johnson, C.Y. , Um, M.E., McHenry, H. , Garmestani, JMMM

Volume 297, issue 2, February 2006, 93-98. 2. N. Sulitanu, F. Brinza, Romanian Patent (Part of Porous membrane

obtaining technology). 3. N. Sulitanu, F. Brinza, Engineering Functional 1D Magnetic

Nanostructures by Electrodeposition, Bul. Inst. Polit. Iasi, Tomul LII (LVI), Fasc.:1-2, Sect.: Math.,Mech. & Phys., 127 (2006).

Fig. 1. Cross-sectional SEM view of

porous polyurethane with magnetic nanoclusters

Fig. 2. Cross-sectional view of porous

PE coated FeCo nanoclusters.

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O-3. NATURAL AND SYNTHETIC ZEOLITES

O – 3-01. Attenuation β-Ray Study through Materials on the Basis of Natural Zeolites

Bogdan-Ion Mocanu*, Nicolae Naum**, Ion Gruia*** * Refinery Petrobrazi, Brazi, Prahova district,

bogdan.mocanu@petrom.com ** Management Programs National Centre from Education and

Research Ministry, No.21-25 Mendeleev street, Bucharest, naum@cnmp.ro

*** University Bucharest, Physics Faculty, Magurele, gruia_ion@yahoo.com

In this paper, it was studied β-ray attenuation through the material

type of “roman concrete”, having in the composition natural zeolites

(clinoptilolite), which carried out before an ionic exchange with strontium.

Purpose of this work was to prove safety stocking possibility with

very low costs, of a mineral ion-exchangers (zeolitic volcanic tuffs),

saturated by ionic exchange with Sr-90, β activity radionuclide.

In the end of this paper, it proposed for safety radioprotection

stocking of the solid residues resulted from the ionic exchange, a efficient

and especially cheap method, by the obtaining concrete by pozzolanic

reaction (due to high reactionable silica content), followed by the stocking

in the abandoned mines (this sort of binder having an enhanced

resistance at the corrosion, which could exceed resistance of the

concretes obtained from the Portland cement).

Key-word: roman concrete, clinoptilolite, strontium, pozzolanic reaction.

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O – 3-02.The Improvement of Retention Capacity of ETS-10 towards Uranyl Ions by Porosity Modification

Claudiu C. Pavel, Karin Popa “Al.I. Cuza” University, Department of Inorganic and Analytical Chemistry, 11-Carol I Blvd., 700506 - Iasi, Romania, e-mail: kpopa@uaic.ro

ETS-10 is a microporous titanosilicate with a unique structure of

linked SiO4 tetrahedra and TiO6 octahedra that attracts interest for shape-

selective photocatalysis, optoelectronics, and selective gas adsorption.

Apart of its catalytic properties, it was found to be a very effective material

in purification of (nuclear) waste waters. In a previous study [1] we have

shown that the radioactive form of some small cations like Co2+

, Cd2+

, and

Hg2+

can be sequestrated by this material up to its ionic exchange

capacity (about 4.5 meq/g). Contrarily, the uptake of UO22+

ions was found

to be much lower [2], perhaps because of the very high ionic radius of the

hydrated uranyl ions. Also the uranium uptake seems to be dramatically

influenced by the synthesis procedure of ETS-10 [2].

Recently, the porosity of ETS-10 was modified by introduction of

supermicropores (essentially as coalescence of neighboring micropores) and

mesoporosity via post-synthesis treatments with hydrogen peroxide [3,4].

A qualitative study of the diffusion properties of ETS-10 as a

function of its porosity has been performed by adsorption of rhodamine

6G. The main results which were found out are: (i) initial time adsorption

kinetics is determined by super- and mesoporosity, (ii) the amount of

adsorbed molecule is proportional to the quantity of introduced porosity,

and (iii) long time adsorption kinetics is determined by microporosity and

can modified by the presence of supermicropores.

This preliminary study has encouraged us to use the modified ETS-10 in

retention of the large uranyl ions from aqueous solution using batch-type

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method. The mesopores-containing ETS-10 samples show a much higher

uptake of uranyl ions compared to the as-made material at different

temperatures. Our results are very satisfactory and the distribution

coefficient (Kd) was double than the one found by Al-Atar et al. [2], as a

function of the experimental temperature and the contact time. It seems

that the increased porosity permits a better contact in the uptake system,

since the diameter of the pores is much higher than the ionic radius of the

hydrated uranyl ion. This hypothesis has to be validated, EXAFS

experiments being ongoing at the present time.

A kinetic and thermodynamic evaluation of the uptake data was

performed and the standard thermodynamic parameters were calculated.

References

1. C.C. Pavel, K. Popa, N. Bilba, A. Cecal, D. Cozma, A. Pui,

J. Radioanal. Nucl. Chem., 258(2) (2003) 243-248. 2. L. Al-Atar, A. Dyer, R. Blackburn, J. Radioanal. Nucl. Chem.,

246(2) (2000) 243-248. 3. C.C. Pavel, So-Hyun Park, A. Dreier, B. Tesche, W. Schmidt,

Chem. Mater., 18(16) (2006) 3813-3820. 4. C.C. Pavel, W. Schmidt, Chem. Commun., (2006) 882-884.

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O – 3-03. Synthesis and Characterisation of Molecular Sieves Titanium and Phosphorus Based for Water Depuration

D. Vuono*, N. A. Turta, P. De Luca*, A. Nastro* * Department of Pianificazione Territoriale, University of Calabria, via P. Bucci, I-87036 Arcavacata di Rende (CS), Italy. e-mail: danivuono@yahoo.it “Al.I.Cuza” University of Iasi, Faculty of Chemistry, Laboratory of Materials Chemistry, Carol I Bvd. No. 11, 700506 Iasi, Romania.

The aim of this research is to synthesise ET(P)S-4 and ET(P)S-10

determining their exchange capacity, variation of crystalline framework

and thermal stability. The study of ion exchange properties of those

materials is useful to determine their own possible application in water

depuration from urban and industrial water wastes. The analyses to

determine chemical composition of molecular sieves are carried out

before and after ion exchanges. The ET(P)S-4 and ET(P)S-10 are

synthesised from two solutions: acidic and basic solutions. In acidic

solution is added P2O5. The synthesis procedure is described in studies of

Pavel et al. [1]. The ion exchange is carried out using Na+, K

+, Li

+, Mg

++

and Ca++

ions. 2.5 gr of ET(P)S (4 or 10) are added to 250 ml of a 1 M

solution of clorures of several cations (NaCl, KCl, MgCl2, CaCl2, LiCl). The

solutions are omogenised for 2 minutes. The ion exchange are carried out

for 24 hours at room temperature. The solutions are regenerated for 3

times to stabilise the exchange conditions during 96 hours of test. The

microporous materials are filtered and dried at ca. 100°C. The so-obtained

powders are characterised by thermogravimetric analysis, XRD analysis

and chemical and morphologic analyses. After the characterisation, the

two molecular sieves present good ion exchange properties. It is noted

ET(P)S-4 has the best exchange capacity (4.7 meq/gr). The monovalent

cations present a best trend to be exchanged than the bivalent cations.

The exchange for both zeotypes is never complete except for Na-ET(P)S-

4 totally becoming sodic. Thermal stability of both sieves was carried out

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for all exchanged cations. The ET(P)S-4 shows a high stability after the

ion exchange with potassium. The ET(P)S-10 presents a high stability

after exchange with calcium. The morphologic studies before and after ion

exchanges do not present changes.

References

1. P. A. Sandomirskii, N. V. Belov, Sov. Phys. Crystallogr., 24, 686-

693, 1979.

2. A. Philippou, M.W. Anderson, Zeolites, 16, 98-107, 1996.

3. C.C. Pavel, D. Vuono, L. Catanzaro, P. De Luca, N. Bilba, A.

Nastro, J.B. Nagy, Microporous and Mesoporous Materials 56,

227–239, 2002.

4. D. Vuono, C. C. Pavel, P. De Luca, J. B. Nagy and A. Nastro,

Journal of Thermal Analysis and Calorimetry, 80, 585–590, 2005.

5. C.C. Pavel, D. Vuono, P. De Luca, N. Bilba, J. B.Nagy, A. Nastro,

Microporous and Mesoporous Materials 80, 263–268, 2005.

6. G. Cruciali, P. de Luca, A. Nastro, P. Pattison, Microporous and

Mesoporous Materials, 21, 143-153, 1998.

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O-5. CATIONIC AND ANIONIC CLAYS

O - 5-01. In Vitro and in Vivo Behavior of Ketoprofen Intercalated in Zn Al Layered Double Hydroxides

Ionel Marcel Popa1, Costin Mungiu2, Mihaela Frunza1, Georgeta Ionescu Dunarea2, Irina Jaba2, Bogdan Tamba2, 1 Technical University, Iasi, Romania, 2 University Medicine and Pharmacy “Gr.T. Popa” Iasi,

Romania; mipopa@ch.tuiasi.ro

Layered double hydroxides (LDH) are amongst attractive

materials for the preparation of a controlled release formulation [1, 2]. The

large variety of anions that can be incorporated in the layered double

hydroxides and the high anionic exchange capacity of these materials

allow us to use them as matrices for tailoring specific organic–inorganic

hybrid nanostructures with new potential applications such as: designing

new pharmaceutics and new biocompatible materials [3, 4].

In the present study, we report the formation of a layered

nanohybrid material by intercalation of ketoprofen (KET) into the ZnAl

layered double hydroxides (ZnAlLDH) for controlled release formulation

purposes. The release of ketoprofen from the interlamella of an organic-

inorganic nanohybrid material could by controlled by adjusting the type

and the concentration of the anion in the release medium, the pH of the

release medium. The rate of drug diffusing out of the matrix is controlled

by the rigidity of the layers and the diffusion path length. These results

demonstrate that intercalation of KET in the interlayer of hydrotalcite

reduces gastric damage.

References

1. S. Y. Kwak, W. M. Kriven, M. A. Wallig, J. H. Choy, Biomaterials

25 (2004) 5995- 6001.

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2. M. Frunza, G. Carja, M. I. Popa, Scientific Study & Research, VI 2, (2005), 173-180.

3. B. Li, D. Evans, X. Duan, Appl. Clay Sci. 27, (2005), 199-207.

4. Z. Wang, E. Wang, L. Gao, L. Xu, J. Solid State Chem., 178, (2005), 736-741.

Acknowledgment: This work has been supported by Ministry of

Education and Research Romania, by CEEX 108/2006.

O – 5-02. Zn/Al Layered Double Hydroxides: Synthesis and

Photocatalytic Application

E. M. Seftela,b, E. Popovicia, P. Coolb, E. F. Vansantb

a “Al. I. Cuza” University of Iasi, Department of Physical and Theoretical Chemistry and Materials Chemistry, Bvd. Carol I, 11, 700506, Romania, e-mail: seftel_elena@yahoo.com

b Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerpen (CDE), Universiteitsplein 1, 2610 Wiljik, Antwerpen, Belgium

Introduction. Layered Double Hydroxides have the general formula [MII1-

xMIII

x(OH)2]x+

·(An-

x/n)·mH2O, where MII and M

III are the divalent and trivalent

cations and An-

the anions that maintain the electro-neutrality of the

brucite-like sheets. The thermal stability of these materials is strongly

related with several factors, such as the nature of the cations and the

cationic ratio in the brucite-like sheets, the nature of the compensating

anions and the crystallinity degree of the LDH lattice [1].

Experimental. Zn/Al-LDHs with the cationic ratio of 1 to 4 were prepared

by the co-precipitation at low supersaturation method at constant pH

[2, 3]. Part of these samples was calcined at 300°C and 500°C in a Lenton

furnace. As a reference sample, ZnO was prepared following the same

method and calcined at 500°C. The photocatalytic activity was evaluated

for the degradation of methyl-orange dye under UV-illumination.

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Results and discussion. The XRD patterns revealed that for all the

cationic ratios the layered structure was formed. Additional ZnO phase is

present in all samples due to the longer hydrothermal treatment at 80°C.

Phase transformations during the calcination were fully investigated by

XRD, TG/TGA, UV-vis DR and Raman Spectroscopy, N2

adsorption/desorption, SEM and EDX methods. The EDX analysis

showed that the increase of the temperature leads to a diffusion of the

Zn2+

cations to the surface of the particles. The band gap energy

decrease as the temperature increase indicating that less energy is

needed for the photocatalytic process. Therefore, the photocatalytic

activity increases with the increase of the cationic ratio and the calcination

temperature.

Acknowledgments This study was supported by the NoE project

“Inside Pores” and the GOA project funded by the Special Fund for

Research of the University of Antwerp. This work is also part of the CEEX

No. 1/S/2005 project.

References

1. Auerbache S. M.,Corrado K. A., Dutta P. K., Handbook of layered

materials (2004) 373-449

2. Cavani F., Trifiro F., Vaccari A., Catalysis Today 11 (1991) 201-206.

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O-6. INDUSTRIAL AND ENVIRONMENTAL APPLICATIONS

O – 6-01. Research Concerning Achievement and Efficiency of some Multicomponent Retention Systems with Micro/Nanoparticles in Paper Industry

Constantin Stanciu “ Dunărea de Jos” University of Galaţi, Faculty of

Engineering Brăila, 29, Calea Calarasi, RO-810017, Romania; e-mail: decanatbr@ugal.ro

The higher speed of paper machine, a lower pollution and higher

quality papers are three requirements for modern paper making:

These challenges can be accomplished by means of retention aids. The

most common synthetic retention aids are PEIs, PAAs and combinations

between these groups of products, and concerning natural products,

cationic starch and manogalactans (guam guar) can be mentioned. Of the

retention systems, multicomponent retention systems based on

micro/nanoparticles made of inorganic, anionic substances (bentonite,

colloidal silica etc ) and various cationic polymers (substitution degree

over 0.08%), PAAs and manogalactans can be mentioned.

The survey shows in its first part a number of theoretical elements

concerning the retention mechanisms as well as the influence factors

(type of microparticles, polymer charge density, influence of calcium

anions, paper stock pH, charge order of system components).

Experimental research aimed the achievement of some

multicomponent retention systems based on PAAs (low and medium

cationic charge), based on PAAEs and anionic colloidal silica. In order to

get some good results with such kind of systems, the charge for each

component should be set, the results varying depending on it.

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The optimum polymer charges were determined at a steady charge of

colloidal silica (0.01% in relation to o.d. material), physico-mechanical and

optical paper properties and waste water load were determined.

An important conclusion is that efficiency of micro/nanoparticles

diminishes with increasing the polymer charge. In order to set the

optimum charge of anionic colloidal silica, a steady charge of low cationic

charge polyacrylamide (0.03%) was used, the physico-mechanical and

optical paper properties and waste water load were determined.

It was noticed that maximum reduction of waste water suspensions

(below 50 mg/l) is recorded at an anionic colloidal silica charge of 0.9%.

To diversify micro/nanoparticle systems, a new retention system made of

a PAAE (61.6%), a commercial product (2%) and anionic colloidal silica

(0.9% and 0.8%) was surveyed and achieved.

The effect of charge order concerning system components

(polymer + colloidal silica or colloidal silica + polymer) was also studied

noticing that inverted system (micro/nanoparticles + polymer) leads to the

drop of strength and optical paper properties as well as to the high load of

waste water from paper machine.

Compared to other retention systems (single component, dual

polymer), the multicomponent systems with micro/nanoparticles have

obvious benefits as regards reduction of suspensions in waste water and

improvement of paper quality.

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O – 6-02. Comparative Study of Cr(VI) Removal from Aqueous Solutions Using Natural Sorbents and Purolite A 400 Resin

B. Robu, C. Balan, D. Bilba, I. Cretescu, M. Macoveanu

“ Gh. Asachi” Technical University of Iasi, Faculty of Chemical Engineering, Department of Environmental Engineering and Management, 71 A D. Mangeron, 700050, Romania,

In this study the retention of chromium (VI) by sorption in batch

conditions onto Romanian sphagnum moss peat and respectively Purolite

A400 resin is discussed. The influence of experimental conditions for

Cr(VI) removal were studied tacking into consideration the initial

concentration of Cr(VI) and pH of solutions, adsorbent dose and

equilibration time. This investigation pointed out that the mechanism of

Cr(VI) removal from aqueous solutions using a sphagnum moss peat is a

complex process, involving both sorption and redox processes, while the

Purolite A400 resin presents a chemical stability, working mainly as ion

exchange material

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O - 7. OTHER ASPECTS OF NANOMATERIALS SCIENCE AND TECHNOLOGY

O – 7-01. Health Risks of Manufactured Nanomaterials

Cristina Rusti, Madalina Laura Popescu, Adrian Motoc, Roxana Piticescu, Stoiciu Maria National R&D Institute for Non-Ferrous and Rare Metals, Pantelimon, Ilfov, mpopescu@imnr.ro

Nanotechnology is an emerging field of research and technology

dealing with the fabrication and engineering of materials, structures, and

systems with nano-scale size at least in one dimension. It is more of an

approach to engineering than a science, although it draws on the scientific

knowledge of biology, physics, chemistry, and materials science and is

expected to change these sciences dramatically. The applications of

nanotechnology range from next generation flat-panel TVs, advanced

solar panels, and chemical and biosensors to nanomedicine and energy

transmission efficiencies. When we talk about the health impact of

nanomaterials we need to differentiate 2 types of nanostructures: 1-

nanocomposites, nanostructured surfaces and nanocomponents

(electronic, optical sensor etc.) where nanoscale particles are

incorporated into a device, substance and material, also called „fixed”

nanoparticles;

2-„free” nanoparticles, where at some stage in production or use of

individual nanoparticles of a substance are present.

This paper is focused on environmental and health impact of

nanostructured materials obtained by hydrothermal synthesis. Some

advantages of hydrothermal method are listed bellow. Nanostructured

powders which cannot be prepared using other synthesis routes are easily

obtained starting from water soluble precursors, hydrothermal reaction

takes place in closed system (autoclave) and non-toxic products are set

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free in environmental medium during synthesis. Based on this aspect we

could say that this method is environmental friendly and is included in the

„fixed” segment of the nanomaterials. The systems obtained by

hydrothermal process are stable ones. Hydrothermal reactions are

influenced by some parameters namely: pH, time, pressure, concentration

of starting materials (soluble inorganic salts). With further analysis we can

determine the grain size and their structure. Depending on the starting

materials and synthesis parameters, NO3-, NH4

+, Cl

- and some other

cations could be present in mother solution and washing waters resulted

from filtering and washing of the precipitate. Their concentration was

controlled with chemical analysis (classical volumetry, gravimetry, spectral

methods such as ICP-inductively coupled plasma, colorimetry, atomic

absorption spectrometry) and is situated in the admitted range according

to national standards for waste waters.

Mapping the evolution of NO3-, NH4

+, Cl

- , and the presence of

nanomaterials in waste waters was performed for different hydrothermal

routes.

Further studies regarding the impact upon health and environment

will take place also because it is a quite new approach regarding

nanomaterials, and it is important to know how nanomaterials influence

our life.

