12™ TIHANY SYMPOSIUM ON RADIATION CHEMISTRY

August 27 - September 1, 2011 Zalakaros, Hungary

PROGRAM AND ABSTRACTS

SPONSORS

The Organizing Committee is grateful to the following Organizations for their financial help:

International Atomic Energy Agency

Hungarian Atomic Energy Authority

Paks Nuclear Power Plant Ltd. Co.

The Municipality of Zalakaros ORGANIZED BY

Institute of Isotopes Hungarian Academy of Sciences (HAS) Hungarian Atomic Energy Authority (HAEA) International Atomic Energy Agency (IAEA)

ORGANIZERS

Honorary Chair: Robert Schiller

General Symposium Chair: László Wojnárovits

Organizing Chair: András Kovács

Local Organizing Committee: Mária Baranyai, Barbara Beiler, Tamás Csay, Csilla Földváry, Katalin Gonter, Péter Hargittai, Renáta Homlok, András Kelemen, Éva Koczog, Tamás Pálfi, Erzsébet Takács

International Organizing Committee: Güneri Akovali {Turkey), Krzysztof Bobrowski {Poland), Andrzej Chmielewski {Poland), Tibor Czvikovszky {Hungary), Piergiorgio Fuochi {Italy), Mohammad Haj i-Saeid {IAEA), Attila Horváth {Hungary), István Kiss {Hungary), Arne Miller {Denmark), Hamid Mirzadeh {Iran), Dusan Razem {Croatia), Sunil Sabharwal {India), Ágnes Sáfrány {IAEA), Mohamad Al-Sheikhly {USA), Eduardo Smolko {Argentina)

International Scientific Committee: Salvatore S. Emmi {Italy), József Farkas {Hungary), Nikola Getoff {Austria), Nicholas Green {UK), Olgun Güven {Turkey), El-Sayed Al-Hegazy {Egypt), Zoltán Homonnay {Hungary), David Hill {Australia), Mehran Mostafavi {France), Joseph Rabani {Israel), Franjo Ranogajec {Croatia), Janusz Rosiak {Poland), Christina Trautmann {Germany), Attila Vértes {Hungary), Árpád Vincze {Hungary) SCIENTIFIC PROGRAM

SATURDAY, August 27

14:00- 19:00 Registration

19:00 - 21:00 WELCOME DINNER Opening greetings: F. Novák, Major of Zalakaros L. Wojnárovits, General Symposium Chair

SUNDAY, August 28

09:00 - 09:20 Opening R. Schiller

Fundamental Processes in Radiation Chemistry I Chair: R. Schiller Co-chair: E. Illés

09:20- 10:00 Invited lecture J. LaVerne and A. Baidak TRACK EFFECTS IN THE RADIOLYSIS OF AROMATIC LIQUIDS

10:0 0 - 10:20 M. Taauchi. K. Iwamatsu, Y. Sugo, S. Kurashima, M. Yamaguchi and Y. Katsumura PULSE RADIOLYSIS OF WATER BY ENERGETIC HEAVY ION

10:20-10:40 Y. Yoshida. J. Yang, T. Kondoh, K. Norizawa, K. Kan, T. Kozawa, T. Toigawa, A. Ogata and S. Tagawa FEMTOSECOND PULSE RADIOLYSIS SYSTEM ON PRIMARY PROCESS OF RADIATION CHEMISTRY

10:40-11:00 COFFEE BREAK

Fundamental Processes in Radiation Chemistry II Chair: S.S. Emmi Co-chair: T. Csay

11:00 — 11:40 Invited lecture A. Dombi SIMILARITIES AND DIFFERENCES IN THE FREE RADICAL GENERATION BY DIFFERENT IRRADIATION METHODS 11:40 12:00 R. Schiller THEORETICAL INTERPRETATION OF THE TEMPERATURE DEPENDENCE OF HYDRATED ELECTRON YIELDS IN LIQUID AND SUPERCRITICAL WATER

