NOVEL CHALLENGES IN EU PROGRAMMES FOR SPACE TECHNOLOGY AND AVANCED

RESEARCH. MICROSENSORS MATRIX

FOR AIR CONTROL IN HUMAN SPACE MISSIONS HABITABLE AREAS

- A STAR PROJECT

COORDINATOR OF P1 –PARTNERCSI.DR. ING. EUGENIA FAGADAR-COSMA

Institute of Chemistry Timisoara of Romanian Academy, M. Viteazu Ave, No. 24, 300223-Timisoara, Romania

ICT- Team specialists members

CSI. Dr. Ing. Eugenia FAGADAR-COSMA- coordinatorCSIII. Dr. Ing. Anca LASCU CS.Drd. Ing. Ionela CREANGA CS.Drd. Chim. Anca PALADE CSII. Dr. Fiz. Mihaela Birdeanu - intra muros expert

Conf. Dr. Ing. Dana Vlascici- intra muros expert

Prof. Dr. Fiz. Mihai Popescu- intra muros expert

Main objective Air quality control on space stations and on long distance space missions Proposed solution: • Colorimetric microsensors matrix to detect the presence

of CO, NOx, excess of CO2 and low level of O2.• The matrix is assembled in a multi chip module (MCM)

technology, the microsensors are done in micro systems technologies (MST) including a microfluidic device

• The sensitive materials are the porphyrin derivatives.

SAFEAIR Project ID: 384 Type : CDI Contract no.: 76 /29.11.2013

Period: 29.11.2013 – 29.02.2016 (27 months)Value for ICT: 270 000 RON

Scientifically, the project represents a challenge from many points of view:

• Colorimetric microsensors are less used. • Sensing with porphyrin as sensing material is not an intrinsic

novelty but the porphyrins that we’ll use will be novel structures of A3B porphyrins or double functionalized symmetrical porphyrins.

• Eventually, the signal amplification and especially the MCM assembling - can be seen as other significant challenges of the project.

Practical relevance and utility is above of any explication. • Supplementary terrestrial applications like: submarines, mining,

underground trains, surgery rooms, nursery incubators.

Relevance.

Expected results• The end-product - a portable microsensor

matrix, containing areas of micro/nanosensing sensors, one of them incorporated in a microfluidic device, the system being able to detect the presence of CO, NOx, high level of CO2 and low level of O2.

• The sensing material will be nanostructured porphyrin (with reference both to microsensors and nanosensors).

ConsortiumThe Consortium offers the multidisciplinary expertise:• Specialists in microsensors, in chemistry, in physics, in informatics, in space

• The efforts for a healthy atmosphere in space habitation areas including International Space Station (MIR and SKYLAB have been afflicted with poor air-quality conditions).

• National R&D Institute for Microtechnology, IMT-Bucharest (CO) is the only Romanian specialist in microsystem technologies and has a modern facility for achieving microsensors DIRECTOR: Dr. Ileana CERNICA

• Institute of Chemistry Timisoara, Romanian Academy, ICT (P1) is specialized in nanostructured porphyrins (used as detective substances and adsorbents) and about their toxicologic issues (avoiding possible health risks of nanotechnologies).

• European Business Innovation and Research Centre is specialized in space applications: ESA quality standards and ESA specific validation requirements for space equipments, specific space environment protection and also will have contribution in sensors simulation and signal analysis design.

Viability and risk.

It was emphasized that project management means entirely risk management, due to the novelty of the research.

• The principle “no person is able to think alone to all things that could go wrong”. Thinking this way, two structures, a “counsel of old men” and a “counsel of young men” will meet every 6 months (or in crisis situations) for project analysis in a brainstorming.