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P-1. NANOSTRUCTURED POROUS MATERIALS

P-1-01. Electrical and Structural Properties of TiO2 Thin Films

Diana Mardare1, Nicoleta Cornei2, G.I.Rusu1 1 ''Al.I.Cuza'' University, Faculty of Physics, 11 Carol I Blvd., R-

700506, Iasi, ROMANIA, 2 ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-

700506, Iasi, ROMANIA

Titanium oxide thin films have received worldwide attention and find

extensive applications in a lot of fields, due to its several advantageous

properties: high refractive index and permittivity, wide bandgap, chemical

stability, good transmittance of visible light, etc.

In this paper, titanium oxide thin films were obtained by a d.c.

sputtering technique. Depositing titanium oxide onto different substrates, at

different temperatures, and using O2 or H2O vapours as reactive gas, induces

structural changes. X-ray diffraction patterns show that the proportion of the

crystalline phases: anatase (tetragonal), rutile (tetragonal) and brookite

(orthorhombic) is the one that changes. A mixed anatase/rutile structure is

observed when deposited onto glass substrates, and only a rutile structure

when deposited onto silicon substrates, in the same deposition run. When

using O2 as reactive gas, both anatase and rutile phases are present for films

deposited onto glass and quartz substrates.

From the values of the lattice parameters, calculated using a refinement

CELREF program, it can be observed a slight dependence on the substrate

nature. The bond configuration of titanium oxide films, deposited onto silicon, was

obtained using FTIR in the wave number range: 400 cm-1 - 4000 cm

-1. The

features show the presence of Ti-O and Si -O bonds and also of small amounts

of water, except for the sample obtained with O2 as reactive gas.

As a consequence of the structural changes, the electrical

conductivities modify. The dependences of the electrical conductivity versus

inverse temperature were studied in a wide range of temperature (from 13 K

to 535 K). The activation energies have been determined, in each

temperature range.

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P-1-02. On The Synthesis and Characterization of Poly (Aspartic Acid)

Iordana Neamţu, Aurica P. Chiriac, Loredana Elena Nita, “Petru Poni” Institute of Macromolecular Chemistry Grigore Ghica Voda Alley no. 41A, 700487 Iasi, ROMANIA

Polyaspartic acid belongs to polyamine acids that are an important

class of synthetic polymers produced by chemical polymerization of the same

amino-acid building blocks found in naturally occurring proteins. Polyaspartic

acids (PAA) occur in nature as polypeptide sequences, i.e. in mollusk shells

or snails, regulating the calcium balance of these organisms.

Due in part to the carboxylate groups, polyaspartate has similar

properties to the polyacrylates. The polyaspartate polymers are analogues of

natural proteins, particularly the aspartate-rich proteins from oyster shells that

play a key role in regulating mineralization. Since the polyaspartate compounds

are derived from natural precursors, they are biodegradable and they can be

used to replace petroleum-derived polymers such as polyacrylate and

polyacrylamide. Because of their unique mineralization and ionic properties,

there exists an enormous range of possible applications for the polyaspartate

materials. In the medical domain it is possible its application as

superabsoebents (diapers), biomedical devices (for prevention of pathological

calcification, microencapsulation for drug delivery, surface coatings for implants

to promote crystallization), dental treatment (tartar control agents).

Currently, two principal chemical procedures are used to produce polyamine

acids. One approach links specifically amino-acid monomer units together by

amide bonds. At less complex chemical procedure, starting from

polysuccinimide that is produced by the polymerization of aspartic acid, and

then the polyimide rings are hydrolyzed with stoichiometric quantities of base

to form polyaspartate.

In the paper there are synthesized and comparatively characterized

the polymers from the viewpoint of zeta potential as a function of pH and

conductivity, with some considerations on the changes induced by the two

procedures and in direct connection with the final application as a biomaterial.

The rheological behaviour in dilute solution is also evidenced

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P-1-03. An EPR Investigation of the Core-Shell Effects in CMR Nanoparticles

C.Craciun, A.Popa(1), M.N.Grecu(2), Al.Darabont(1), D.Toloman(1), O.Raita(1), V.V.Grecu(3), M.Glinchuk(4), M.Fardis(5) , I.M.Giurgiu(1) Faculty of Physics, University “Babes-Bolyai”, Cluj-Napoca, Romania (1) National Institute for Research and Development of Isotopic and

Molecular Technologies, Cluj-Napoca, P.O.Box 700, Romania (2) National Institute for Materials Physics, 077125 Bucharest,

P.O.Box MG-7, Romania (3 )Faculty of Physics, University of Bucharest, 077125 Bucharest,

P.O.Box MG-11, Romania (4 )Institute for Problems of Materials Science, Kiev, Ukraine (5)

Institute of Materials Science, NCSR Demokritos, Athens, Greece, popa@s3.itim-cj.ro

An EPR investigation in the paramagnetic regime of

La0.67Ca0.33MnO3-δ nanoparticles (radius ~ 45 nm) was carried out. In order

to obtain the core (∆c) and shell (∆s) line widths the experimental spectra

were fitted with the core – shell model. As resulting from our previous

investigations, the small – polaron hopping model could well describe the

line width temperature dependence for nanosized La0.67Ca0.33MnO3-δ

manganites [1]. Based on it, the analysis of the temperature dependence

of the core line width results in a value of ~ 89 meV for the polaron

activation energy in the core part of the nanoparticles.

We also discuss the theoretical EPR spectra of smaller nanoparticles

(radius < 45 nm) where the increased contribution of the shell component

causes an asymmetric distortion of the line shape.

References

1. L.M.Giurgiu, M.N.Grecu, Al.Darabont, O.Raita, X.Filip, O.Pana and

D.Toloman, Appl. Mag.Reson., 27, 139 (2004).

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P-1-04. Supramolecular Assemblies of Gold Nanoparticles

Mediated by Amino Acids and Aleurone Globular Protein

Aurora Mocanu,* Ossi Horovitz,* Emil Indrea,**Gheorghe Tomoaia,*** Ioan Bratu**, Maria Tomoaia-Cotisel* * ”Babes-Bolyai” University, Faculty of Chemistry and Chemical

Engineering, Physical Chemistry Department, Kogalniceanu Str., no. 1, 400028 Cluj-Napoca, mcotisel@yahoo.com

** National Research and Development Institute of Isotopic and Molecular Technologies, P.O. Box 700, 400293 Cluj-Napoca

***”Iuliu Hatieganu” University of Medicine and Pharmacy, Department of Orthopedic Surgery, Traian Mosoiu Str., no. 47, 400132 Cluj-Napoca

Gold nanoparticles (size from 10 to 50 nm) were synthesized by

three different methods and were characterized by UV-Vis spectroscopy

and transmission electron microscopy (TEM). The shape and size

distribution of gold nanoparticles were determined. Gold nanoparticles

(GNP) were utilized both in colloidal solutions and as an nanostructured

gold film to investigate the interactions of GNP with various organic

compounds, such as amino acids (e.g., lysine, arginine, cysteine) and

aleurone globular protein. The gold films were prepared from gold

colloidal aqueous solutions on glass slides silanized with 3-aminopropyl-

triethoxysilane at room temperature and with a thermal treatment at high

temperature (e.g., 200oC). The globular protein is a major storage protein

extracted and purified from aleurone cells of barley. The binding

behaviour of organic molecules and GNP was studied using UV-Vis and

FTIR spectroscopy, scanning probe microscopy (e.g., AFM), transmission

electron microscopy (TEM) and X-ray diffractions.

By monitoring the evolution of the surface plasmon resonance

absorption of gold nanoparticles in colloidal solutions in the presence

of amino acids, the supramolecular assembly was shown to be

dependent on the amino acid structure and concentration, particularly

on their side groups such as thiol or amine group. These findings

provide new insights into the fabrication and physical characterization

of biomaterials made of gold nanoparticles and amino acids or globular

protein with potential applications in the nanoscience and

biotechnology.

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P-1-05. Multifunctional Assemblies of Gold Nanoparticles

Mediated by Aleurone Protein and Chitosan

Maria Tomoaia-Cotisel,* Gheorghe Mihailescu,** Liliana Olenic,** Gheorghe Tomoaia,*** Ioan Bratu,** Emil Indrea,** Irina Kacso,** Liviu Bobos,* Simina Dreve,** Aurora Mocanu*, Ossi Horovitz*

* Babes-Bolyai” University, Faculty of Chemistry and Chemi-cal Engineering, Physical Chemistry Department, Kogalni-ceanu Str., no. 1, 400028 Cluj-Napoca, mcotisel@yahoo.com

** National Research and Development Institute of Isotopic and Molecular Technologies, P.O. Box 700, 400293 Cluj-Napoca

***”Iuliu Hatieganu” University of Medicine and Pharmacy, Department of Orthopedic Surgery, Traian Mosoiu Str., no. 47, 400132 Cluj-Napoca

We report an investigation of the aleurone protein interaction with

GNP in colloidal solutions and in gold nanostructured films. The results

indicated a remarkable effect of protein binding on GNP in colloidal

solutions and especially on the gold nanostructured films, where a

stronger interaction was evidenced than with gold colloids. The results

indicate that aleurone protein provides a versatile mediator for assembling

GNP into organized composite in the absence and in the presence of

chitosan directing to materials with varied functional response. The self-

assembly process provides nanocomposites with controlled interparticle

(clusters) spacings as determined by X-ray scattering, TEM and AFM and

modular optical behavior, as examined through UV-Vis spectra.

The cyclic voltammetry is used to study the electrochemical

behavior of multifunctional composite made of GNP, chitosan and

protein, and deposited on gold electrode. From cyclic voltammograms,

it is clearly evidenced that protein molecules near the gold electrode

surface are electroactive. Therefore, direct electron transfer between

the adsorbed protein and the electrode is achieved. This can lead to

the application of aleurone protein to direct electron communication in

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bioelectronic devices and biosensors using compozite materials based

on protein, GNP and chitosan. The compozite material is

multifunctional and offers a matrix where the protein is immobilized.

The three-dimensional, compozite material was deposited on gold

electrode and it appears that the protein has its role of a linker and of a

direct electron communicater.

These data provide new insights into the control of interfacial

interactions in the fabrication and chemical and physical characterization

of multifunctional materials made of gold nanoparticles, globular protein

and chitosan with potential significant applications (sensing material) in

the development of optical, electronic and analytical devices.

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P-1-06. Polysiloxanes Reinforced by in situ Precipited Silica Processed as Thin Films

Maria Cazacu, Mihaela Alexandru, Felicia Iacomi 1” P. Poni” Institute of Macromolecular Chemistry Iasi, Romania

2 “Al.I.Cuza” University, Faculty of Physics, Iasi. Romania

Cross linked polydimethylsiloxanes in situ reinforced with silica

have been prepared and processed as thin films by spin coating or thick

films by casting.

The procedure occurred in the absence of a solvent. The

prepared composites having different content of silica were investigated

by different techniques: XRD, IR, AFM. The structure and the surface

morphology are dependent in great measure on the composition.

Comparative studies were made on polydimethylsiloxanes

reinforced with ex situ silica. References

1. Z. Li, W. Han, D. Kozodaev, J. C. M. Broken-Zijp, G. de With, P. C. Thűne, Polymer 47, 1150-1158, 2006

2. Cazacu, M., Marcu, M., Macromol. Rep. A 32(7), 1019-1029, 1995 3. R. Saito, J. Polym. Sci.: Part A: Polym. Chem. 44, 5174-5181, 2006

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P- 1-07. Effects of Surfactant Adsorption on Nanomagnetic Particles Studied by Structural Methods

M.Balasoiu1,3, M.L.Craus2,3, A.I.Beskrovnyj3, D.Bica4, L.Vekas4. M.Lozovan2

1 Horia Hulubei National Institute for Physics and Nuclear Engineering Bucharest, Romania

2 National Institute of Research and Development for Technical Physics, Iasi, Romania

3 Joint Institute of Nuclear Research, Dubna, Russia

4 Romanian Academy- Section of Timisoara, Timisoara, Romania; balasoiumaria@yahoo.com

The properties of nanostructured magnetic materials and

devices are extraordinarily different from those of conventional

magnetic systems. The very interest in the study of nanostructured

magnetic materials is related to the basic notion that novel effects and

properties may be expected whenever “crossing length scales”

appear in a system [1,2]. The synthesis and characterization of

nanomagnetic materials are essential to the future top applications

like these of data storage and biotechnology/medicine. To active

investigations are subjected a class of such magnetic nanostructured

systems the ferrofluids.

The ferrofluids represent colloidal suspensions of single domain

ferromagnetic particles of about 100A in diameter, stabilized with

surfactant molecules, in a suitable liquid carrier. From a considerable

number of experimental results (for example, EM analysis and

magnetic measurements) Comparing the particle size distribution

obtained from magnetic measurements it was concluded that the

physical and magnetic dimensions of the nanomagnetic particle are

different. This might be caused by magnetite surfactant interactions.

In latest publications such a behavior is considered to be due to an

intrinsic property of nonstructured magnetic materials.

The purpose of presented work is to investigate the influence of the

absorbed surfactant layer on the magnetic structure of the particles by

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structural methods (XRD, neutron diffraction, SANS). Conventional -2

X-ray diffraction scans using CoK radiation were recorded in order to

identify the crystallographic phases and to determine the average

coherent sizes and the microstrains of the samples In Fig.1 is presented

the diffractogram of Fe3O4 nanoparticles with adsorbed on their surfaces

an oleic acid layer

Fig.1. XRD diffractogram of Fe3O4 nanoparticles with adsorbed on

their surfaces an oleic acid layer

References

1. L.Vekas, D.Bica, O.Marinica, M.Rasa, V.Socoliuc, F.D.Stoian,

J.Magn.Magn.Mater, 289 (2005) 50

2. V.Kuncser, G.Schinteie, B.Sahoo,W.Keune, D.Bica, L.Vekas, G.Filoti, J.Phys.:Condens. Matter 19 (2007) 1-16

3. M.V.Avdeev, D.Bica, L.Vekas, O.Marinica, M.Balasoiu, V.Aksenov, L.Rosta, V.M.Garamus, A.Schreyer, J.Magn.Magn.Mater 311, (2007), 6-9.

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P- 2. ADVANCED MULTIFUNCTIONAL MATERIALS

P-2-01. Sisteme liante cu continut de MgO multifunctionale

Mohanu Ileana, Ionela Petre, Amzica Florin, Ilie Gabriela, Andreescu Ecaterina, Roxana Fechet

S.C.CEPROCIM S.A.

Abordări moderne in cercetarea materialelor de constructii sunt

orientate spre realizarea unor noi lianti performanti, cu implicatii benefice

asupra mediului. Una dintre acestea se refera la sistemele liante avand in

componenta oxid de magneziu reactiv. Prezenţa MgO în proporţii diferite

imprimă sistemului liant caracteristici specifice determinând

multifuncţionalitatea acestuia şi anume: densitate ridicată, rezistenţe

mecanice ridicate, rezistenţă la medii corozive, imobilizarea deşeurilor,

captarea CO2 din atmosferă.

In lucrare sunt prezentate rezultatele cercetarilor efectuate

pentru obtinerea unor sisteme liante pe baza de ciment portland cu

proportii variabile de MgO.

S-a urmarit mecanismul de hidratare al liantilor din acest sistem la

termene scurte si lungi precum si influenta compusilor de hidratare asupra

caracteristicilor sistemului intarit.

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P-2-02. New Pyrrolopyrimidine Derivatives under Ultrasounds Irradiation

Costel Moldoveanu,a Geanina Mangalagiu,b Dan Maftei,a Ionel I. Mangalagiu*a a “Al. I. Cuza”University, Carol I-st Bd., No 11, Iasi 700506, Romania. E-mail: moldcos@chem.uaic.ro b National Colleague, Iasi, Arcu Street, No. 4, Iasi, 700125

The literature describes a large variety of pyrimidine compounds

with different biological activities: anti-HIV, anticancer, antituberculosis ,

antimicrobial, antihypertensive, platelent, etc. The emphasis of this work

was to obtain pyrimidine derivatives using cycloimmonium ylides as

reactive species, under classical conditions and under ultrasounds

irradiation. The reaction pathway involves, a Huisgen 3+2 dipolar

cycloaddition of ylides to dipolarophiles (activated alkynes).

The problems of stereo- and regiochemistry involved in these

types of cycloadditions are discussed. Under ultrasounds irradiation the

reaction times decrease, the amount of solvent used decrease also and,

the yields are much better.

Acknowledgements: to CNCSIS Bucharest, grant no.

1155/2006, for financial support.

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P-2-03. SDM in Advanced Nanomaterials fine-tuning for some Perovskites type AHE Study

S. Mohorianu, F.-V. Rusu, M. Lozovan National Institute of Research and Development for Technical Physics, 47 Mangeron Blvd., Iasi,700050, Romania. e-mail: sergium@phys-iasi.ro

Nanostructured materials that have tailored properties to achieve

improved mechanical, electrical, optical, magnetic and other functional

properties are now essential for future applications in the current industrial

manufacturing. The continuous evolution in the actual technology of

nanomaterials requires a careful understanding of chemical and physical

properties of materials, structures and processes at the micro- and

nanoscale. The major research objectives in advanced nanostructured

and multifunctional materials are still the modelling, the design, the

characterization and the fabrication of such a useful functional materials.

On the worldwide framework of computational nanotechnology [1]

it clearly appears that the software required to design and model complex

molecular structures become progressively available. In this context, in

the last few years we have also contribute [2, 3] to the effort of the

nanomaterial modelling and in the computer assisted design of some

magnetic nanomaterials. The atomic structure of nanostructured materials

is different than that seen in crystals or glasses because of the large

volume fraction >50% of grain boundaries or interfaces. Nanometer sized

materials (1 to 100nm) contain about 900 atoms if zero-dimensional

shape nanomaterial is considered. The magnetic permeability, the

magnetic anisotropy, the electrical conductivity are strong and effectively

correlated with the grain size of the nanomagnetic material [4, 5].

In the present paper we describe how a Simulation and Design

Method (SDM) attempt, based on our last results, and are applied on two

perovskites type materials, La2/3Ca1/3MnO3 and La2/3SrMnO3 in order to

study the Anomalous Hall Effect (AHE).

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References

1. R.C.Merkle, Computational nanotechnology, Nanotechnology, vol.

2, p. 134, 1991 2. S.Mohorianu, M. Lozovan, Rom.Journ.Phys., Vol. 52, Nos. 3-4,

2007 p. 337. 3. S.Mohorianu, M. Lozovan, C. Baciu, JOAM, Vol. 9, No. 5, May

2007, p. 1499 – 1504. 4. J.Ivcov, The Halleffect in amorphous alloys of early and late

transition metals, Fizika A4 3, 1995 561-570 5. T.Fukumura, H. Toyosaki, K.Ueno, M. Nakano, T. Yamasaki and

M. Kawasaki, A Scaling Relation of Anomalous Hall Effect in Ferromagnetic Semiconductor and Metals, JJAP Express Letter, vol. 46, No. 26, p. L642-644

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P-2-04. New Polysilane - Diazine Materials

Ionel Mangalagiu,1* Dorina Mantu,1 Rodinel Ardeleanu,2 Gabriela Sacarescu,2 Mihaela Simionescu2, Liviu Sacarescu2 1. “Al. I. Cuza” University of Iasi, Organic and Biochemistry Department, Bd. Carol 11,700506 Iasi, Romania; e-mail: ionelm@uaic.ro 2. Institute of Macromolecular Chemistry “Petru Poni”, Aleea Grigore Ghica Voda 41A, 700487 Iasi, Romania; e-mail: livius@icmpp.tuiasi.ro

Oligo- and polysilanes form a specific class of materials, which

have been subjected to many investigations during the last decades. [1,2]

Some of their intriguing electrical properties are related to the specific ó-

electron delocalization which endow polysilanes directional conductivity,

strongest along the axis of the chain.[3,4] Among these, polyhydrosilanes

are a relatively new class with specific properties.[5,6] Recently[7] our

group discover a new class of hybrid polysilanes with N-allyl-

cycloimmonium salt skeleton.