12:00 12:20 V.I. Feldman. E.V. Saenko, D.N. Laikov and I.A. Baranova REACTIONS OF EXCESS ELECTRONS WITH ORGANIC MOLECULES IN GLASSY MATRICES: MEDIUM EFFECT ON STABILIZATION OF RADICAL ANIONS

12:30 14:00 LUNCH BREAK

Radiation Chemistry of Biological Systems Chair: A. Faucitano Co-chair: L. Trandafir

14:00 14:40 Invited lecture S. Goldstein SUPEROXIDE RADICALS MEDIATE HEPTATOXICITY INDUCED BY THE HEAT SHOCK PROTEIN 90 INHIBITORS BENZOQUINONE ANSAMYCINS

14:40 -15:00 H. Durchschlae. C. Seidl and K-J. Tiefenbach DARWIN’S LEFT HAND: ANALYSIS OF CHIROPTICAL PROPERTIES OF UNIRRADIATED AND IRRADIATED L- AND D- AMINO ACIDS

15:00 -15:20 D. Dondi. A. Buttafava, A. Faucitano, R. Cherubini, V. De Nadal and S. Gerardi THE SOLID STATE RADIOLYSIS OF THE H20/DM S0 BINARY SYSTEM: THE ORIGINE OF THE RADIOBIOLOGICAL DAMAGE OF CELLS IN CRYOSTATIC CONDITIONS

15:20 15:40 COFFEE BREAK

Environmental Protection Chair: A. Chmielewski Co-chair: A. Lopes Antonio

15:40 -16:20 Invited lecture B. Han. S-M. Kim and W. Kang ELECTRON BEAM WASTEWATER TREATMENT WITH MOBILE ELECTRON ACCELERATOR

16:20 -17:00 Invited lecture M. Chaychian, J. Silverman and M. Al-Sheikhly ON THE MECHANISM OF DECHLORINATION OF POLYCHLORINATED BIPHENYLS (PCBs) INDUCED BY ELECTRON BEAM IRRADIATION IN AQUEOUS AND AQUEOUS MICELLAR SOLUTIONS, TRANSFORMER OIL AND SEDIMENT

17:00 - 17:20 E. Illés. E. Takács, A. Dombi, K. Gajda-Schrantz, K. Gonter and L. Wojnárovits RADIATION INDUCED DEGRADATION OF KETOPROFEN IN DILUTE AQUEOUS SOLUTION M. Virgolici, P. Bugheanu, I.R. Stanculescu. A.V. Medvedovici, M.M. Manea, C.D. Negut, M. Cutrubinis, I.V. Moise and C.C. Ponta DECOMPOSITION OF ORGANOCHLORINE INSECTICIDES FROM WASTEWATER BY GAMMA IRRADIATION

S.A. Hashim. C.S. Wong, M.R. Abas and K.Z.Hj Dahlan DIESEL EMISSION REMEDIATION USING ELECTRON BEAM

A.G. Chmielewski, A. Pawelec, J. Licli, S. Witman, Y. Sun and Z. Zimek PLASMA PROCESSES INCLUDING ELECTRON BEAM FOR OFF- GASES PURIFICATION

DINNER MONDAY, A ugust 29

Radiation Chemistry of Macromolecular Systems I Chair: 0 . Güven Co-chair: M. Akbulut

08:20 - 09:00 Invited lecture D. Khandal, P-Y. Mikus, P. Dole, C. Bliard, S. Baumberger and X. Coqueret TAILORING THE STRUCTURE AND PROPERTIES OF AMORPHOUS STARCH BY BLENDING AND EB-RADIATION PROCESSING

09:00 - 09:20 G. Ranoux and X. Coqueret THERMO-MECHANICAL PROPERTIES AND STRUCTURAL FEATURES OF EPOXY RESINS CURED BY ELECTRON BEAM RADIATION