• From the technical point of view, the success chances are high. The project is perfectly viable and with results that could be used for future industrial deployment

• The foreseen risks – entering in the category of impossible to solve foreseen risks – are linked to the economic instability and could lead to limitations in the actions of one or other of the partners

• Another problem is occurred because the results cannot be tested in real functioning conditions

ICT-group specific objectivesSynthesis of symmetrical and

asymmetrical porphyrins , and of their metallocomplexes; Obtaining

of the mesoporous silica hybrid with controlled incorporation of

porphyrin as an organic moiety Characterization and sensitivity tests for

porphyrin derivatives

Study of auto-assembling and self-organizing of porphyrin structures in air, solution, thin films

and hybrids

Langmuir-Blodgett and MAPLE deposition of thin films with porphyrins and metalloporphyrins for the

selective detection of gasesIntegration of microsensor structure

with the sensitive porphyrins

Achieving the methodology and the

functional and parametric testing flows

of the microsensors

Technological optimization of the

microsensor &

Demonstration of functionality

Symmetrical mono- and di-substituted

porphyrin derivativesand

Asymmetrical A3B porphyrins

R1=OCH3 or OH, R2=HR2=R1; Me=Co(II), Fe(III) and Mn(III)

A=OPh or 3,4-OCH3; B=Py or HOOC-PhAnd the metalloporphyrins Me=Co(II), Fe(III) and Mn(III)

An original combined solutionmicrosensors, coupled with

nanostructured porphyrins as sensitivesubstances for air contaminants

Sensitive A3B Porphyrin Nanomaterial for CO2Detection

NH

N

CH O CH O

OMe

MeO

N NH

NNH+ 4

+ H+

+ 3

R1

R2

R3

R4

N NH

NNH

N

OMe

OMe

OMe

OMe

MeO

MeO

The UV-vis spectra of the five separated porphyrins, line (2): 5-(4-pyridyl)-10,15,20-tris(3,4-dimethoxyphenyl)porphyrin

Multicomponent Reaction

1 H NMR (400 MHz,CDCl3): 8.91 (6H, m, β pyrr ), 8.81 (2H, d, β pyrr), 8.20

(2H, d, 3,5-Py), 7.78 (3H, d, 5-Ph), 7.26 [8H, s (6H, 2,6-Ph and 2H, 2,6-Py)], 4.18 (9H, s, p-MeO), 3.99 (9H, s, m-MeO),- 2.78 (2H, bs, internal pyrr);

Preliminary testsA novel A3B porphyrin asymmetrically mixed substituted: 5-pyridyl-10,15,20-tris(3,4-di-methoxy-phenyl)-porphyrin Gas adding increased the Soret band intensity in agreement with a linear dependence

Figures. The increase and widening of the Soret band of (PyTDMeOPP) porphyrin function of increasing amounts of CO 2. AFM porphyrin ring aggregates (left side) and filled after CO2 absorption (80 minutes).

E. Fagadar-Cosma, D. Vlascici, G. Fagadar-Cosma, A. Palade, A. Lascu, I. Creanga, M. Birdeanu, R. Cristescu, I. Cernica, A Sensitive A 3B Porphyrin Nanomaterial for CO2 Detection, Molecules 19(12) (2014) 21239-21252.

In a colorimetric gas sensor, an optical system measures the color change of the dye, which depends on the gas to be detected and on its concentration

Detection of high level of CO2 in space habitation areas:Selection of an optical/colorimetric responsive metalloporphyrinThe improving of the response by using complex host–guest molecules or by using additives (indicators or silver colloids)A novel structure Fe (III)-5,10,15,20-tetra(3,4-di-methoxy-phenyl)-porphyrin (FeTDMeOPP) was sensitive to CO2 adding by increasing the Soret band intensity in agreement with a linear dependence. Adding of small amounts of silver colloids to this system significantly increased the sensitivity and also changed the color from greenish to red-brownish.

Thin Coating Deposition Techniques for achieving the best properties of the obtained materials

Deposition Technique Selection strongly depends on:

Physicochemical Properties of MaterialRequirements for Film QualitySubstrate to Being CoatedCosts