This work describes the first synthesis of a new polymer

poly[methyl(H)-comethylphenylsilane] with pendant diazine heterocyle.

This material was obtained by catalytic addition of Si-H groups within a

poly[methyl(H)-co-methylphenylsilane] backbone to the N-heterocycle.

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This hybrid polymer was characterized by spectral analysis,

thermogravimetric analysis and gel permeation chromatography (GPC).

References

1. J. P. Wesson, T. C. Williams, J. Polym. Sci., Part A; Polym.

Chem. Ed. 1979, 17,2833.

2. R. West, L. David, P. I. Djurovich, K. L. Stearly, K. S. Srinivasan, H. J. Yu, J. Am. Chem.Soc. 1981, 103, 7352.

3. A.Herman, B. Dreczewski, W. Wojnowski, Chem. Phys. 1985, 98, 475.J. Roncali, Chem. Rev. 1992, 92, 711.

4. G. Sacarescu, R. Ardeleanu, L. Sacarescu, M. Simionescu, J. Organomet. Chem. 2003,685, 202-206.

5. J. E. Frommer, R. R. Chance, “Encyclopedia of Polymer Science and Engineering”,J.Wiley & Sons, New York 1986, Vol. 5.

6. R. Ardeleanu, I. Mangalagiu, G. Sacarescu, M. Simionescu, L. Sacarescu, Macromol.Rapid Commun. 2004, 25, 1231.

Acknowledgements: to Romanian Ministry of Research and

Education - MATNANTECH program, grant no. 36/2005, for financial

support.

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P-2-05. Average Size of A Places and Cation Disorder Effects on Transport Phenomena in

La0.54Ho0.11Ca0.35Mn1-xCoxO3Manganites

Mihail-Liviu Craus1,2, Carmen Mita3, Nicoleta Cornei3, Mihai Lozovan1

1 Institute of Research and Development for Technical Physics, Iassy, Romania,

2 Joint Institute of Nuclear Research, Dubna, Russia, 3 Chemistry Departament, “Al.I.Cuza” University, Iassy, Romania,

loz@phys-iasi.ro

ABO3 simple perovskites, with A=rare earth elements and/or alkali

(earth) elements, B=Mn (or transition cation) exhibit a large decrease of

the resistivity in an applied magnetic field. Transport phenomena in

manganites, implicitly the transition temperature from metallic to insulator

state, can be controlled by hole doping and the average size of the A

places ( rA ). In agreement with Zener’s theory, the strength of double

exchange is determined by the Mn-O length (dMnO) and Mn-O-Mn angles

( ∠ − −( )Mn O Mn ). A part of the manganites are ferromagnetic, the

Curie temperature increases with band width, determined by dMnO

distances and ∠ − −( )Mn O Mn angles. The ferromagnetism and

transport behavior are correlated with the crystalline structure of

manganites. Tolerance factor (t=dAO / 2.d MnO ) is an indicator of the

departure of ideal structure of the simple perovskites. For an ideal cubic

structure t=1, while for distorted structure (due to the Jahn-Teller Mn3+

cation presence on B places) t≠1. If the A or/and B places are occupied by

more cations, local structure can be quite different by the observed

crystallographic structure. A strong dependence exists between the

Curie/transition temperature, on a side, and tolerance factor and chemical

degree (σ 2 2= −∑ y r ri i A A, , where yi is concentration of i cation on A

place, ri A, - radius of i cation on A place), on other side. The substitution

of Mn with Co should lead to disorder on B places, a local modification of

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the B-O distances and B-O-B angles, due to different crystalline radii of Mn

and Co cations. We will to investigate the influence of substitution of Mn

with Co on the crystalline structure and transport characteristics in

La0.54Ho0.11Ca0.35Mn1-xCoxO3 manganites. The samples were prepared by

sol gel method to improve the purity and homogeneity of the samples:

stoichiometric amounts of La2O3, Ho2O3, CaCO3, MnO2 and CoO (99.9%)

were dissolved in nitride acid. Citric acid and ethylene glycol were added to

the previous solution. The mixture was heated giving a black-brown powder.

The resulted powder was pressed, heated at 800°C 17 hours, grinded, cold

pressed and finally sintered in air at 1200°C for 8 hors. The Mn3+

/Mn4+

concentrations were determined, to establish the correlation between the

Jahn-Teller cation concentration, on a side, and the crystalline structure and

transport characteristics, on other side. The sintered samples were

investigated by XRD, to determine phase composition, atoms positions,

lattice parameters, microstrains and average size of coherent lattice blocks.

XRD data were handled by means of DICVOL, CellRef and a Rietveld type

programs (FullProf). Some different structures (unit cells) were tested by

means of FullProf program. It was established the samples contain only

simple perovkite phase; unit cell volume is changing with the Co

concentration. The resistance of the samples, depending on temperature

and intensity of the magnetic field, was also determined by four probes

method. A decrease of the transition temperature from metallic to insulator

state with Co concentration was observed. The La0.54Ho0.11Ca0.35Mn1-xCoxO3

manganites exhibit a large magneto-resistance near room temperature.

Average size of coherent blocks and microstrains determine the transition

temperature and the ratio between extrinsic and intrinsic magnetoresistance

components. The small polarons hopping and variable range hopping

mechanisms were tested.

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P-2-06. Synthesis, Structure and Properties of Potassium-Doped La0.54Ho0.11Sr0.35-yKyMnO3 Manganites

Nicoleta Cornei1, Carmen Mita1, Mihail-Liviu Craus2,3, Mihai Lozovan2, Francis Abraham4, Nathalie Tancret4, Olivier Mentre4

1 Chemistry Departament, “Al.I.Cuza” University, Iassy, Romania, 2 Institute of Research and Development for Technical Physics,

Iassy, Romania, 3Joint Institute of Nuclear Research, Dubna, Russia, 4Ecole

Nationale Supérieure de Chimie Lille, UCCS, Lille, France, loz@phys-iasi.ro

Lantanum orthomanganites of general formula La1-xAxMnO3 (A=

alkali earth elements) are subjects of recent interest due to their

properties: insulator-to-metal transition, orbitals ordering, charges ordering

and colossal magnetoresistance (CMR). These compounds exhibit

ferromagnetic and antiferromagnetic ordering depending on the relative

concentrations of trivalent and tetravalent manganese ions. The magnetic

structure observed in these compounds can be understood by considering

the competing ferromagnetic and antiferromagnetic exchange

interactions. Highest CMR intrinsic effect was observed near the

ferromagnetic transition temperature TC, and hence the search for new

materials having TC near 300 K. Monovalent ions (K, Na or Rb) doped

lanthanum manganites show similar electrical and magnetic properties to

that of the divalent ion doped lanthanum manganites.

We studied the influence of the potassium concentration on the

structure and the physical properties for La0.54Ho0.11Sr0.35-yKyMnO3 (y =

0.0; 0.05; 0.1) manganites. The samples were obtained by sol-gel

method, using citric acid as gelifiant agent, and flux method using an

excess of KCl. The precursors (La2O3, Ho2O3, Sr and Mn acetates and K

nitrate, K chloride, respectively) were mixed in stoichiometric ratio.

Powders resulted from gel calcinations were presenter and finally sintered

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at 1200°C for 10 hours. For the flux method the mixture of the solid

precursors were melted at 900°C for 24 h in air atmosphere. The melt was

cooled and washed with hot water. The resulting black powder was dried,

pelletized, and sintered at 900°C for 24 hours in oxygen atmosphere.

Sintered manganites were monitored by X-ray analysis a

diffractometer Huber Guinier CAMERA 670 with Cu Kα.1 radiation,

electronic microscopy using a JEOL JSM-5300 microscop, electronic and

IR methods using a VSU-2P spectrophotometer and JASCO 660 Plus FT-

IR spectrophotometers, respectively. Lattice constants, space group,

positions of cations/anions in the unit cell were determined by using

DICVOL and FullProf programs. Magnetic and electrical measurements

were performed with a Foner type magnetometer and, respectively, by

means of four probe method, between 77 and 600 K. The samples

contained only orthorhombic phases (S.G. Pnma). The substitution of Sr

with K leads to a decrease of the unit cell volume and the increase of

Curie temperature. The dependence of the transition from metallic to

insulator (semiconductor) state on chemical composition was also

investigated. The average of the transition temperature from metallic to

isolator state is 220-230 K.

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P-2-07. New Coronands with Aromatic Arms

Ondina - Cecilia Florea, Ana-Maria Balan (married Zbancioc), Ionel Mangalagiu* “Al. I. Cuza” University, Organic Chemistry and Biochemistry Dep. 11 Carol I Bd.700506 Iasi-6, Romania, e-mail: ondinaro2003@yahoo.com

Supramolecular chemistry1 is one of the most expansive field in

chemistry. Coronands are targets of high interest in supramolecular

chemistry, being used as “hosts molecules” for cations, anions or organic

molecules. We report herein the synthesis of a new type of coronands

with aromatic arms using alpha-halogenated dihydroxy-acetophenone

units in reaction with aromatic dicarbonyl chloride. The structures of all

new compounds were confirmed by elemental and spectral analysis (IR,

1H RMN, 13C RMN, COSY, HMQC, HMBC)

.

Acknowledgements: to Romanian Ministry of Research and

Education – MATNANTECH program, grant no. 36/2005, for financial support.

References:

1. Godbert N., Batsanov A.S., Bryce M.R., Howard J.A.K., J. Org. Chem., 66, 3313, 2001.

2. Mertens I.J.A., Jenneskens L.W., Vlietstra E.J., van der Kerk-van Hoof A.C., Zwikker J.W., Smeets W.J.J., Speak A.L., J. Chem. Soc., Chem. Commun., 1621, 1995.

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P-2-08. Martensite-austenite and Ferromagnetic-paramag-netic Transformations in Ni2-xAxMn1-yByGa1-zCz (A, B=Co; C=Al) Heusler Alloys

Mihail-Liviu Craus1,2 , Viorel Dobrea1, Mihai Lozovan1 1 National Institute of Research and Development for Technical

Physics Iassy, Romania, 2 Joint Institute of Nuclear Research, Dubna, Russia,

dobrea@phys-iasi.ro

Ni2MnGa Heusler alloy is known as potential smart material. At

room temperature it has a L21 type structure, undergoing a martensitic

transition (TM) at lower temperatures. Some authors have classified Ni-

Mn-Ga Heusler alloys on the martensitic transformation temperature and

Curie temperatures: first group formed by alloys with TM below room

temperature and TC, second group with TM around room temperature and

third group with TM>TC. The partial substitution of Ni with Mn leads to an

increase of the transition temperature and a decrease of the Curie

temperature. The Ni2-xMn1+xGa alloys have a complex tetragonal structure

at room temperature. The substitution of Ga with Al can change the

crystalline and magnetic structure of Heusler alloys: Ni2MnAl is

antiferromagnetic for a B2 (CsCl type, with Mn and Al randomly distributed

in the center of the cube) structure and ferromagnetic for a L21 (BiF3 type

with Mn and Al ordered distributed in the cube center) structure. A

dependence between the transition temperature and the magnetic field

was observed for some Ni2+xMn1-xGa (x=0.19) and Ni2+yMnAl1-y (y=0.12)

Heusler alloys. For some Heusler alloys a dependence of the transition

temperature on the applied magnetic field was observed.

We intend to put in evidence the structural change and the

dependence between the applied magnetic field on a side, and the

transition temperature, on other, for the Ni2-xAxMn1-yByGa1-zCz (A, B=Co;

C=Al) Heusler alloys.

The Ni2-xAxMn1-yByGa1-zCz (A, B=Co; C=Al; x=0.25; y=0.125;

z=0.125) Heusler alloys with stoichiometric compositions were melted in a

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furnace in Ar atmosphere, homogenized for 72 hours at 1273 K and aged

at 1073 K for 48 hours followed by air cooling. The alloys phase

composition and structural parameters (lattice constants, texture,

microstrains, average size of the coherent blocks were investigated by X-

ray diffraction at room temperature. XRD data were handled by DICVOL,

CeckCell and FullProf programs. The aged alloys are formed by a mixture

of tetragonal/orthorhombic and cubic phases. Only Al substituted alloys

contain a foreign phase (Al-rich). Large microdistortions and small size

coherent blocks were observed. The magnetic measurements were

performed between 77 K and 673 K, by using a Foner type magnetometer

(Hmax = 4 kOe). The Curie and martensitic transformation temperatures

were determined from the variation of specific magnetization with the

temperature. Ni2MnGa alloys have a Curie temperature around 50oC and

a transformation point from austenite to martensite below room

temperature. The presence of the Co in investigated Heusler alloys lead

to an increase of the Curie temperature. In the investigated range of

temperatures no martensite-austenite transition was observed for the

samples with Co. The substituted with Al alloys have Curie temperatures

around 50oC and transition point below room temperature, depending on

the Al concentration.

A correlation between the type of substitution, on a hand, and the

microstrains and size of coherent blocks was established. For the

Ni2MnGa Heusler alloys a dependence of Curie temperature on the

intensity of the magnetic field was observed.

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P-2-09. New Coronands with Aliphatic Arms

Ana-Maria Balan (married Zbancioc), Ondina-Cecilia Florea, Ionel Mangalagiu* “Al. I. Cuza” University, Organic Chemistry and Biochemistry Dep. 11 Carol I Bd.700506 Iasi-6, Romania, e-mail: sweetyanamaria@yahoo.com

During the last decades [1, 2], supramolecular chemistry became

a real paradigm in organic chemistry. We report here, synthesis of a new

type of oxacoronand using aromatic dihydroxi compounds and

polyfunctionalized reagents of type haloacyl chloride.

The novelty of these reactions consists in using alpha-halogenated

dihydroxy-aceto-phenone units which allow further a synthetic route of

obtaining ligands possessing multiple binding sites with many applications.

Acknowledgements: to Romanian Ministry of Research and Education –

MATNANTECH program, grant no. 36/2005, for financial support.

References

1. J. M. Lehn, Angew. Chem., Int. Ed. Engl., 1988, 27, 89; ibid,

“Supramolecular Chemistry – Concepts and Perspectives”, VCH, Weinheim, 1995.

2. T. Bogaschenko, S. Basok, C. Kulygina, A. Lyapunov, N. Lukyanenko Synthesis 2002, 15, 2266-2270.

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P-2-10. Effect of Ce and/or Gd Dopping on the Micro-structure Properties of PT Type Ceramics

M.Balasoiu1, V.Tripadus1, M.-L.Craus2, A-M. Moisin3

1 “Horia Hulubei” National Institute for Physics and Nuclear Engineering Bucharest, Romania; balasoimaria@yahoo.com

2 National Institute of Research and Development for Technical Physics, Iasi, Romania;

3 INCDIE ICPE-CA, Bucharest, Romania;

Advanced ceramic materials are now well established in many

areas of every day use. The improvements in performance, service life,

savings in operational costs and savings in maintenance are clear

evidence of the benefits of advanced ceramic materials. Life

expectancies, now in years instead of months with cost economics in the

order of only double existing component costs, give advanced ceramics

materials a major advantage. The production of these advanced materials

is a complex and demanding process with high equipment costs and the

requirement of highly specialised and trained people. The ceramic

materials of tomorrow will exploit the properties of polycrystalline phase

combinations and composite ceramic structures, i.e. the co-precipitation

or inclusion of differing crystalline structures having beneficial properties

working together in the final compound. Neutron scattering methods are

intensively used to obtain structural information about these materials.

We will analyze the structure, grain morphology and porosity of

sample of two different perovskite type systems lead titanate with rare

earths substitutions prepared at different temperatures by means of XRD

and small angles neutron scattering (SANS).

Conventional -2 X-ray diffraction scans using CoK radiation

were recorded in order to identify the crystallographic phases and to

determine the average coherent sizes and the microstrains of the

samples. Some lead titanate with Ce/Gd substitutions, with a structure

similar to makedonite were obtained by ceramic standard technology. The

structure and the phase composition of the samples were tested by

means of XRD.

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Sintered samples have a tetragonal structure, similar to

makedonite (PbTiO3) (s.Fig.1). PT have a phase transition from cubic to

tetragonal structure, which determine the appearance of large strains and

a decrease of mechanical stability. The doping with trivalent or tetravalent

cations as Gd3+

, respectively, Ce4+

etc seems to enhance the mechanical

stability and the to preserve the electric properties. We obtained

information concerning the geometry of the pore space, chemical

aggregation and defects in investigated materials. Small grain sizes

and/or high densities of inner pores could lead to a spectacular changes

of the mechanical properties.

Figure 1 The difractograms of: 1) PT(Gd) sintered at 1180ºC / 1h (green) (experimental) and 2) PbTiO3 (tetragonal structure, calculated with FullProf)

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P-2-11. Steroid Analogous through Ultrasounds Assisted Reactions

Vasilichia Bejan, Maria Caprosu, Ionel Mangalagiu* “Al. I. Cuza” University, Organic Chemistry Dep., 11 Carol I Bd., 700506 Iasi-6,Romania. e-mail: ionelm@uaic.ro

Literature describes a large variety of phthalazine compounds

with different biological activities: anticancer, antimicrobial,

antihypertensive, platelent aggregation inhibitor, etc.

A facile way to obtain diazine derivatives, are using cycloimmonium

ylides, as reactive species in organic synthesis. Considering the steroid

skeleton as the pharmacophoric group for the activity, in this work we

aimed to obtain new steroid analogous with potential antimicrobial activity,

having diazine heterocycles incorporated.

In order to synthesize the desired steroid analogous with

phthalazine skeleton incorporated, first we obtained the corresponding

cycloimmonium salt (1) which in alkaline medium (Et3N) generated the

ylide (2) in situ. Dienophiles, reacts with ylides (2) giving the steroid

analogous (3). The [3+2] cycloaddition occurs with high stereospecificity

and no formation of other isomers was observed. Under ultrasounds

irradiation the reaction times decrease, the amount of solvent used

decrease also and, the yields are much better. Antimicrobial activity was

tested in vitro on germs Gram positive (Staphylococcus aureus Oxford,

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Sarcina luteea, Bacillus subtillis, Bacillus cereus), germs Gram negative

(Escherichia coli, Klebsiella spp., Acinetobacter spp., Pseudomonas

aeruginosa), fungus (Candida albicans).