09:20 - 09:40 T. Jurkin and I. Pucic GAMMA IRRADIATION OF SOLID, MOLTEN AND DISSOLVED POLYETHYLENE OXIDE) AND ITS NANOCOMPOSITES

09:40 - 10:00 L. Dumas. S. Rouif, D. Portinha and E. Fleury CROSSLINKING OF VDF-BASED POLYMERS BY y-RADIATION: IMPROVEMENT OF NETWORK DENSITY

10:00 - 10:20 A.B.C. Geraldo. E. Moura, E.S.M. Somessari, C.G. Silveira, H.A. Paes, C.A. Souza, W. Fernandes and J.E. Manzoli EFFECTS OF SOLVENT POLARITY ON MUTUAL POLYPROPYLENE GRAFTING BY ELECTRON BEAM IRRADIATION

10:20 - 10:40 COFFEE BREAK

Radiation Chemistry of Macromolecular Systems II Chair: F. Ranogajec Co-chair: I. Dzeba

10:40 - 11:20 Special lecture N. Bartoszek, S. Kadlubowski, J.M. Rosiak and P. Ulanski DETERMINATION OF PROPAGATION RATE CONSTANTS IN RADICAL POLYMERIZATION BY ELECTRON PULSE POLYMERIZATION - SIZE EXCLUSION CHROMATOGRAPHY

11:20 - 11:40 M.H. Casimiro. A.G. Silva, J.V. Pinto, A.M. Ramos, J. Vital and L.M. Ferreira CATALITIC POLY(VINYL ALCOHOL) FUNCTIONALIZED MEMBRANES OBTAINED BY GAMMA IRRADIATION

11:40-12:00 L.I.Sanli and S.A. Gürsel PROTON-EXCHANGE MEMBRANES FOR HIGH TEMPERATURE FUEL CELLS BY RADIATION-INDUCED GRAFTING

12:00 - 12:20 L.M. Ferreira. J.P. Leal, P.A. Rodrigues, L.C. Alves and A.N. Falcao CHARACTERIZATION OF PE-g-HEMA FILMS PREPARED BY GAMMA IRRADIATION THROUGH NUCLEAR MICROPROBE TECHNIQUES 13: 00 - 14:30 LUNCH BREAK

Radiation Chemistry of Macromolecular Systems III Chair: T. Czvikovszky Co-chair: B. Yarar

14:30-15:10 Invited lecture P.I. Pavlova-Schmitz, J.A. LaVerne and S.M. Pimblott PRODUCTION AND POST IRRADIATION RELEASE OF HCL AND H2 IN THE RADIOLYSIS OF PVC

15:10-15:30 M. Copuroglu and M. Sen ULTRAVIOLET RADIATION CURING OF AN ORGANICALLY MODIFIED SILICATE-BASED MATERIAL SYSTEM WITH EPOXY FUNCTIONALITY AND THE ROLE OF TITANIUM

15:30- 15:50 M.A.G. Bardi and L.D.B. Machado ACCOMPANYING OF PARAMETERS OF COLOR, BRIGHTNESS AND HARDNESS ON POLYMERIC FILMS COATED WITH PIGMENTED INKS CURED BY DIFFERENT RADIATION DOSES OF ULTRAVIOLET LIGHT

15:50 - 16:10 N. Fortin, S. Rouif, D. Portinha and E. Fleury y-RAY INDUCED GRAFTING POLYMERIZATION FROM A PA-66 REINFORCED PVDF MICROPOROUS ORGANIC MEMBRANE: ARE BOTH POLYMERS CHEMICALLY MODIFIED?