Aerosol Spraying

Langmuir-Blodgett Dip Coating

Spin CoatingLaser Deposition Techniques: PLD

Plasma Polymerization

Electrochemical Processes

Photoactivated Processes

INDICATORI DISEMINARE-ARTICOLE ISI Porfirinele A3B nou sintetizate precum si metaloporfirinele cu Fe III, au fost caracterizate fizico-chimic si electrochimic si au fost incorporate in material hybride, cu scopul de a obtine nanomateriale sensibile pentru detectia de gaze: O2, CO2. 1.Baschir L., Fagadar-Cosma E., Creanga I., Palade A., Lascu A., Birdeanu M., Savastru D., Savu V., Antohe S., Velea A., Fagadar-Cosma G., Popescu M., Simandan I.D.UV sensing effect in Langmuir-Blodgett complex films containing a novel synthesized Fe(III) porphyrinDig. J. Nanomat. Bios. 9(2): 847 – 857, 2014, FI=1.092 2. Taranu B.O., Fagadar-Cosma E.*, Popa I., Plesu N., Taranu I.Adsorbed functionalized porphyrins on polyaniline modified Platinum electrodes. Comparative electrochemical properties.Dig. J. Nanomat. Bios. 9(2), 667 – 679, 2014, FI=1.092 3. Fagadar-Cosma E., Dudás Z., Birdeanu M., Almásy L.Hybrid Organic - Silica Nanomaterials Based on Novel A3B Mixed Substituted PorphyrinMat. Chem. Phys. In press (2014) http://dx.doi.org/10.1016/j.matchemphys.2014.07.023, FI=2.395 4. Fagadar-Cosma E., Vlascici D., Fagadar-Cosma G., Palade A., Lascu A., Creanga I.,Birdeanu M., Cristescu R., Cernica I.Sensitive A3B porphyrin nanomaterial for CO2 detection, Molecules (Basel) –19(12) (2014) 21239-21252, FI=2.1.

5. Fagadar-Cosma E., Vlascici D., Birdeanu M., Fagadar-Cosma G., Novel fluorescent pH sensor based on 5-(4-carboxy-phenyl)-10,15,20-tris(phenyl)-porphyrin, Arabian Journal of Chemistry (2014), doi:http://dx.doi.org/10.1016/j.arabjc.2014.10.011, FI=2.684

BREVETE Cerere OSIM A/00096/06.02.2014DETECTOR DE PRAG DE IRADIANTĂ UV PE BAZĂ DE Fe(III)-METALOPORFIRINĂ, NANOTUBURI DE CARBON SI STEARAT DE Ba SI PROCEDEU DE REALIZARE A ACESTUIABaschir Laurentiu, Savastru Dan, Miclos Sorin, Popescu Mihai, Lorinczi Adam, Alin Velea, Simandan Iosif, Birdeanu Mihaela, Eugenia Fagadar-Cosma Conferinte plenareFagadar-Cosma E , PORPHYRINS IN SENSING APPLICATIONSThe 38th International Symposium on Environmental Analytical Chemistry ISEAC38, Lausanne, Switzerland, June 17-20, 2014, Book of Abstracts, Plenary Lecture E02, pg 36, www.iseac38.ch

Fagadar-Cosma E , Novel challenges in EU PROGRAMMES for Space Technology and Avanced Research. Microsensors matrix for air control in human space missions habitable areas - A STAR PROJECTNew Trends and Strategies in the Chemistry of Advanced Materials with Relevance in Biological Systems, Technique and Environmental Protection, 5-6 June 2014, Timisoara, Romania, Book of abstracts, Plenary Lecture p. 13, ISSN 2065-0760

Anca Lascu , The Influence of Silver Colloids in Increasing the Colorimetric Response of Fe(III) Metalloporphyrin to CO2 DetectionAutori: Lascu A., Palade A., Creanga I., Fagadar-Cosma E.Modul de prezentare a lucrării: Comunicare orala20th INTERNATIONAL SYMPOSIUM ON ANALYTICAL AND ENVIRONMENTAL PROBLEMS, 22 September, Szeged, 2014 Lucrări comunicate şi publicate integral în volume ale unor manifestări ştiinţifice internaţionale 1. Palade A., Creanga I., Szabadai Z., Lascu A., Vlascici D., Fagadar-Cosma G., Fagadar-Cosma E.Synthesis, Chromatographic Separation and Spectroscopic Characterization of A3B Free Porphyrin Used in Gas SensingProceedings of the 20th International Symposium on Analytical and Environmental Problems, 22 September 2014, Szeged (Hungary) Edited by Zoltán Galbács,Page 209, File Z209-212