Acknowledgements: to Romanian Ministry of Education-

BIOTECH program, grant no. 49/2005 and, to CNCSIS Bucuresti, grant

no. 1155/2006 for financial support.

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P-2-12. 1, 2-Diazine with Biological Activity,

Roxana M. Butnariu (maried Tucaliuc), Maria Caprosu, Gabi Drochioiu, Ionel Mangalagiu “Al. I. Cuza” University, Organic Chemistry Dep., 11 Carol I Bd., 700506 Iasi-6,Romania. e-mail: ionelm@uaic.ro

The interest for synthesis of heterocyclic compounds is receiving

much attention due to their potential biological activities. The emphasis of

this work was to obtain new diazinic derivatives with potential biological

activities. In this reaspect, the cycloimmonium ylides (generated in situ

from the corresponding salts), was treated with variously non-symmetrical

substituted dipolarophiles. The reactions occurs as [3+2] cycloadditions

and involves additionl regiochimical problems.

The structure of the new compounds was proved by elemental

and spectral analysis (SM, IR, 1H NMR, 13C NMR, and two-dimensional

experiments 2D-COSY, 2D-HETCOR (HMQC), long range 2D-HETCOR

(HMBC)); the in vitro biological test was realized for the new heterocyclic

compounds synthesized.

Acknowledgements: to CNCSIS Bucuresti, grant no. 1155/2006,

for financial support.

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P-2-13. Poly (Aspartic Acid) Template for a Bioactive Structure

Aurica P. Chiriac, Loredana Elena Nita, Iordana Neamţu “Petru Poni” Institute of Macromolecular Chemistry Grigore Ghica Voda Alley, no 41A, 700487 Iasi,

ROMANIA

Poly (aspartic acid) belongs to the new family of biodegradable,

environmentally friendly poly(amino acid) polymers in which amide linkages

extend the chain. The biodegradability as well the chelating properties of

partially derivative poly (aspartic acid) determines the numerous

applications of this polymer. Thus, peptide hormone-polyamino acid

complexes can be used in medicine, for example for the therapy of

hormone-sensitive tumours, such as breast and prostate carcinoma, benign

prostate hypertrophy and in gynaecology for the treatment of endometriosis,

hysteroscopy and for the treatment of fertility disorders. The poly(amino

acid) – peptide hormone complexes can furthermore be prepared with a

controllable hormone content by lyophilization of the aqueous solutions. By

means of the nature and the molecular mass of the poly(amino acids) –

poly(aspartic acid) –, by incorporation of hydrophobic amino acids into the

polymer structure or by partial esterification, the release rate of the active

compound can be controlled. As it is well known Zeta potential

measurements give information about the overall surface charge of the

particles and how this is affected by changes in the environment (e.g. pH,

presence of counter-ions, and adsorption of proteins). Charge shielding by

hydrophilic groups can be used to predict the effectiveness of the barrier

function against opsonisation in vivo. Zeta potential is also used to

determine the type of interaction between the active substance and the

carrier; i.e. whether the drug is encapsulated within the body of the particle

or simply adsorbed on the surface. This is important because adsorbed

drug may not be protected from enzymatic degradation, or may be released

very rapidly after administration. The study presents the poly(aspartic acid)

characterization from the viewpoint of its zeta potential measurements in

order to be used as template for a bioactive compound preparation.

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P-2-14. Microstructure of La0.54Ho0.11Sr0.35-xNaxMn1-yCuyO3

Manganites

Mihail-Liviu Craus1,2, Nicoleta Cornei3, Carmen Mita3 1 Institute of Research and Development for Technical Physics,

Iassy, Romania, craus@phys-iasi.ro 2 Joint Institute of Nuclear Research, Dubna, Russia, 3 Chemistry

Departament, 3 “Al.I.Cuza” University, Iassy, Romania,

Manganese perovskites, Re1-xAlkxMnO3 (Re= rare earth; Alk=

alkali earth/alkali elements) were intensively investigated in the last ten

years, due to the observed colossal magnetoresistance (CMR) near

ferromagnetic-paramagnetic transition temperature. The CMR effect is

most prominent for x≈0.3. Spin structure and electric properties are

controlled by Zener mechanism, despite some experimental results,

which can not be explained by means of double exchange theory. We

will establish a correlation between the radius and distribution of the

cations in the unit cell, on a side, and physical properties on other side

for La0.54Ho0.11Sr0.35-xNaxMn1-yCuyO3 manganites. The samples were

obtained by sol-gel method, using oxides (La2O3, Ho2O3; 99.99% purity),

Sr and Mn acetates (99%) and Cu nitrate (99%). Oxides and acetates

were solved in an aqueous solution of nitric acid, respectively, an

aqueous solution of acetic acid. The gel was obtained by adding an

aqueous solution of citric acid to a stoichiometric mixture of precursors.

Powders resulted from gel calcinations were presintered and finally

sintered at 1200°C in air. Presintered and sintered manganites were

monitored by X-ray analysis to determine begin of solid-state reaction,

the phase composition, the parameters of unit cell, the average size of

coherent blocks and the microstrains. XRD data were obtained with a

diffractometer with data acquisition system and Cu anode X-ray tube, at

room temperature, and handled with DICVOL, CELLREF and

FULLPROF programs. Mn-O distances, Mn-O-Mn bonds angles and

atoms positions in the unit cell were determined. Magnetic and electrical

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measurements were performed with a Foner type magnetometer and,

respectively, by means of four probe method, between 77 and 600 K.

The sintered samples contain only perovskite phases. A variation of the

average size of the coherent blocks and microstrains with Cu and Na

concentrations was observed. The substitution of Sr with Na leads to a

decrease of the unit cell volume, while the Cu substitution produced a

non-monotonous variation of the unit cell. We discussed the

dependence between the tolerance factor (experimental and calculated),

the chemical disorder degree and the band width, on a side, and the

Curie temperature on other side. The dependence of the transition from

metallic to insulator (semiconductor) state on chemical composition was

also investigated.

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P-2-15. Ferromagnetic Materials Synthesized in Silica Matrix

N. Suliţanu, V. Nica, F. Brînză Solid State and Theoretical Physics Dept., Faculty of Physics, Al.I.Cuza University, 700506, Iasi, Romania

The importance of nanosized and nanostructured magnetic

materials is established from many times ago. The played role is

sustained by new magnetic properties relieved at nanoscale. Various and

new application was developed e.g. materials for drugs carrier, contrast

agents for magnetic resonant images, EMI protective paintings,

information storage. In this paper we intend to present new obtained

results in synthesis of nanosized clusters of ferromagnetic elements, Fe,

Ni and Co and their various alloys. A chemical method was used in order

to obtain embedded nanoclusters of mentioned materials in a silica matrix.

A new shape of clusters is obtained and similarity with silicon and

silicon dioxide diffusion in some steels can explain those shapes. A

magnetic property was also investigated. Using proposed method, new

shapes of nanosized ferromagnetic clusters can be obtained and used for

new micro and nanoactuators application.

References

1. T. Sourmail, Near equiatomic FeCo alloys: constitution, mechanical and

magnetic properties, Prog. Mater. Sci., 2005:50, p816-880. 2. F. Johnson, C.Y. , Um, M.E., McHenry, H. , Garmestani, JMMM

Volume 297, issue 2, February 2006, 93-98. 3. F. Hamadache et all, J. Mater. Res., Vol. 17, No. 5, May 2002.

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P-2-16. Synthesis and Magnetic Properties of Fe3O4 Nanoparticles Embedded in a Zeolite Matrix

N. Suliţanu, F. Brînză Department of Solid State Physics and Theoretical Physics, “Al.I.Cuza” University of Iasi, Blvd. Copou 11, 700506 Iasi, Romania

In this paper we presented a theoretical and an experimental method

for embedding magnetite (Fe3O4) in a porous zeolite (ZSM-5 and

mordenite) using chemical and electrochemical methods.

Zeolites are crystalline aluminisilicate materials used extensively as

shape-selective and acid catalysts in many different industries. The

topology of the frameworks of these materials creates pores and channels

of varying sizes (for different zeolite materials) that admit or exclude

different adsorbate molecules. The channel systems in the zeolite

materials can range from simple unidimensional channels to complex 3D

pores networks.-

The structure of zeolites with pores or channels of well-defined size

are particularly suitable for the study of magnetic properties of ultrafine

particles of Fe3O4 introduced into the zeolites structure using chemical

and electrochemical methods. We obtained experimentaly a hysteresis

Magnetic

moment of

Fe3O4

electrodeposited

nanoparticles in

ZSM-5 zeolite.

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loop for a zeolite sample impregnated with Fe3O4, using electrochemical

method for embendding feromagnetic sample.

At low fields the sample have the tendance to behave like a

ferromagnetic substance, but, with incrising field, appear a diamagnetic

component (who alternate proportional with the field but with minus sign)

which tend to changes the hysteresis.

References

1. Ch. Baerlocher, W.M. Meier, D.H. Olson, Atlas of Zeolite Frame-

work Types, Elsevier, 2001. 2. Ch.J.-M.Y. Houssin, Nanoparticles in zeolite synthesis, Thesis,

Tech. Univ. Eindhoven, Netherland, 2003. 3. I.Zhang, A. Manthiram, Fine Magnetic Particles in Layered

Silicates and Zeolites, IEEE Transactions on Magnetics, 31, 6, 1995.

4. Despina Mehedintu Davis, Electrodeposition of magnetic nanowires and nanotubes, Thesis, Texas Tech. University, USA, 2005.

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P-2-17. Multilayered Thin Films with Selective Spectral Properties

Felicia Iacomi1, R. Apetrei1, G.M. Rusu1, C. Baban1, E.Budeanu2, M. Purica2, D. Luca1 1 “Al.I.Cuza” University, Faculty of Physics, Iasi. Romania 2 National R&D Institute for Microtechnologies, Bucuresti,

Romania

Multilayer structures formed from Al, SiO2, TiO2, Ag thin films were

deposited on glass substrates by using vacuum thermal evaporation and

RF magnetron sputtering methods.

The structure and morpho;ogy of thin films were studied by

means of X-ray diffraction (DRON2, CuKα) and atomic force mycroscopy

(home-made equipment). Transmittance and reflectance spectra of thin

films were analysed by using a STEAK-ETA-OPTIK instrument.

The obtained multilayerd structures exhibit an UV-Viz

transmittance maxima, more intence and more sharp as the thickness of

dielectric thin films and substrate temperature increase.

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P-3. NATURAL AND SYNTHETIC ZEOLITES

P-3-01. Compositional Particularities of the Piatra-Verde Slanic Volcanic Zeolitic Tuffs. Hump Effect.

Bogdan-Ion Mocanu*, Nicolae Naum**, Cristian Lungu*** * Refinery Petrobrazi, Brazi, Prahova district,

bogdan.mocanu@petrom.com ** Management Programs National Centre from Education and

Research Ministry, No.21-25 Mendeleev street, Bucharest, naum@cnmp.ro

*** National Institute for Lasers Plasma and Radiation Physics, Magurele, cristian.lungu@inflpr.ro

Using up-today analysis methods, this paper confirms existence

like majority phase of the natural zeolite – clinoptilolite, to the prejudice of

the heulandite, and proves the presence alongside of the clinoptilolite, an

amount fine crystallizated silica in the Piatra-Verde Slanic zeolitic tuffs.

This quantity of the fine crystallizated silica causes the appearance

an „Hump effect” on the X-ray diffraction patterns in the range of the 15-

35° (2θ angles) and confers to this zeolitic tuff an very good pozzolanic

activity.

Pozzolanic activity together with the good ionic exchange capacity

could represent the premises a complex utilizations of this clinoptilolitic

tuff, such as nuclear decontamination of a contaminated with

radionuclides streams and theirs safety stocking.

Key-words: clinoptilolite, heulandite, fine crystallizated silica,

pozzolanic activity.

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P-3-02. Could the ESR Investigation Support the Presence of Au Nanoparticles Stabilized in Zeolites ?

S.Farcas, A.Popa, L.M.Giurgiu, Z.Qu(1) , E.Roduner(1)

National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj-Napoca, P.O.Box 700, Romania (1)Institut fur Physikalische Chemie, Universitat Stuttgart, D-70569 Stuttgart, Germany sorin120@yahoo.com

Zeolites are very promising to act as support for stabilizing

metallic particles because of the crown-ether-like ring structures in their

cages and channels. In this communication we used ESR spectroscopy to

study the possible anchoring of Au nanoparticles in Y-type zeolites. In a

previous paper we have reported for the first time the ESR observation of

the square-planar complex of Au(II) with four nitrogen atoms of two

ethylenediamine ligands in the super cage of the zeolite [1].

In the temperature range 4 – 300 K a sharp ESR signal was

observed in Au/NaY zeolites pretreated with oxygen at different

temperatures. The characteristic spectral parameters g = 2.008 and ∆H =

8 G are almost temperature independent.

A discussion is given concerning the possibility that this

resonance to be attributed to the conduction electron spin resonance

(CESR) of Au nanoparticles. Kawabata’s conditions and the quantum size

effects are taken into account [2].

References

1. Z.Qu, L.M.Giurgiu and E.Roduner, Chem. Commun. 26, 2507 (2006)

2. L.M.Giurgiu, 5-th National Conference “New Research Trends in Material Science”, Sibiu, Romania, 2007 – invited lecture

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P-3-03. Utilization of Natural Clinoptilolite for Reducing the Risk of Gall Stones Renal Calculus and Tumor Formation

N. Izmirova1, E. Djourova2, B. Aleksiev2, M. Baeva3, P. lagoeva4, P. Uzunov5, I. Tomova6, A. Boyanova3, Tz. Mircheva4

1 “Clinalex - Nedylka Izmirova” Pte, 2 SU “St. Kliment Ohridski” Faculty of Geology and Geography, 3 BAS Institute of Solid State Physics, 4 Sofia hospital for active treatment of onco-patients,

5 SU “St. Kliment Ohridski” Faculty of Physics, 6 “First obstetrics and gynecology hospital” St. Sofia,Sofia,

Bulgaria

The present study offers a possibility to use natural clinoptilolite

(Cpt) as a means for reducing the risk of tumor, gall-stones, and renal

calculus formation. It is based on the result of optical investigation of

central openening spherulites (Sph) in human urine of ill and healthy

organism /1/.

In experiments carried out on mice during a period of 24 months,

we observed that there exists a certain tendency toward reduction of

tumor (appearing spontaneously) formation in mice treated orally or

dermal with Cpt when compared to the untreated mice, especially in

regards to the Limphoma - Lymphosarcoma and Reticulum-cell Neoplasm

Type B /2/.

Comparative analysis of the XRD patterns of Cpt and Sph shows

that in most cases d-spaces of Sph fall into intervals or coincide with the

d-spaces of Cpt. Most probably in analogy with Cpt, Sph in human

organism exhibit adsorption, ion-exchange, catalytic and molecular sieve

properties.

Sph develop and reproduce normally when the symmetry and the

composition of the growth environment are not influenced by endo- and

exogenic factors. In case of intoxication of the organism the symmetry and

composition of the environment it changes. Then the polymorph

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transformation becomes slower, the central pores of the Sph close. The

latter tighten and display not typical for them processes – capsulation and

concentric growth. In the concentric layer thus formed radial orientation of

the crystals which is a predisposition for gall-stones and renal calculus.

For reducing the risk of tumor, gall-stones, and renal calculus formation

per oral application of natural Cpt alone or in combination with vitamin C is

recommended.

References

1. N. Izmirova, B. Aleksiev, Method for Diagnosis, Patent №

63679/1999, BG. 2. P. Blagoeva, Z. Gendgev, N. Izmirova, and Tz. Mircheva,

Investigation for Carcinogenesis of Natural Clinoptilolite on mice and rats, Report to the Ministry of Science and Education, № 54919/20.12.2001, Sofia, Bulgaria.

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P-3-04. On the Use of Zeolitic Volcanic Tuff in the Decontamination of Wastewaters

Doina Humelnicu1, Evelini Popovici2

1 “Al.I. Cuza” University, Iasi, Faculty of Chemistry, Dept. of Inorganic and Analitycal Chemistry, doinah@uaic.ro

2 ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

The significant cation exchange capacity of natural zeolites and

their availability at the low cost are the main reason useful for

radionuclides immobilization and implicit decontamination of radioactive

wastewaters.

Natural zeolite volcanic tuff was tested for its ability to remove

radioactive ions (UO22+

and Th4+

) from wastewaters. The sorption

behavior of U(VI) and Th(IV) from aqueous solutions has been studied in

the absence of the ionic competition as a function of contact time,

radioactive ions concentration, temperature and pH.

Distribution coefficients of uanium and thorium on zeolitic volcanic

tuff were measured using batch technique.

The apparent thermodynamic parameters ∆Ho and ∆S

o for the sorption

process were calculated. The results obtained indicate that this process is

endothermic. The negative values obtained for ∆Go and the increase of these

absolute values with increasing temperatures are consistent with the fact that higher

temperatures favor the sorption process.

References

1. D. Humelnicu, G. Drochioiu, M.I. Sturza, A. Cecal, K. Popa – J. Radioanal. Nucl. Chem., 270, (2006), 637.

2. S. Akyil, M. Eral - J. Radioanal. Nucl. Chem., 266, (2005), 89. 3. A. Kilincarslan, S. Akyil - J. Radioanal. Nucl. Chem., 264(2005), 541. 4. E. Popovici, D. Humelnicu, C. Hristodor – Rev. Chim. Bucharest,

57, (2006), 675.

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P-3-05. Synthesis and Characterization of Ferrierite/ZSM-35 Type Zeolite in the Presence of Ethylenediamine

Ioana Droahna, Iuliean Asaftei, Nicolae Bilba ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

Ferrierite is an intermediate port zeolite between small port (8-

MR) zeolites of 0.3-0.5 nm effective diameter and the large port (12-MR)

zeolites which sorbs the cyclic hydrocarbons. The FER framework

contains a 2-D system of intersecting channels, one straight, along [001]

direction with 10-ring elliptical openings (0.54x0.42 nm) and the other

(cages) parallel to [010] direction with 8 ring openings (0.48x0.35 nm). At

the 2-D intersections there are pseudo-spherical cavities (“ferrierite cage”)

with free diameter of 0.6-0.7 nm and with two 8-MR openings. FER is of

interest as a molecular sieve and of acid catalyst due to channels formed by

10-MR, high SiO2 /Al2O3 ratio (6-60), thermal stability and to good chemical

stability in either acidic or basic solution. FER possesses interesting

adsorption properties, exhibits an excellent shape-selectivity in the

isomerization of n-butene to iso-butene (an intermediate for the production

of MTBE, an additive in lead-free gasoline), in skeletal isomerization of 1-

hexene and a good activity for the selective reduction of NOx.

FER and ferrierite-type zeolites (Sr-D, ZSM-35, Fu-9, ISI-6, Nu-

23, ZSM-38) have been prepared in the reactant system without or with

organic templates. Synthesis of Sr-FER from aqueous gels in the

temperature range 340-3800C has been first reported by Barrer and

Marshall in 1964. Zeolite ZSM-35 was first synthesized in aqueous gels in

presence of organic compounds as template by Plank et al. in 1977. ZSM-

35 is isostructural with natural FER but have unit cell parameter a=1.892

nm instead of 1.92 nm and in the powder DRX pattern the strong line at

1.13 nm present in FER is absent or is of very low intensities. Most of the

reports on synthesis of FER required high crystallization temperature and

products were of low SiO2/Al2O3 ratio. Usually, FER/ZSM-5 zeolite is

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synthesized in an alkaline system containing different organic compounds

as templates, including pyrrolidine, pyridine, n-alkylamine, piperidine,

TMAOH, TPABr, 1,4-dimethylpiperazine, 1,4-butyldiamne, ethylenediamine,

diethanolamine, cyclohexyldiamine, choline, morpholine, dioxan,

hexamethyleneimine.

In this study FER/ZSM-35 materials with good phase purity and

crystallinities were prepared by hydrothermal synthesis using mixtures of

sodium silicate, aluminium sulphate, sulphuric acid and distilled water in

the presence of EDA as template in an autoclave at 1800C for 1 to 6 days.

The zeolites obtained were characterized with XRD, SEM, NH3/TPD, N2

sorption and n-hexane, benzene, cyclohexane, methanol and water

adsorption. XRD patterns have confirmed FER structure and are

consistent with a literature data. Close examination of FER/ZSM-35 show

the absence or presence of a very weak line at 1.13-1.15 nm. The

intensity of the peak appearing at 25.3o (2θ) was selected as a measure of

crystallization degree. According to their SEM photos, FER/ZSM-35

samples appear as a rectangle-shaped, sheetlike morphology. The N2

sorption isotherms at 77 K belongs to Langmuir type I, the surface area

being in the range 270-380 m2.g

-1 and the pore volume of

0.15-0.18 mL.g-1

. The NH3-TPD curve of the acid form of FER/ZSM-35

present two peaks of ammonia desorption: one at 2800C (in the range of

200-4000C) specific to weak acid sites and another at 600

0C (in the range

of 400-9000C) specific to strong acid sites.

The ability of synthetic FER/ZSM-35 to selectively sorbs normal-,

branched chain and cyclic hydrocarbons (non-polar compounds) and

water and alcohols (polar compounds) is possible due to the presence of

10-MR in channels and to surface hydrophilic/hydrophobic character.

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P-3-06. Synthesis of SnO2 Controlled size Nanoparticles in Zeolite Matrices

Aurelia Vasile, Eveline Popovici

''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

Zeolites have open crystalline structures with well-defined and

well-ordered channels of nanoscale dimensions which provide an ideal

environment for synthesizing and stabilizing clusters and nanoparticles.

Synthesis and stabilization of semiconductor nanoparticles encapsulated

in different zeolitic hosts has been studied for CdS, PbS, ZnS, MnS, ZnO.

The impregnation, ion exchange, heat dispersion, chemical vapour

deposition or direct synthesis for preparing of zeolite-nanoguest systems

are the main methods.

This research work was focused on the synthesis of SnO2

nanoparticles inside the channels of the silicalite-1 using the following

methods: the conventional method of impregnation, the original modified

impregnation method and in situ formation during silicalite-1 synthesis.

Influence of synthesis parameters, tin content of the impregnation

solution, temperature and duration of the calcination on in situ SnO2

nanoparticles formation was studied. The samples were characterized by

X-Ray powder diffraction method (Phillips diffractometer using filtered

CuKα radiation), SEM (JEOL-JSM-6300 scanning microscope), DRS UV-

VIS (Shimadzu UV 2401PC spectrophotometer with a integrating diffuse

reflective sphere and BaSO4 as reference), FT-Raman (Nicolet Nexus FT-

Raman spectrometer) spectroscopy. DRS UV-VIS spectra showed for all

synthesized samples an absorption edge in the range 250~270 nm that is

significantly blue shifted compared to that of bulk SnO2 (358nm). The blue

shift of the absorption edge indicates the presence of nanosized SnO2.

The blue-shift of the absorption edge in the DRS UV-VIS spectra is most

pronounced for the nanoparticles SnO2-silicalite-1 systems prepared by in

situ formation of SnO2 nanoparticles. The presence SnO2 nanoparticles

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encapsulated in the silicalite-1 pores was demonstrated and by the

Raman spectroscopy. The intensity of the peak of 634 cm-1

, due to the

nanosized SnO2 formation, is higher in the case of in situ method

comparatively with the other studied methods. It is found that all used

methods lead to nanoparticles SnO2-zeolite systems formation, but in situ

formation during silicalite-1 synthesis method is preferable because it is

more simple and efficient. The study suggested that a Silicalite-1 channel

system is a good confinement environmental for formation and

stabilization of SnO2 nanoparticles. In situ formation during silicalite-1

synthesis of the SnO2 nanoparticles is one-step preferable method.

Acknowledgments. The authors are grateful for the

MATNANTECH financial support, Project CEEX No.1/S1/2005.

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P-3-07. Synthesis and Properties of Au and Pt-Au Nanoparticles Dispersed in Nanoporous Materials

Eveline Popovici, Aurelia Vasile, Emiliana Dvininov ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

The stabilization of metallic nanoparticles inside the well-defined

microporous and mesoporous materials lead to an interesting class of

organic-inorganic hybrids with important catalytic properties. Among the

transition metals, gold and palladium are intensively studied. Gold had, for

a long period of time, the reputation of being catalytically inactive. Haruta

[1] demonstrated that nanosized gold particles, when are deposited on an

oxide support, exhibit surprisingly high catalytic activity in oxidation of

carbon monoxide at/or below ambient temperature.

Preparation of supported gold and palladium catalysts can be

achieved by the following different traditional routes: (i) impregnation of a

performed support with those salt solutions followed by drying and

reduction [2]; (ii) cation exchange with support by cationic gold and

palladium complexes followed by washing, drying and reduction [3]; (iii)

coprecipitation of hydroxides of both support and gold followed by drying,

calcination and reduction [4] deposition-precipitation of metal hydroxides

to a suspension of the support followed by drying, calcination and

reduction [5] and (iiii) chemical vapor deposition of a volatile compound of

gold and palladium to a high area support through an inert gas. Another

possibility for gold nanoparticles obtaining is in situ reduction of

chloroaurate ions (AuCl4-) via silanol groups present in inner surfaces of

organo-functionalized MCM-41 or on the surface of amorphous silica.

Metal nanoparticles embedded in titania - matrices could be obtaining by

photo-catalytic reduction of Pd2+

and Au3+

ions under mild conditions.

In this paper, we report the synthesis and characterisation of Au/,

Pd-Au/ and Pt-Au/ nanoparticles dispersed into channels system of the

mordenite (MOR). While Au3+

is a metal cation that is very easy to reduce,

gold nanoparticles are the most difficult to disperse and to anchor in

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zeolites [1-5]. The hydrogen form of the zeolites are characterised by high

dispersion of the metal and the high thermal stability of the obtained

nanoparticles, explained by chemical anchoring of metal clusters by the

Brønsted sites of the framework. Based on these properties of the zeolites

in the present study we have chosen to employ the H-MOR. It was applied

UV-mediated photoreduction method which consists in reduction of Au3+

,

Pd2+

and Pt4+

and ions in presence of a low amount of TX-100 and under

UV-irradiation.

In order to obtain metal nanoparticles dispersed into channels

system of the H-MOR were used solutions of HAuCl4, PtCl4 and PdCl2

with constant concentrations (5·10-3

M). The solutions of metallic

precursors were mixed with a proper amount of TX-100. After stirring for

few minutes, the H-MOR was added in order to obtain a solid/liquid ratio

in order to obtain a loading by 1% (wt%). These mixtures were irradiated

for 3 hours by using a 12W Vilber-Lourmat UV-lamp. The solids were

separated by centrifugation and dried at 80°C for 8 hours. For bimetallic

nano-composites, we synthesized first the H-MOR loaded with gold seeds

by using a similar procedure. In these systems, TX-100 plays roles of both

reducing agent and particles stabilizer.

The sample properties have been studied employing powder X-

ray diffraction, DRS UV-VIS, FTIR, TEM and AFM methods. Powder X-ray

diffraction (XRD) patterns were collected on a BRUKER D8 Advance

Instrument using CuKα1 radiation (Ni λ= 0.15401nm, 40 kV and 50 mA).

TEM images were taken with a JEOL LEM-100CXII transmission electron

microscope at an accelerating voltage of 100 kV. The DRS UV-VIS

spectra were recorded on a Shimadzu UV 2401PC spectrophotometer

with an integrating diffuse reflective sphere and BaSO4 as reference, in

the range 200nm –600 nm.

Different states of ionic and metallic gold were detected in the

mordenite channels and on the external surface of the mordenite – Au+

and Au3+

ions, charged clusters Aunδ+

and neutral nanoparticles. The gold

loading in each mordenite sample was strongly related to the aluminium

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content; the gold species were reduced in the pores of the mordenite only

at lower temperatures.

Acknowledgments. The authors are grateful for the

MATNANTECH financial support, Project CEEX No.1/S1-2005.

References

1. Haruta, M., Size and Support Dependency in the Catalysis by Gold, Catalysis Today, 36 (1997), 153-162.

2. Galvagno, S., Parravano, G., Chemical reactivity of supported gold IV. Reduction of NO by H2, Journal of Catalysis, 55 (1978), 178-190.

3. Guillemot, D., Borovkov, V.Y., Kazansky, V.B., Polisset-Thfoin, M., Fraissard, J., Surface characterization of Au/HY by 129XeNMR and diffuse reflectance IR spectroscopy of adsorbed CO. Formation of electron-deficient gold particles inside HY cavities, Journal of the Chemical Soociety, Faraday Transaction, 93 (1997), 3587-3593.

4. Haruta, M., Yamada, N., Kobayashi, T., Ijima, S., Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide Journal of Catalysis, 115 (1989), 301-309.

5 Haruta, M., Tsubota, S., Kobayashi, T., Kageyama, H.,Genet, M.J, Delmon, B., Low- Temperature Oxidation of CO over Gold Supported on TiO2, α-Fe2O3, and Co3O4, Journal of Catalysis 144 (1993), 175-192.

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P-3-08. Mns Clusters into Zeolite Matrices

Felicia Iacomi1, Aurelia Vasile2, Eleni Pavlidou3,

E.K. Polychroniadis3 1 Faculty of Physics, “Al.I.Cuza” University, Iasi, Romania, iacomi@uaic.ro 2 ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-

700506, Iasi, ROMANIA

3 Department of Physics, Aristotle University of Thessaloniki, Greece

Well defined MnS clusters were prepared within the pore structure

of natural zeolite matrix (clinoptilolite, laumontite and heulandite) by using

two procedures: aqueous ion exchange and impregnation followed by a

sulfidation process with H2S{1-3].

SEM examinations revealed that no disintegration of zeolite framework

had occurred during the synthesis. Optical absorption spectra evidenced

that impregnation method favors the formation of crystalline aggregates.

Optical spectra of MnS clusters formed by using the ion exchange method

are blue shifted and evidence bands at 276 nm and 233 nm. Some

emission spectra were studied as a function of temperature. The emission

band located at 410 nm was attributed to band-band transition of intra-

zeolite MnS cluster.

References

1. F. Iacomi, Surface Science, 532-535 (2003) 816. 2. F. Iacomi, A. Vasile, E.K. Polychroniadis, Material Science and

Eng. B101 (2003) 275. 3. F. Iacomi, M. Vasilescu, S. Simon, Surface Science 600 (2006)

4323.

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P-3-09. Synthesis and Characterization of SnO2 Nanoparticles Encapsulated in Zeolite Hosts

Aurelia Vasile, Carmen Mita

''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

Zeolites are the aluminosilicate members of the family of

microporous solids known as molecular sieves. This is due to a very

regular pore structure of molecular dimensions. The maximum size of the

molecular or ionic species that can enter the pores of a zeolite is

controlled by the diameters of the channels. Zeolites have diversified

areas of conventional application, including separation and adsorption

agent, shape selective solid catalyst, ion exchange agent,

chromatographic column filler, chemical reaction substrate, moisture

control agent, building materials.The nanosized channel system of the

zeolites provides a size- and shape-selective matrix for absorbed

molecules while maintaining a high surface-to-mass ratio. Molecules can

be organized within the framework with a high spatial precision on the

nanometer scale. In the area of optical materials, zeolites will be of

particular interest when specific distances or a spatial pattern of atomic,

ionic, molecular or nanoscaled quest species are required in order to

obtain the desired physical effects.

Synthesis and stabilization of semiconductor nanoparticles

encapsulated in different zeolite hosts has been studied for CdS, PbS, ZnS,

MnS, ZnO /1-6/. The methods for preparing of zeolite-entrapped nanoguests

are usually impregnation, ion exchange, heat dispersion, chemical vapour

deposition or direct synthesis. Synthesis of SnO2 zeolite-entrapped

nanoparticles by ion exchange from aqueous solution is not possible because

strong hydrolysis of Sn (IV) and complex cations formation.

This study presents the synthesis of zeolite-entrapped SnO2

nanoparticles by MSSIE method. The method allows incorporation of

SnO2 nanoparticles in zeolite hosts preventing the hydrolysis in the

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exchange slurry. Influence of zeolite structure type, SiO2/Al2O3 ratio (SR),

exchangeable cation, weight ratio (WR) and irradiation time on

incorporation of SnO2 nanoparticles was studied

Zeolites MOR and ZSM-5 were crystallized by hydrothermal

synthesis.The pure Na-forms were obtained by ion exchange from

aqueous solution of NaNO3 and H-form via NH4+

form. Tin tetrachloride

pentahydrate (SnCl4.5H2O) used was the reagent of analytical purity.

SnO2 nanoparticles semiconductor entrapped in zeolite hosts was

synthesized by the following procedure. The activated zeolite powder was

first mixed with SnCl4.5H2O at a given weight ratio and ground in a mortar.

The mixtures obtained were microwave irradiated using a non-modified

domestic oven (2450GHz, 700W) for 30 min. After heating, the samples

were washed with distilled water and ethanol, dried at 373K and calcined

at 573K for 3h. Zeolite samples used have high crystallinity and purity.

XRD, SEM, FTIR and DRS UV-VIS spectroscopy were used for

characterization of the prepared samples.

The XRD patterns show that after microwave irradiation the loss

crystallinity was not detected. Also, no crystalline SnO2 was detected in all

samples. DRS UV-VIS spectra of zeolite entrapped SnO2 show the

absence of the absorption band in the range 310~380 nm which is

attributed to crystalline SnO2. However, the absorption band in the range

250~270 nm was observed for all zeolite entrapped SnO2.The absorption

edge was determined as crossing point of the tangent through the point of

inflexion with the x-axis. For all the zeolite entrapped SnO2 samples the

absorption edge (in the range 250~270 nm) is significantly blue-shifted

compared to that of bulk SnO2 (358 nm). This blue- shift of the absorption

edge in comparison to bulk SnO2 indicates the presence of SnO2 very

small particles exhibiting quantum size effects. Zeolite structure type, SR,

exchangeable cation, WR and irradiation time influenced the properties of

the resulting samples. Na-zeolite is superior to H-zeolite and the lower

values of the SR lead to formation higher quantity of SnO2 nanoparticles in

zeolite hosts.

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SnO2 nanoparticles entrapped in zeolite hosts were prepared by

MSSIE method. The Sn (IV) can be effectively introduced into the

channels of zeolite hosts by MSSIE method avoiding the hydrolysis and

complex cations formation in the exchange slurry. The study showed that

microwave irradiation is a practical and simple technique and non-

modified domestic microwave ovens can be used as safe and convenient

laboratory devices.

References

1. Stucky, G. D., MacDougall, J. E., Science, 1990, 247, 669. 2. Wang, Y., Herron, N., J. Phys. Chem., 1991, 95,525. 3. A. Vasile, F. Iacomi, M. Caraman, Sci.Anal.”.Al.I.Cuza” Univ Iassy,

Physics. Plasma and Spectroscopy, tom XLVII, 2001, 157. 4. F.Iacomi A.Vasile,13

th IZC, Montpellier, France, 2001, Recent

Research Reprints 14-r-01. 5. F.Iacomi, A. Vasile, M. Caraman, Bul. Inst. Pol. Iaşi, tom XLVIII (LII)

fasc.1-2, 2002, 135 6. F.Iacomi, A.Vasile, E.K.Polychroniadis, Materials Science and

Engineering B101, 2003,275

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P-3-10. Some Studies on Natural Zeolite from Chilioara Area -

Romania

Eveline Popovicia, Maria Alexandroaeia, Aurelia Vasilea, N.Sulitanua, I.Calbb

a ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

b Exploatarea minieră Zalău

Natural zeolites – microporous crystalline aluminosilicates – have

found wide application in ion - exchange, adsorption/separation and

catalytic processes [1-3].

New discovered clinoptilolite deposits from Chilioara areal –

Romania represent a promising material for theoretical studies and

applications.

Samples from 5 zones of this areal were structural characterized

by X-ray diffraction, RES and FTIR analysis.

The Na-form samples -1, obtained by ultrasound assisted ion -

exchange with NaCl solution, were following subjected for ion-exchange

with Au3+

and Ag+ solution.

Special behavior was observed in the case of gold – clinoptilolite

samples: three types of gold species, inside the zeolite channels were

decelated: (a) Au3+

cations, (b) neutral onAu clusters and, (c) Au

nanoparticles located on the external surface of zeolite icrocrystals. Gold

nanoparticles were observed only as the result of reduction of the Au-

exchanged forms at elevated temperatures due to reduction of Au3+

species and aggregation of clusters.

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Figure 1. XRD patterns of samples 1-5 from Chilioara deposit.

The DRS spectra of all studied samples were observed. The

absorption band at 61500; 61472; 220 nm is assigned to the Au3+

ions

and the peaks with the maxim in the region 230 - 380 nm are supposed

to be attributed to the gold clusters [4].

In contrast, silver – clinoptilolite, after similar treatment, contains

only onAg clusters.

References

1. Horvath D., Polisset-Thfoin M. etc., Solid State Ionics, 2001, 141-142, 153.

2. Mohamed M., Ichikawa M., J. Colloid and Interface Science, 2000, 232, 381.

3. G. Riahi, D. Guillemot etc., Catalysis Today, 2002, 72, 115. 4. Y. Kang, B. Wan, Catalysis Today, 1997, 35, 379.

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P-3-11. Synthesis and Characterisation of Alumina Supported ETS-4

Pierantonio De Luca, Danilo Vuono, Alfonso Nastro. Department of Pianificazione Territoriale, University of Calabria, Via P. Bucci, I-87036, Arcavacata di Rende (CS), Italy. p.deluca@unical.it, phone-fax (+39) 0984 496783

In this paper we report on own results concerning the preparation

of ETS-4 supported on α-Al2O3. First, the pre-treatment conditions of the

support are optimised using a basic solution. Second, the best conditions

are searched for the deposition of the ETS-4 crystal.

The so-obtained materials are characterised by XRD, SEM, EDS

analysis, XR fluorescence. The adhesion strength of the crystals to the

support is checked by ultrasound bath, abrasion tests and thermal

treatment.

Keywords Molecular sieve, ETS-4, microporous.

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P- 4. MESOSTRUCTURED MATERIALS - SYNTHESIS AND MODIFICATION

P-4-01. Adsorptive Removal of Cationic and Anionic Dyes from

Aqueous Solutions on Si-MCM-41 Mesoporous Material

Camelia Luchian*, Iuliean Asaftei, Nicolae Bilba ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA *kamelia_luchian@yahoo.com

The discharge of coloured wastewater from textile and dyeing

paper, plastic, cosmetic leather and printing industries into natural water

bodies is currently a major environmental concern. Dyes in water affect

the nature of the water, impedes sunlight penetration into the stream and reduce

the photosynthetic reaction. Many dyes are toxic and even carcinogenic to some

organisms causing destruction of aquatic communities. The removal of colour

from dye-baring effluents is a major problem due to difficulty in treating such

wastewaters by conventional treatment methods (coagulation/flocculation, froth

flotation, reverse osmosis, chemical oxidation and adsorptive techniques).

Currently, the adsorption process provides an attractive viable and effective

alternative treatment due to its sludge free clean operation and completely

removed dyes. A large number of adsorbents have been used for the removal

studies of dyes: activated carbon, sepiolite, alunite, coal, fly ash, clayey soil, red

mud, perlite, zeolites, bagasse, rice husk, coir pith, peat, hardwood, chitosan.

In present work, the use of ordered mesoporous Si-MCM-41 as

adsorbent has been investigated as an ideal alternative for removal of

cationic (crystal violet, methylene blue, rhodamine B) and anionic dyes

(crysoidine, xylenol orange) from their aqueous solutions.

The Si-MCM-41 was synthesized by sol-gel method through a

hydrothermal route. The synthesis comprises alkaline hydrolysis of TEOS

in presence of C16TMAB as surfactant according to the modified reported

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procedure from one mixture with molar composition: 1.0TEOS:

0.2C16TMAB: 5.7NH4OH: 113 H2O.

The structure and the porosity of the calcined Si-MCM-41 sample

were characterized by XRD and N2 sorption. The highly ordered

hexagonally packed 1-D cylindrical pore was confirmed by the presence

of typical four-peaks, one, very strong at a low angle (d100 reflection lines)

and three weaker at a higher angle (d110, d200 and d210 reflection lines). N2

adsorption/desorption isotherm at 77 K is of type IV with a steep increase

at intermediate relative pressure (p/po) between 0.2 and 0.35, indicating

the capillary condensation related to the diameter of the mesopore. The

physical properties of Si-MCM-41 sample are: surface area, SBET=1200

m2.g

-1, pore volume, PV=0.83 cm

3.g

-1 and BJH pore size, DBJH=2.36 nm.

In order to evaluate the efficiency of Si-MCM-41 in adsorptive

removal of dyes from synthetic wastewaters, batch adsorption

experiments of cationic (CV, MB and RB) and anionic (CRI, XO) dyes

were achieved. The scope included the sorption isotherms, the initial dye

concentration and solution pH, temperature, contact time and adsorbent

dosage for all dyes. It was found that the percent of dye removed is

strongly depended on the solution pH, this affecting the surface charge of

the adsorbent. In the case of cationic dyes the adsorption increases when

pH was increased to 5.5-6 but in case of anionic dyes the maximum

adsorption is attained at pH = 1-2 after which decreases. For all studied

systems, percent of dye removal increases with the adsorbent dose and

temperature and decreases with increase of concentration of solution: the

required time for equilibrium establish is of maximum 1 hour. The

equilibrium adsorption data were analyzed using the sorption isotherms

models Freundlich and Langmuir.

Acknowledgments. This study was supported by the CEEX grant

No.1/S1/2005.

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P-4-02. Nanomaterials Based on Cyclodextrins Inclusion Compounds with Antioxidant Properties

C. Luca1, A.-M. Grigoriu1, B. Stoica2, A. Grigoriu3

1 „Gh.Asachi” Technical University, Iaşi, Faculty of Chemical Engineering

2 „Gr.T.Popa” University of Medicine and Pharmacy, Iaşi, Facultaty of Medicine 3 „Gh.Asachi” Technical University, Iaşi, Faculty of Textile and Leather Engineering

Cyclodextrins are substances which present nanocavities (with

the diameter in the range 0.57-0.97 nm) that include molecules of the

same size order (Fig. 1).

Fig. 1 The molecular structure and the schematical representation

of α-, β- and γ-CDs

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The term „antioxidant” refers to the capacity of molecules to

neutralize the so-called free radicals. Inclusion compounds of

β-cyclodextrin and of monochlorotriazinyl-β-cyclodextrin with different

guests with antioxidant properties (ascorbic acid, cinnamic derivatives –

ferulic acid, ethyl ferulate, caffeic acid) have been obtained. The inclusion

compounds have been prepared by crystallization from a mixture of a host

water solution and a guest alcoholic one. The products have been

characterized by ATR-FT-IR spectroscopy and chemiluminiscence. Both

the formation of the inclusion compounds and their antioxidant character

were emphasized. These compounds can find applications in the

cosmetically (toothpastes, creams, lotions, emulsions), pharmaceutical,

textile industries („wellness” textiles with an improved wearing comfort).

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P-4-03. Synthesis Characterization and Photocatalytic Activity of MCM-41 Containing ZnO Nanoparticles

G. D. Mihai1,2*, P. Cool1, N. Bilba2, E. F. Vansant1 1 University of Antwerpen, Laboratory of Adsorption and Catalysis,

Department of Chemistry, Universiteitsplein 1, B-2610 Wilrijk, Belgium; *E-mail: pgdgina@yahoo.com

2 ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

Due to its semiconductor properties, nanometer-sized ZnO has

attracted extensive attention as a photocatalyst for the degradation of

organic pollutants in water and air [1].

Mesoporous solids have received considerable attention in recent

years as host matrices for metal and semiconductor nanoparticles, which

may find important applications in photocatalysis and optoelectronic

devices. Due to its very high surface area and its narrow size pore

distribution, MCM-41 seems to be a good support material for ZnO

nanoparticles to be used as catalyst in potential applications in waste

water treatment and air purification. Methods that are based on the

impregnation of mesoporous silica matrices with zinc precursors have

become popular, but it is generally difficult to achieve high particle

loadings of the host matrix with this method. In this present investigation,

high ZnO particle loadings were prepared using MCM-41 support through

an impregnation method using non aqueous solution of organic salts [2].

X-ray powder diffraction, N2 sorption, EPMA and UV-vis spectroscopy are

used to characterize the ZnO-loaded MCM-41 materials. The influence of

the synthesis parameters on the pore characteristics and the

photocatalytic activity towards degradation of methylene blue in water

under the illumination of ultraviolet rays are investigated.

We have shown that the MCM-41 siliceous matrix can be loaded

by impregnation with Zn(ac)2 changing different parameters and some

structure modifications occur without the collapse of the porous

framework. XRD patterns confirm the existence of ZnO nanoparticles with

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hexagonal wurzite structure. Also, it was found that the ZnO loaded MCM-

41 exhibits high photocatalytic activity for degradation of methylene blue,

indicating that these materials are promising as semiconductor

photocatalysts.

Acknowledgments This study was supported by the NoE project

“Inside Pores” and the GOA project funded by the Special Fund for

Research of the University of Antwerp. This work is also part of the CEEX

No. 1/S1/2005 project.

References

1. M. D. Driessen, T. M. Miller, V. H. Grassian, J. Mol. Catal. A:

Chem. 131 (1998) 149. 2. Ying Xiong, Lei Z. Zhang, Guo-Qing Tang, Gui-Lan Zhang, Wen-

Ju Chen, J. Lumin 110 (2004), 17.

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P-4-04. Modification of Porous Supports for the Development of Hybrid Materials.

V. Meynen1,2, M. Özen1, A. Buekenhoudt2, P. Cool1, E.F. Vansant1

1 Laboratory of Adsorption and Catalysis, Department of Chemistry, University of Antwerpen, Campus Drie Eiken, Universiteitsplein 1, B-2610 Wilrijk, Belgium, email: vera.meynen@ua.ac.be

2 Flemish Institute for Technological Research, VITO, Boeretang 200, B-2400 Mol, Belgium

Zeolites are the best known nanoporous materials with a wide

variety of applications in technology, industry and medicine. However, due

to their microporous nature (ø < 2 nm) large molecules and viscous liquids

are excluded from their porous network. Therefore, mesoporous

materials with large pore dimensions (2 < ø < 50 nm) are gaining

increasing interests due to their applicability in these type of processes

like in fine chemistry, biotechnology, biology, pharmacy. They create

accessibility for large molecules and the ability to allow and control high

mass transfers. Nevertheless, they are inferior to zeolites with regards to

stability, selectivity and activity.

Therefore, hybrid mesoporous materials are being developed in

order to create selectivity and stability which gives them more

opportunities in industrial applications.

Two main synthesis approaches can be applied for the creation of these

hybrid materials, which implement high selectivity and stability in

mesoporous materials. On one hand, mesoporous materials can be

impregnated with zeolitic nanoparticles creating materials with bimodal

porosity and unique porous characteristics.

On the other hand, mesoporous materials can be modified with

organic molecules which form functional and selective groups on the

surface of the carrier material (hybrid organic-inorganic materials).

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P-4-05. Mesoporous Carbons Obtained by Nanocasting Route

Maria Ignat, Eveline Popovici ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA evelinepopovici@yahoo.com

Nanocasting, using highly ordered mesoporous silica as a

template, has brought forward large possibilities in preparing novel

mesostructured materials, like nanostructured carbons. These materials

with controllable pore size, high surface areas, and large pore volumes

have been greatly investigated in many fields of science and technology,

such as storage of hydrogen and methane, supercapacitor, molecular

separation, and catalysis [1].

The nanostructured carbons have been synthesized by various

methods e.g. electric arc discharge, laser evaporation and chemical vapor

deposition. Will be described a method to prepare mesoporous carbon by

using mesoporous silica with an interconnected pore system, type SBA-

15, as nanocasting molds.

The resulting porous carbon obtained after removal of the silica

mold by leaching is a negative replica of the host. The obtained carbon

materials can then be used as a mold for further replication to other metal

oxides, where the carbon is removed by combustion.

In the present work several nanostructured carbons were

synthesized by means of liquid impregnation of SBA-15 and

montmorillonite, as template, with sucrose – as reference – and polyol,

respectively. The precursors (sucrose or polyol) were converted to carbon

inside the mesopores of the silica molecular sieves through a mild

carbonization process using a sulfuric acid catalyst. The starting silica

monoliths were synthesized according to the procedure described by

Nakanishi [7].

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X-ray diffraction, nitrogen sorption, transmission electron

microscopy, atomic force microscopy and FTIR methods were used to

characterize the obtained nanostructured carbons.

The silica template allows a control of the pore morphology of the

obtained carbons. The nature of the carbon precursor influences the

characteristics of the obtained materials.

Keywords: nanocasting, hard template, mesoporous carbon

Reference

1 Ryoo, S. H. Joo, S. Jun, J. Phisical Chemistry B, 103, 37, 1999 2. M.S. Fuhrer, J. Nygard, L. Shih, M. Foreco, Y.G. Yoon, M.S.C.

Mazzoni, H.J. 3. Choi, J. Ihm, S.G. Louie, A. Zettl, P.L. McEuen, Science 288, 494

(2000) 4. A. Bachtold, P. Hadley, T. Nakanishi and C. Dekker, Science 294,

131 (2001) 5. R.H. Baughman, A.A. Zakhidov and W.A. de Heer, Science 297,

787 (2002) 6. A. Srivastava, O. N. Srivastava, S. Talapatra, R. Vajtai and P. M.

Ajayan Nature Materials; 3, 610 (2004) 7. K. Nakanishi, J. Porous Mater., 1997, 4, 67. 8. K. Jurewiczb, C. Vix-Guterla, E. Frackowiak, Journal of Physics

and Chemistry of Solids 65 (2004) 287–293 9. Smalley et al., 7125534, Catalytic growth of single- and double-

wall carbon nanotubes, Oct. 24, 2006 10. M. Monthioux, H. Allouche, R. Jacobsen, Chemical vapour

deposition of pyrolytic carbon on carbon nanotubes, Carbon 44 (2006) 3183–3194

11. John C. Hulteen, Charles R. Martin, A general template-based method for the preparation of nanomaterials, J. Mater. Chem., 1997, 7(7), 1075–1087

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P-4-06. Synthesis of Nanostructured Carbons by Solid Waste Valorization

Maria Ignat, Eveline Popovici ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA mary_rud@yahoo.com

The controlled assembly of nanoparticles has been proposed as

one of the most promising ways to achieve the targets of Nanotechnology.

Once we are capable of such control, the creation of components and

devices which can exploit the fascinating, size-dependent properties of

nanomaterials will be possible.

Carbon nanotubes (CNT), both SWNT and MWNT, are unique

nanostructures with remarkable electronic and mechanical properties and

could be used as key components in the production of high-strength

composites, and advanced sensors, electronic and optical devices,

catalysts, batteries and fuel cells.

Conventionally, carbon nanotubes have been manufactured by a

physical method, such as discharging or laser vaporization, or by a

chemical method such as chemical vapor deposition.

We present a simple, generally applicable procedure for the

assembly of nanoparticles on carbon nanotubes in aqueous solution. This

method for manufacturing carbon nanotubes using waste binding carbon

nanoparticles (pitch) resulted in house ovens, based on coal [1]. Binding

carbon nanoparticles (pitch) are dispersed in a strong acid solution and

heated at 130º C , under reflux, followed by its transformation into carbon

nanotube. By this method, a solid waste was transformed into a

mesoporous nanostructured materials. It was realized a valorization of

solid waste by its transformation into carbon nanotubes.

X-ray diffraction, nitrogen sorption BET, Transmission electron

microscopy, Atomic force microscopy, FTIR were used to characterize the

obtained nanostructured carbons.

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Keywords: carbon nanoparticles, pitch, valorization.

Reference

1. Patent USA 7078007 Yu et al., Jul. 18, 2006. 2. R.K Gupta and I. Dwivedy, Current Applied Physics, Volume 5,

Issue 2 , 2005, Pages 163-170. 3. Y. Cheng, J. Gerald, L. Chadeerton et al., Nanoporous carbon

produces by ball milling, Apl. Ph. Letters, V 74, 1999. 4. S. Iijima, helical microtubules of graphitic carbon, Nature 354, 56-

58 5. Erik Oscar Sunden, Carbon nanotube synthesis for microsystems

applications, Georgia Institute of Technology, august 2006. 6. K. Elias, R. Price, T. Webster, Enhanced functions of osteoblasts

on nanometer diameter carbon fibers, Biomaterials, vol. 23, p. 3279-3287, 2002.

7. H.Hu, Y. Ni, V. Montana, R. Haddon, V. Parpura, Chemzcalyz functionalized carbon naotubes as substrates for neuronal growth, Nano Letters, vol.4, p. 507-511, 2004.

8. V..Lovat, D. Pantarotto, L. Lagostena, B. Cacciari, M. Grandolfo, M. Righi, G. Spalluto, M. Prato, L. Ballerini, Carbon nanotube substrate bosst neuronal electrical signaling, Nano Letters, vol.5, p. 1107-1110, 2005.

9. J. Charest, L. Bryant, A. Garcia, W. King, Hot embossing for micropatterned cell substrates, Biomaterials, vol.25, 4767-4775, 2004.

10. M. Savopulo, B. E. Burakov, Development, Fabrication and Study of Fullerene-Containing Carbon Material (FCC) for Immobilization of Iodine, Saint-Petersburg - 2004

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P – 4-07.Study of Grafted Layer of Mesoporous Alumina Modified with Alkylphosphonic Esters by Spin Label Technique

P.E.Burtseva, P.G.Mingalev, G.V.Lisichkin Moscow State University, Chemistry Department Moscow, Russia, glo@petrol.chem.msu.ru

Phosphonic esters are new, promising type of modifiers for the

surfaces of various oxides, such as oxides of aluminum, iron, copper etc.

At the same time, in order to make the samples of modified oxide with

predictable properties, one should have a clear knowledge of the structure

of the grafted layer and of the factors, which can have influence on this

structure.

Spin label technique is a convenient and powerful method for the

investigation of the grafted layer structure. We used it to study the grafted

layer structure of mesoporous alumina, modified with esters of various

phosphonic acids. It was shown that these esters can give a dense

monolayer, which, however, have some defects. As was found,

submonolayers of grafted phosphonic groups have a pronounced island-

like character, and these islands merge as the surface density value is

increased.

It was also shown that the increase of the modifier concentration

and the temperature of reaction results in the increase of the surface

density value.

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P-4-08. Carbon Nanotubes Decorated with Fe, Co, Zn Nanoparticles

Maria Ignat 1, P.Barvinschi2 , Eveline Popovici1, A. Nastro3

1 ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA, mary_rud@yahoo.com. 2 West University of Timisoara, Faculty of Physics, Bvd. V.Parvan

4, 300223, Timisoara, Romania 3 University of Calabria, Department of Pianificazione Territoriale, Via P. Bucci, 87036 Arcavacata di Rende (CS), Italy.

In recent years, carbon nanotubes (CNTs ) have received a great

deal of attention due to their special physico-chemical, mechanical and

electronic properties [1–3].

By decoration with the catalytically active metal nanoparticles,

impregnated in pores volume or attached to the external walls [4-8], the

carbon nanotubes bring new possibilities of uses in catalysis. The

electronic properties of CNTs have stimulated many applications as

conductors or semiconductors and in the magnetic data storage media.

The results of this research are based on a rapid, convenient and

environmentally benign method for the fabrication of metal nanoparticle–

multiwall carbon nanotube (MWCNT) composites. Functionalized carbon

nanotubes it was prepared by impregnation of CNTs with Fe, Co, Zn, organic

aqueous solutions as metal precursors. Metal nanoparticles were synthesized

by decomposition of metal organic compounds inside CNTs pores.

X-ray diffraction, Raman spectroscopy, Transmission Electron

Microscopy, FT-IR spectroscopy was used to characterize the obtained

metals nanoparticles coated with carbon nanotubes.

Keywords: carbon nanotubes, metal nanoparticles, functionalization.

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References

1. P. M. Ajayan, Chem. Rev., 1999, 99, 1787. 2. J. Hu, T. W. Odom and C. M. Lieber, Acc. Chem. Res., 1999, 32, 435. 3. E. W. Wong, P. E. Sheehan and C. M. Lieber, Science, 1997, 277, 1971. 4. X. R. Ye, Y. Lin and C. M. Wai, Chem. Commun., 2003, 642. 5. Z. L. Liu, X. H. Lin, J. Y. Lee, W. D. Zhang, M. Han, L. M. Gan,

Langmuir, 2002, 18, 4054. 6. B. Xue, P. Chen, Q. Hong, J. Lin and K. L. Tan, J. Mater. Chem.,

2001, 11, 2378. 7. V. Lordi, N. Yao and J. Wei, Chem. Mater., 2001, 13, 733. 8. X.R. Ye, Y. Lin, C. Wang, M. H. Engelhard, Y. Wanga, C. M. Wai,

J. Mater. Chem. , 2004 , 14 , 908 – 913

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P-5. CATIONIC AND ANIONIC CLAYS

P-5-01. Removal of Cr (VI) from Wastewater by Sorption on Isomorphic Substituted Mg/Zn-Al - Type Hydrotalcites

Laura Cocheci1, Rodica Pode1, Eveline Popovici2, Elena Seftel2, Emiliana Dvininov2 1 “Politechnica” University, Timisoara, 300006, Romania

laura.cocheci@chim.upt.ro 2 ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

Chromium (VI) is generally produced via industrial processes

(electroplating, mining, tanning and synthetic fertilisers) and it is

commonly found at contamination sites. Exposure to Cr(VI) may increase

one’s risk of contracting cancer or developing hypersensitivity of the skin

or respiratory system. Moreover, because Cr (VI) exhibits high mobility in

most neutral and alkaline soils, it poses a great threat to surface and

groundwater. Therefore, it is necessary to eliminate Cr (VI) from the

environment.

Layered double hydroxides (LDHs) or hydrotalicite-like

compounds exhibit properties such as anionic mobility and surface

basicity, and they are effective sorbents for the removal of oxoanions,

heavy metals as oxometallate anions and cations and organic pollutants.

The chemical composition of the LDHs can be described by the formula

[M2+

1-xM3+

x (OH)2]x+

[An-

x/n . mH2O]

x-, short denoted [M

2+R - M

3+ - A], where

M2+

and M3+

are metal cations, An-

is an exchangeable anion, and R is the

molar ratio M2+

/M3+

. The decomposition of LDHs when heated at around

500°C leads to mixed metal oxides, which are characterized by high

specific surface areas and homogeneous dispersion of metal cations.

The aim of this study was to investigate the role of a second

bivalent cation intercalation (isomorphic substitution) in the LDHs structure

on the sorption of Cr (VI).

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The sorption experiments used the mixed oxides obtained after

calcination of Mg/Zn-Al - type hydrotalcites, where Mg/Zn = 3; 2; 1; 0. All

experiments were conducted batch wise, at 20±2°C, in an orbital shaker

model GFL 3017.

The aim of the equilibrium experiments was to establish the

optimum conditions (LDHs concentration and granulation, mixing rate) of

the sorption process, and to determine the maximum sorption capacities

of the mixed oxides for the Cr (VI) removal. The calcined LDHs were able

to remove more than 50% of Cr (VI) anionic species within a wide range

of concentration.

The data from the kinetic experiments were processed based on

Lagergren equation and the results fitted satisfactory.

Acknowledgments. The results are obtained as part of the

Project CEEX No. 1/S1 – 2005 activities, under the auspices of

MATNANTECH Scientific Authority.

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P-5-02. Preparation and Characterization of nano SnO2 –Cationic Clays

Aurelia Vasile, Eveline Popovici, Claudia Hristodor

''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA

In the last year’s metal-clays, aluminosilicates with properties and

characteristics of microporous materials have received more attention, as

the possibility of their use as matrix for encapsulation and stabilization of

the nanoparticles. The recognized importance of size quantized

semiconductor particles has prompted their extensive investigations and

the appearance of an ever increasing number of publications. Tin dioxide,

a material with versatile applicability in a large number of physicochemical

procedures, is one of the most intensively studied semiconductors. As an

n-type semiconductor, it is extremely sensitive to reducing gases (CO, H2,

ethanol, hydrocarbons) and may therefore be made use of as a gas

sensor.

This study was focused on the synthesis of nano SnO2 by in situ

between the lamellae clay synthesis, the conventional impregnation

method and the original modified impregnation method followed by

calcination or microwave irradiation. Influence of tin content of the

impregnation solution, surfactant content of the modified sodium-

montmorillonite, temperature and duration of the calcination on in situ

SnO2 nanoparticles formation was studied. The tin oxide content of nano

SnO2-montmorillonite varied between 15 and 40 wt%.

The starting material Romanian industrial montmorillonite, fraction

of size between 0.060 and 0.125 mm, from Valea Chioarului area was

used as starting material. The clay was firstly purified and homoionized by

ionic exchange with NaCl solution. The clay had the following composition

(% wt): SiO2-72.87; Al2O3-14.5; MgO-2.15; Fe2O3-1.13; Na2O-0.60; K2O-

0.60; CaO-0.90; PC-5.70. The clay mineralogical composition consists of

kaolinite (K), illite (I), montmorillonite (M) and nontronite (N), besides small

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quantities of feldspar–albite (F) and quartz (Q). The cationic exchange

capacity (CEC) value of the Na-clay was found to be 82 meq/100g

(determined by ammonium acetate method). The specific surface area of

98m2g

-1 was measured using the methylene blue adsorption method.

Also, a surfactant modified Na – montmorillonite with CTAB was prepared

and used as starting material. The nano SnO2-montmorillonite were

prepared in the following way: a 1% Na-montmorillonite or surfactant

modified Na – montmorillonite suspension was added different amount of

SnCl4.5H2O (as tin precursor) with constant stirring (magnetic stirrer);

stirring was continued for 1 day for ion exchange processes to be

completed. Then, solution of 0.5 M NaOH was added drop wise.

Formation of tin oxide nanoparticles between the lamellae of the

clay or surfactant modified clay was verified by X-ray diffraction (BRUKER

D8 Advance instrument using CuKα1 radiation; Ni filter, λ = 0.15401nm, 40

kV and 50 mA), diffuse reflectance DR-UV/Vis (Shimadzu UV 2401PC

spectrophotometer with a integrating diffuse reflective sphere and BaSO4

as reference), FT-Raman (Nicolet Nexus FT-Raman spectrometer) and

gas adsorption (BET) technique. The photocatalytic activity of the

obtained nano SnO2 - montmorillonite samples was investigated by

degradation of salicylic acid. XRD measurements indicated the sizes of tin

oxide particles to be in the 2-6nm diameter range between the layers of

clay. The distinct blue-shift of absorption edges in DR-UV/Vis spectra

point to a decrease of the particles size in comparison to the bulk material.

It was established that the sizes of the SnO2 nanoparticles depend

strongly on the preparation method. Also, the size of the SnO2

nanoparticles is correlated with the photocatalytic activity of the obtained

nano SnO2 - montmorillonite samples. Due to the smaller sizes of the tin

oxide species obtained, the surfactant modified sodium-montmorillonite

appears to be the most promising matrix for hostage of tin oxide

nanoparticles. It was established that the photocatalytic activity of the

nano SnO2 - montmorillonite prepared is mainly due to presence of

nanosized tin oxide particles. By selecting the appropriate experimental

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conditions, was accomplished size-controlled synthesis of nanoSnO2 -

montmorillonite. In the case of the surfactant modified Na–montmorillonite

with 0.14 mmol CTAB/g, the spectra showed the absorption centred on

315-318 nm, 230-233nm.The observed blue-shift of absorption edges in

DR-UV/Vis spectra point to a decrease of the particles size in comparison

to the bulk material. The similar behaviour was observed and in the case

of samples prepared with 0.05 mmol CTAB/g. The surfactant modified

sodium-montmorillonite appears to be the most promising matrix for

hostage of tin oxide nanoparticles.

Acknowledgments. The authors are grateful for the

MATNANTECH financial support, Project CEEX No.1/S1/2005.

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P-5-03. TiO2-Pillared Montmorillonitic Clay for Sustainable Development

Evelini Popovici1, Rodica Pode2, Aurelia Vasile1, Vasile Pode2, Laura Cocheci2 1 ''Al.I.Cuza'' University, Faculty of Chemistry, 11 Carol I Blvd., R-700506, Iasi, ROMANIA, evelinepopovici@yahoo.com 2 University “Politehnica” Timisoara, Faculty of Industrial

Chemistry and Chemical Engineering, Victoriei Sq. No.2, 300006 Timisoara, Romania

Reports within the last years pointed towards the presence of new

xenobiotic substances in the environment as a consequence of massive

utilization of chemicals for various manufacturing purposes and in day-by-

day life. The incapacity of the conventional wastewater treatment

techniques to fully eliminate most of the biorefractory pollutants has

increased the environmental awareness with respect to set up and

development of more effective treatment systems (FORANO, 2004). A

strong carcinogenic potential was ascribed to azoic dyes and their

degradation products. In addition, they contribute to eutrophication and

disturbance of aquatic ecosystems.

This paper studied the sorption and photodegradation of Congo red

on TiO2-pillared montmorillonite and TiO2-pillared montmo- rillonite

modified by surfactant intercalation. The main goals were equilibrium and

kinetics of photocatalysis, and identification of the appropriate theoretical

models (SAFA OZCAN et al., 2005, GUETTAI & AIT AMAR, 2005). The

equilibrium data interpreted by using the Langmuir model allowed the

determination of the specific thermodynamic constants and identification

of the process as a physical sorption. The Langmuir – Hinshelwood model

was the base for interpreting kinetic data and working out of the rate

constant and reaction order. Under the conditions of the adsorbent

excess, from the kinetics point of view, an apparent first-order model can

be assumed and the pseudo-first-order rate constant was determined

(k’=3.85·10-1 min-1). Also was finding that, under well determined

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conditions, the efficiency of the photocatalysis was double as compared to

sorption.

The study highlighted the role of photocatalysis as part of the dye

removal process. Given the working conditions (Congo Red

concentration: 20 mg L-1 and adsorbent concentration: 0.4 g L-1), the

photocatalysis practically determined double Congo Red removal

efficiency on Ti-PILC as compared to the simple adsorption of the dye.

The experiments carried out on montmorillonite-monocationic form, TiO2-

pillared montmorillonite and TiO2-pillared montmorillonite modified by

surfactant intercalation showed that pillaring increased the dye removal

yield and intercalation enhanced the process. Clay samples incorporating

various concentrations of cetyltrimethylammonium bromide (CTAB) were

synthesized to determine the optimum concentration of surfactant. To get

data concerning the optimum surfactant concentration required to modify

the clay to increase efficiency, three clay samples were studied for

surfactant intercalation by using various surfactant concentrations and the

results were compared to the pillared clay. After ten minutes contact time,

the dye removal efficiency increased from 25.4% in the presence pillared

clay (Ti-C) to 42.7% in the presence of 0.059 g surfactant /g clay. After the

same time interval, the dye removal efficiencies on S2-Ti-PILC and S3-Ti-

PILC samples were similar, which concluded that a concentration of 0.29

g surfactant/g clay was not justified. The intercalation of the surfactant

within clay lattice was reasonable up to 0.29 g surfactant/g clay. For the

same duration, the increase of the photocatalytic material concentration,

i.e., increase of catalytic surface area, led to the increase of removal

efficiency.

Based on results, beyond a certain CTAB concentration the

positive effect of surfactant was not noticed.

Acknowledgments. The authors are grateful for the

MATNANTECH financial support, Project CEEX No.1/S1/2005.

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References

1. FORANO, C. (2004): Environmental Remediation involving

Layered Double Hydroxides.– In: WYPYCH, F. & SATYANARARAYANA K. G. (eds.): Clay Surfaces. – Elsevier, London, 425 p.

2. GUETTAI, N. & AIT AMAR, H. (2005): Photocatalytic oxidation of methyl orange in presence of titanium dioxide in aqueous suspensions. – Desalination, 185, 439-448.

3. SAFA OZCAN, A., ERDEM, B. & OZCAN, A. (2005): Adsorption of Acid Blue193 from aqueous solutions onto BTMA - bentonite. - Colloid Surface A, 266, 73-81.

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P-6. INDUSTRIAL AND ENVIRONMENTAL APPLICATIONS

P-6-01. Removal of Copper (II) Ions from Aqua Solutions by Adsorption on Poplar Sawdust

Corneliu Cojocaru *, Mariana Diaconu, Matei Macoveanu, Igor Cretescu Department of Environmental Engineering and Management, Technical University of Iasi Bvd. D. Mangeron 67, 700050 Iasi, Romania cojocaru_c@yahoo.com

The applying of natural organic materials as low-cost adsorbents

for the removal of heavy metals ions from wastewater is an actual trend in

environmental protection science and technology. Locally available

sawdust of Populus sp is a waste material derived from the commercial

processing of poplar wood. This type of sawdust was found to be a low-

cost adsorbent promising for the removal of copper (II) ions from aqua

solutions and wastewater. In the present work, the ability of poplar

sawdust to remove Cu (II) ions from aqueous solution has been

investigated. In this respect the batch techniques were employed. The

equilibrium adsorption level was determined to be a function of the

solution pH, initial Cu(II) concentration and temperature. Freundlich,

Langmuir, Redlich-Peterson and Sips isotherm have described the

equilibrium adsorption capacity of poplar sawdust for copper. In addition,

the equilibrium nature of copper (II) adsorption at different temperature

(20-50C) has been investigated. The thermodynamic parameters like

free energy and enthalpy changes for adsorption of Cu(II) by poplar

sawdust have been computed and discussed.

Also the poplar sawdust has been employed in the studies

concerning the optimization of sorption removal efficiency of copper from

aqua solutions. The prior investigations indicated that the initial pH of

solution, initial concentration of Cu(II) ions and the sorbent dose are the

most important factors that affect the sorption removal efficiency.

Therefore, the present paper discusses also the experimental design and

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response surface methodology (RSM) as an efficient approach for

predictive model building and optimization of removal efficiency using the

sawdust of Populus sp as inexpensive sorbent. All experiments were

statistical planned according to central composite experimental design

(CCD) of orthogonal type. Based on experimental design the response

surface model was developed and the optimization of factors was

accomplished in order to ensure high sorption removal efficiency. The

developed response model has been validated from statistical standpoint

to ensure the goodness-of-fit. Likewise, the 3D plots and contour-line plots

were drawn for spatial representation and analysis of the response

surface.

P-6-02. The Use the Zeolite Molecular Sieves for CO2 Capture

from Exhaust Gases of Power Plants

Aurelia Bolma1, Dorin Bombos2, Gheorghe Bumbac3, Fanica Bacalum4, Rodica Ganea5, Marcela Pitu5, Mihaela Bombos4, Agnes Serbanescu1 1 ICEMENERG S.A, 8 Energeticienilor Blvd. Bucharest 3, Romania

2University Gas & Oil Ploiesti, 39 Bucuresti Bldv., Ploiesti, Romania,

3 University Politehnica Bucuresti, CTTIP, Polizu #1, Bucharest 6, Romania

4 INCD - ICECHIM, 202 Independentei Blvd. , Bucharest 6, Romania

5 ZECASIN S.A., 202 Independentei Blvd. , Bucharest 6, Romania bolma@icemenerg.ro

The global pollution produced by the greenhouse gases represents now

one of the most complex problems of global environmental protection. The

greenhouse gases (GES) participate in the modification of the

atmospheric strata, having direct consequences on the Earth’s

temperature, process known as “global warming” or, of late, as “global

climatic change”. The GES specified in the Kyoto International Agreement

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are: carbon dioxide, methane, nitrogen oxide, hydrofluorocarbons,

perfluorocarbons, sulphur hexafluoride.

This paper presents a modern post-burning technology for capturing the

green house effect gases produced of power plants in the adsorbant

structure, such as zeolite molecular sieves. The process operates on a

repeated cycle with the basic steps being adsorption and regeneration. In

the adsorption step, gas is fed to a bed of solids that adsorbs CO2 and

allows the other gases to pass through. When a bed becomes fully loaded

with CO2 the feed gas is switched to another clean adsorption bed and

the fully loaded bed is regenerated to remove the CO2. In pressure swing

adsorption (PSA), the adsorbent is regenerated by reducing pressure.

The paper also presents the characterization of the composition of

burning gases resulted from energetic industry and the adsorbants

synthesis. The adsorbant structure was synthetised so that the adsorption

process should present a high selectivity for the component which is to be

removed. In achieving this process, the main role is played by the

physical-chemical characteristics of the adsorbant: specific surface,

volume of pores and medium pore radius, which must approach the

molecular dimensions (micropores).

Index Terms: burning gases, CO2 , post-burning technology, zeolite

molecular sieves, physical-chemical characteristics of the adsorbant.

References

1. H. J. Maldonado and R. T. Yang, Industrial Engineering Chemistry

Research, 42, 2003, 3103

2. Khelifa, Z. Derriche, 13th International Zeolite Conference,

Montpellier, France, July 8-13, 2001, 17-P-14

3. E. Munoz, E. Diaz, S. Ordonez and A. Vega, Annual Meeting: Environmental Applications of Adsorption, 2006

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P-6-03. The Role Played by the Convergent Technologies in Accomplishing Textile Structures

Carpus Eftalea, Dorogan Angela, Scarlat Razvan - The Research – Development National Institute for Textile and Leather certex@ns.certex.ro Ignat Mircea - The National Institute for Electrical Engineering Research – Advanced Research

New materials, nanotechnologies and production processes are

among the most attractive research areas and they remain a mystery for

the public. At the beginning of the 3rd

millennium, humanity is at a

crossroad. The fascination offered by the recorded achievements in

physics, chemistry, biology, medicine and engineering led to new

technological approaches having an overwhelming economic – social

impact. There occurred a shift in the consumers’ values: instead of

wishing for the finest natural materials, people look at beauty through

engineering, innovative design and the intelligent aspect of products.

The scientists, engineers and political factors of the convergent

technologies sketched general domains in which there will probably result

human benefits and social problems:

� the assembly potential of the convergent technologies;

� the extending of human knowledge and contact;

� the improving of human health and physical capacities;

� the improving of the social and group results;

� the national security;

� the unifying of science and education;

The need of convergence in textiles is defined by the following

requirements: the garment as a universal interface; the miniaturization of

technologies; the satisfying of the customers’ needs; the improving of life

quality; textiles as the third dimension of intelligence. The

nanotechnology, biotechnology, information technology and cognitive

science convergence under the generic title “Convergent technologies for

improving human performance” implies human creativity and innovative

ideas aiming at accomplishing personalized, adaptable, synchronized -

with - people textiles that are used in information processing at any

moment, in any place and for anybody.

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P-6-04. The Pb (II) Sorption from Aqueous Solutions by Sphagnum Moss Peat

L.Bulgariu, B. Robu, M. Macoveanu Technical University of Iasi, Faculty of Chemical Engineering, Department of Environmental Engineering and Management, D. Mangeron 71 A, 700050 Iasi, Romania Phone/fax: 00 40 232 271 759, email: lbulg@ch.tuiasi.ro

The lead is a biological poison; it has a high toxicity and could

bring out the obstruction of human nervous central system. Due of the fact

that there are so many industrial sources of lead pollution; there is a high

interest of his removal from industrial wastewaters. The actual interest is

to remove toxic metals such as lead from wastewaters using very

economical materials and very accessible experimental procedures.

The sorption of lead from aqueous solutions by Sphagnum moss

peat from Poiana Stampei, Romania has been studied as a function of

several experimental parameters. The aqueous solution influence of

various pH, also the initial metal concentration, peat dose and contact

time were studied in batch experiment, for three types of peat. The

Sphagnum moss peat was collected from different deeps such as 5 cm

deep, 1 m deep and from 3 m deep. For each experiment was used the

natural peat as collected from site Poiana Stampei, Romania, and the

activated peat with solutions of NaOH and H2SO4 1N.

For natural peat analysed, the sorption percent of lead has a

maximum value (99.3%) when the solution has a pH = 6.0, and is still

increasing with the increase of peat dose. The maximum concentration of

lead that can be removed is 33.2 mg Pb/g peat, and it is considerable

higher than the actual values from literature. Concordant to literature the

activated peat has more efficiency for lead adsorption, so that the

Sphagnum moss peat can successful used for removal of lead ions from

wastewaters.

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P-6-05. Basic Investigation on Phase Behavior of Hydrogenated Castor Oil and Possible Applications in Encapsulation Using PGSS Technique

Lucian Hanu, Sabine Kareth, Eckhard Weidner Chair for Process technology, Ruhr-Universität, Bochum, Germany, e-mail: hanu@vtp.rub.de

Hydrogenated Castor Oil can be used as an additive for

formulations or encapsulation for food and pharmaceutical industry.

Additionally, hydrogenated Castor oil can be designed with tailor-made

morphologies and sizes by supercritical spray processes.

For these processes, the need of knowledge about phase behavior and

fluid dynamic properties in presence of supercritical fluids is evident.

Phase behavior analyses were performed to see the influence of

temperature and pressure (induced by CO2) on physical properties of

the fat. The solubility of CO2 in the fat, the viscosity and density of

CO2 saturated fat were measured. It was of special interest whether a

decrease of the melting point of hydrogenated Castor oil with

increasing pressure would occur. The dissolved gas causes a

decrease in the melting temperature.

High pressure technologies like PGSS (Particles from Gas

Saturated Solutions) allow generating powders with properties which are

difficult to achieve by classical methods like milling, crystallization or

spray drying [1]. A very promising possibility is to use PGSS process to

obtain filled micro particles, solid - solid or solid – liquid composites [2].

Encapsulation of sensitive substances can form an effective protection

against stress factors. The objective is not only the protection of the

sensitive substances, but additionally the micro encapsulation opens

new possibilities for the control of the release of the active substances.

Using a matrix like hydrogenated Castor oil the aim is to generate

particles with the active substance (e.g. a natural plant extract)

encapsulated.

References

1. E. Weidner, Proc. 6th International symposium on supercritical

fluids, Versailles, (2003), 1483– 1495;

2. G. Brandin, Herstellung pulverförmiger Komposite mittels Hochdrucksprühverfahren, Dissertation Bochum, 2005.

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P-6- 06. Ecological Pesticides Based on Layered Double Hydroxides Nanocomposite

Mihaela Frunza, Ionel Marcel Popa Technical University, Iasi, Romania, mfrunza@ch.tuiasi.ro

Pesticides are nowadays widely used in modern agriculture. Only

a small quantity of the applied pesticide is bioactive while a high quantity

is released in the environment (e.g. migrating on or in the soil and

groundwaters, being volatilized in air or being photocatalytically

degraded). The high amount of the used pesticides gives rise not only to

environmental problems but also can affect our health.

Layered double hydroxides (LDHs) represented by the empirical formula

[M(II)1-x M(III)x ·(OH)2]x+

(An-

)·mH2O are a class of ionic lamellar solids with

positively charged layers, counterbalanced by exchangeable interlayer

anions. The large variety of anions that can be incorporated in the brucite-

like layer and the high anionic exchange capacity of these materials allow

using them as matrices for tailoring specific organic – clay hybrid

structures with new potential applications.[1-3]

The incorporation of the organic pesticides in the structure of

layered double hydroxides (LDH) can offer premises to increase the

pesticide active life by reducing its volatilization, controlling the release of

the pesticide from the layered structure and decreasing the pesticide

adsorption in soil and groundwaters.

We want to report in this work the synthesis and characterisation

of layered double hydroxides intercalated with some pesticide (4,6-dinitro-

o-cresol, 2,6-dichlorobenzonitril and 2,4-dichlorophenoxyacetic acid).

References 1. Carja G., Frunza M., Popa M.I. and Popescu C., 2005: The

Polytechnic Institute Bulletin, Iaşi, Tomul LI (LV), Fasc. 1. 2. Hussein M. Z., Long C. W., 2004: Materials Chemistry and Physics,

85, p.427-431. 3. Van der Ven L., Van Gemert M. L. M., Batenburg L. F, Gielgens J.J.,

2000: Appl. Clay Sci., 17, p.25-34.

Acknowledgements: This work has been supported by Ministry

of Education and Research Romania, by CNCSIS cod 53/2006.

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P-7. OTHER ASPECTS OF NANOMATERIALS SCIENCE AND TECHNOLOGY

P-7-01. Small Angle Neutron Scattering from Ferrofluids in

Magnetic Elastomers

E.M. Anitas1, C. Muresan1, M. Balasoiu1, A.I. Kuklin1, I. Bica2 1 Joint Institute for Nuclear Research, Dubna, Moscow

region, Russian Federation. 2 The West University of Timisoara, Timisoara, Timis County,

Romania. Email address: eanitasro@yahoo.com

We report small angle neutron scattering (SANS) from ferrofluids

in magnetic elastomers. SANS method is a powerful technique for

studying the microstructure of ferrofluids (magnetic liquids) under different

conditions and is based on the interaction of thermal neutrons with atoms

of the studied medium. Neutrons are charactarised by a large penetration

depth, which makes it possible to study the unmodified bulk samples.

Fig.1. Experimental data (points) and the theoretical model (curve) of non-interacting polydisperse core-shell particles

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SANS was applied for determining the structure of colloidal

suspensions of a magnetic liquid embedded in a composite material. The

mathematical model founded, which fits experimental data well, see Fig.

1, and is of non-interacting polydisperse core-shell particles. The

magnetic liquid consists of magnetic particles and oleic acid in mineral oil.

The composite material is a polymer matrix of stomaflex crème.

Keywords: Ferrofluids, small angle neutron scattering, magnetic

elastomers, stomaflex crème, oleic acid

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P-7-02. Investigations on the Micronisation of Cacao Butter by the PGSS Process

L.Gontaru, S.Kareth, M. Petermann, M., E.Weidner Chair for Process Technology – Faculty of Mechanical Engineering, Ruhr-University Bochum, Universitätstr.150, 44780 – Bochum, Germany. Contact E-mail: gontaru@vtp.rub.de

High pressure technologies allow to generate powders with tailor

made properties (like: size, size distribution, morphology, crystalinity) that

are difficult or even impossible to achieve by classical methods like

milling, crystallization, spray drying or agglomeration. One of these

technologies is the PGSS process (Particles from Gas Saturated

Solutions) which offers the possibility not only to generate particles from

pure substances, but can also be applied for the formation of composites.

This process runs at low temperatures with pressurized carbon dioxide

and is suitable for products that are sensitive to heat or oxidation. The use

of organic solvents, emulsifying agents or other additives can be avoided.

For these reasons the PGSS process operates at especially gentle

conditions and is environmentally compliant. The possibilities of the PGSS

process have successfully been demonstrated over the last years for

numerous substances. Solid as well as liquid substances are transferred

into a form, which is easy to be dosed and admixed. One of the

applications for the PGSS process is to obtain powderous cocoa butter in

form V. Six polymorphic forms of cocoa butter are known. However, only

form V shows the optimal melting behavior for cocoa butter in chocolate.

Recently it was demonstrated, that the PGSS technology is suitable for

generating fluid-filled particles for food applications (e.g. powderous

chocolate encapsulated with liqueur).

Keywords: PGSS, Particles from Gas Saturated Solutions, high pressure,

food products.

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P-7-03. Magnetic Field Effect upon Bioactive Substances

Adsorption

Loredana Elena Nita1, Aurica Chiriac1, Sossio Cimmino2, Clara Silvestre2, Donatella Duraccio 2 1 “Petru Poni” Institute of Macromolecular Chemistry

Grigore Ghica Voda Alley no. 41A, 700487 Iasi, achiriac1@yahoo.com 2 Istituto di Chimica e Tecnologia dei Polimeri,Via Campi Flegrei,

34, 80078 POZZUOLI, ITALIA

Methyl methacrylate (MMA) copolymers with 2, 3 epoxypropyl

methacrylate (GMA) and styrene (S) copolymers with GMA were tested as

matrices for the coupling of the bioactive products. The preparation of

polymeric matrices was realized by classic emulsion polymerization (CW)

and also comparatively obtained through unconventional procedure in the

presence of a magnetic field (MF) of 1500 Gs intensity.

In the paper, the albumin (BSA) adsorption onto the

synthesised polymeric matrices, it was study. Thus, it was compared

the coupling process performed with or without the magnetic field

presence.

It was also studied the influence of the temperature, pH and ratio

between BSA and polymer upon the albumin adsorption yield. The yield of

BSA adsorption is higher in case of the copolymers matrices synthesised

in the MF presence. At the same time the BSA adsorption performed in

the MF presence evidences decreased yields of coupling.

Keywords: albumin adsorption, magnetic field effect, methyl methacrylate

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P-7-04. Azaheterocycles: Effect on Germination and Seedling Growth on Plants

Marian Risca, Elena I. Perju, Maria Caprosu, Gabi Drochioiu, Ionel Mangalagiu* “Al. I. Cuza” University, Organic Chemistry Dep., 11 Carol I Bd., 700506 Iasi – 6 Romania, email: ionelm@uaic.ro

Higher plants are recognized as excellent indicators of

cytogenetic and mutagenic effects of some chemicals and are applicable

for the etection of environmental noxious compounds. Recently it was

proved that some diazine salts with similar structures to phenoxyacetic or

indolylacetic phytohormones, could have on plants either inhibitory or

stimulating activity, according with their concentrations. Having in view the

above consideration, the emphasis of this work was to synthesize new

salts analogous of phytohormones and to test their influence on plants

germination. The cycloimmonium salts were prepared treating the

nitrogen heterocyles with variously halogenated derivatives, under

classical conditions or under ultrasounds irradiation.

Studies on the germination and seedling growth of Norway spruce

have been done. The experiments were conducted in controlled

temperature room and results showed that germination percentages,

shoot and root lengths and fresh weights varied as a function of

concentration and structure of each investigated compound. Higher

concentrated solutions of the investigated compounds exhibited highly

inhibitory activity on spruce germination, while the lower concentrations

resulted in a stimulating action, especially for the radical’s length.

Acknowledgements: to CNCSIS Bucharest, grant no.

1155/2006, for financial support.

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P-7-05. Synthesis of Highly Fluorescent Materials through Eco-friendly Methods

Gheorghita Zbancioc, Costel Moldoveanu, Maria Caprosu, Ionel Mangalagiu* “Al. I. Cuza” University of Iasi, Organic and Biochemistry Department, Bd. Carol 11, 700506, Iasi, Romania,e-mail: ionelm@uaic.ro

The synthesis of highly fluorescent material continues to arouse strong

interest in the field of biochemistry as well as in the field of material science

because of their fascinating applications such as sensors and biosensors,

electroluminescent materials, lasers, and other semiconductor devices.1-4

The overall goal of this work was to develop a new, efficient and general

method for preparation of highly fluorescent pyrrolo- diazine derivatives

using MW. In this respect, variously dazinium ylides (derived from

pyridazine, phthalazine and pyrimidine), generated in situ from the

corresponding cycloimmonium salts, were treated with activated

electronwithdrawing –alkynes or alkenes under MW and classical heating

conditions.

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Under MW heating the reaction times decrease dramatically (from

several hours to 5 min.) and the amount of solvent used had decreased

also (several times). Most remarkably the yields are much higher with the

use of MW heating, being, in some cases, almost double. Stereo - and

region - chemistry of the Huisgen 3+2 dipolar cycloaddition it was also

discussed.

Acknowledgements: to CNCSIS Bucharest, Romania (grant

A, cod 1155/2006) and NATO(PDD(CP)-(CBP.EAP.CLG 982499)

/20.11.2005), for financial support.

References

1. Valeur, B.’Molecular Fluorescence’, Willey-VCH, Weinheim, 2002. 2. Lee, S.; Nakamura, T.; Tutsui, T. Org. Lett. 2001, 3, 2005. 3. Thompson, M.A.; Forrest, S.R. Nature 2000, 403, 750. 4. a). Rotaru, A.V.; Druta, I.I.; Oeser, T.; Muller, T.J. Helv. Chim. Acta

2005, 88, 1798; b). Mitsumori, T.; Bendikov, M.; Sedo, J.; Wudl, F. Chem. Mater.

2003, 15, 3759; c). Zbancioc, Ghe.; Mangalagiu, I.I. Syn Lett. 2006, 5, 804.

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P-7-06. Optical Properties of Ni(NiOx)/Al2O3 Cermet Solar Absorber Deposited by Spray Pyrolysis

Elena Purghel*, Luminita Isac*, Anca Duta* * The Centre: Product Design for Sustainable Development,

Transilvania University of Brasov, Eroilor 29, 500036, Romania, e-mail: e.purghel@unitbv.ro

In order to increase the conversion efficiency of solar energy into

thermal energy, a selective surface with high absorbance (α>0.90) over

the solar spectrum and low emittance (ε<0.1) in the infrared domain is

required. Cermets, consisting of fine metal particles embedded in a

ceramic matrix, are considered promising materials for selective surfaces

due to their optical properties and costs. The Ni(NiOx)/Al2O3 cermets, with

maximum absorption (α = 0.92÷0.98) and minimum emission (ε =

0.07÷0.03), are widely used as absorbers of solar energy in solar

selective coatings.

The Ni/NiOx films were deposited onto micro-glass and Al2O3/micro-glass

substrates by spray pyrolysis (SPD). As precursors, aqua-ethanolic

solutions of nickel chloride and nickel acetate were used. Deposition

parameters such as temperature, precursor’s concentration and the

number of spraying sequences were varied for optimizing the nickel

cermet properties. The optical properties of the films (UV-VIS, IR) were

correlated with their chemical composition, crystalline structure and

morphology.

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P-7-07. Synthesis of New Imidazole Derivatives of Potential Interest as Phytohormones under Ultrasounds Irradiation

Marian Risca, Elena I. Perju, Maria Caprosu, Gabi Drochioiu, Ionel Mangalagiu* “Al. I. Cuza” University, Organic Chemistry Dep., 11 Carol I Bd., 700506 Iasi – 6 Romania, email:ionelm@uaic.ro

It is well know that imidazole is one of the most important

biologically potent heterocycle. Certain imidazole derivatives was proved

to be phytohormones, and could have on plants either inhibitory or

stimulating activity, according with their concentrations. Having in view the

above consideration, the emphasis of this work was to synthetise new

imidazole derivatives analogous of phytohormones and to test their

influence on plants germination. The cycloimmonium salts were prepared

treating the imidazole heterocyles with variously halogenated derivatives,

under classical conditions or under ultrasounds irradiation.

Studies on the germination and seedling growth of Norway spruce

have been done. The experiments were conducted in controlled

temperature room and results showed that germination percentages,

shoot and root lengths and fresh weights varied as a function of

concentration and structure of each investigated compound. Certain

influence on germination was found, the imidazole derivatives being of

interest as grow up factors.

Acknowledgements: to CNCSIS Bucharest, grant no.

1155/2006, for financial support.

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P-7-08. Liant hidraulic multifunctional pe baza de ciment portland

Dumitrescu Cristina*, Menicu Mirela*, Georgeta Voicu**, Ionela Popovici*** * S.C. CEPROCIM S.A. ** Universitatea POLITEHNICA Bucuresti *** Universitatea Ovidius Constanta

Prezenta lucrare face obiectul unui proiect CEEX si are ca

obiectiv final realizarea unui ciment cu adaos de calcar fin macinat si alte

adaosuri corectoare cum sunt silicea ultrafina, TiO2 si aditivi

superplastifianti.

Adaosurile corectoare au rolul de a influenta mecanismul

hidratarii cimentului, compozitia fazala si microstructura cimentului intarit.

De asemenea adaosul de TiO2 ii confera produsului finit proprietatea de

autocuratare, fiind eficace in reducerea anumitor poluanti (NOx,

hidrocarburi aromatice etc.).

Prin analize de difractie de raze X, ATD, RMN, SEM, TEM si

analize chimice s-au obtinut informatii privind microstructura cimentului

intarit, compozitia mineralogica si porozitatea la scara nano (2-50 nm) a

acestuia.

Aceste informatii permit imbunatatirea performantelor materialului

cimentoid propus a se realiza.

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P-7-09. Iron Complexes with Ligands Containing Siloxanes

M. Cazacu1, A. Vlad1 F. Iacomi2, L.V.Giurgiu3 1 “P. Poni” Institute of Macromolecular Chemistry Iasi, Romania 2 “Al.I.Cuza” University, Faculty of Physics, Iasi. Romania 3 ITIM Cluj-Napoca, Romania

A series of iron complexes with siloxane-containing Schiff bases

ligands have been prepared by one pot reaction and characterized [1-3].

Depending on the carbonylic compound nature, either macromolecular or

low molecular chelates have been obtained. The polyesteric structures

based on the difunctional chelate monomer have lower thermal stability as

compared with directly synthesized macromolecular chelate. A low iron

content was obtained in all synthesized chelates in the chosen conditions.

Based on IR and ESR spectra, in all these compounds, the complexed

iron was found to be paramagnetic. References

1. Welch, K.D., Davis, T.Z., Aust, S.D. Arch.Biochem. Biophys, 397 (2002) 360.

2. Gabryszewski, M. Spectr. Lett. 34 (2001) 57. 3. J. Sima, Croatica Chemica Acta, 74(3) (2001) 593.

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P-7-10. Nanostructured Materials Type Layered Double Hydroxides Intercalated with Piroxicam: Preparation and Characterization

Mihaela Frunza1, Ionel Marcel Popa1, Viorel Melnig2 1 Technical University, Iasi, Romania, 2 University Al.I.Cuza Iasi, Romania, mfrunza@ch.tuiasi.ro

Piroxicam is a non-steroidal anti-inflammatory drug used to

relieve the symptoms of rheumatoid and osteoarthritis, primary

dysmenorrhoea, postoperative pain; and act as an analgesic, especially

where there is an inflammatory component. Piroxicam use can result in

gastrointestinal toxicity, tinnitus, dizziness, headache, rash, and pruritus.

The most severe adverse reactions are peptic ulceration and

gastrointestinal bleeding.

The pharmacological studies show that intercalation of the drugs

in the layered double hydroxides (LDH) has a synergic effect. On one

hand the presence of the layered double hydroxides ensures a buffered

environment and on the other hand it reduces the ulcerating side effects

of the intercalated drug [1-3].

In this work we have investigated the intercalation behavior of

piroxicam into LDHs by coprecipitation method and ion-exchange

reaction. The intercalated compounds were examined by X-ray diffraction

(XRD), FTIR spectroscopy, thermo gravimetric analysis and SEM

techniques.

References

1 Z. Wang, E. Wang, L. Gao and L. Xu, J. Solid State Chem. 178, 736-741,(2005).

2 B. Li, J. He, D. G. Evans and X. Duan, Appl. Clay Sci., 27, 3-4, 199-207, (2004).

3 V. Ambrogi, G. Fardella, G. Grandolini, L. Perioli, Int. J. Pharm., 220, 23-32. (2001).

Acknowledgements: This work has been supported by Ministry

of Education and Research Romania, by CNCSIS cod 53/2006.

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