16:10- 16:30 COFFEE BREAK

Radiation Chemistry of Macromolecular Systems IV Chair: P. Ulanski Co-chair: R. Homlok

16:30 - 16:50 W. Liu, M. Wang, Z. Xing and G. Wu RADIATION INDUCED CROSSLINKING OF POLYACRYLONITRILE FIBER: AN ESR STUDY

16:50 - 17:10 J.J.H. Lancastre. N. Fernandes, F.M.A. Margaca, I.M. Miranda Salvado, L.M. Ferreira, M.H. Casimiro and M.C. Corvo STUDY OF PDMS CONFORMATION IN PDMS-BASED HYBRID MATERIALS PREPARED BY GAMMA IRRADIATION

17:10- 17:30 H.P. Ferreira. D.F. Parra and A.B. Lugao RADIATION-INDUCED GRAFTING OF STYRENE ONTO POLY(VINYLIDENE FLUORIDE) FILM BY SIMULTANEOUS METHOD WITH TWO DIFFERENT SOLVENTS

19:00-20:30 DINNER TUESDAY, August 30

Dosimetry and Process Control Chair: A. Miller Co-chair: M. Saracino

08:20 - 09:00 Invited lecture A. Miller and J. Helt-Hansen CHALLENGES IN VALIDATING RADIATION STERILIZATION WITH LOW ENERGY ELECTRON IRRADIATION

09:00 - 09:20 K. Farah. A. Kovács, A. Mejri and F. Hosni THE EFFECT OF TIME AND DOSE FRACTIONATION ON THE RESPONSE OF HARWELL GAMMACHROME YR PMMA DOSIMETERS

09:20 - 09:40 D. Mesterházv. M. Osvay, A. Kelemen and A. Kovács ACCIDENTAL AND RETROSPECTIVE DOSIMETRY USING TL METHOD

09:40 - 10:00 M. Ignatovich and A. Kelemen DOPED LITHIUM TETRABORATE AS ADVANCED PHOTOLUMINESCENT AND THERMOLUMINESCENT MATERIALS

10:00 - 10:20 O. Túrák. M. Osvay and L. Ballay MEDICAL DOSIMETRY IN HUNGARY

10:20 - 10:30 COFFEE BREAK

10:30- 11:30 POSTER SESSION Introduction to the posters Chair: B. Katusin-Razem Co-chair: D. Mesterházy Reviewers: O. Güven, P.G. Fuochi, Á. Sáfrány and C. Dispenza

11:30 - 12:30 LUNCH BREAK

12:30 - 24:00 CONFERENCE EXCURSION DISCOVER THE NATURE AND WILDLIFE DISCOVER HUNGARIAN WINE - WINE TASTING CONFERENCE DINNER WEDNESDAY, August 31

Radiation Chemistry of Nanoscale Systems I Chair: M. Al-Sheikhly Co-chair: D. Isik

08:20 - 09:00 Invited lecture M. Haii-Saeid. Á. Sáfrány, M.H.de O. Sampa and N. Ramamoorthy RADIATION-ENGINEERED NANOMATERIALS: THE ROLE OF THE IAEA IN COORDINATING RESEARCH

09:00 - 09:40 Invited lecture C. Dispenza RADIATION-ENGINEERED MULTI-FUNCTIONAL NANOGELS AS NANOSCALE BUILDING BLOCKS OF USEFUL BIOMEDICAL DEVICES

09:40 - 10:00 D.K. Smietanko-Chmielewska and A.G. Chmielewski APPLICATION OF IONIZING RADIATION FOR METAL NANOCLUSTERS SYNTHESIS

10:00- 10:20 B. Yarar and O. Giiven LAYER BY LAYER ASSEMBLY OF POLYANILINE/CHLORINATED POLYMER FILMS AND THEIR RESPONSE TO RADIATION

10:20 - 10:40 COFFEE BREAK

Radiation Chemistry of Nanoscale Systems II Chair: A. Lugao Co-chair: H.P. Ferreira

10:40- 11:20 Invited lecture M. Solouk, H. Mirzadeh and A.M. Seifalian PLASMA SURFACE MODIFICATION OF POSS-PCU NANOCOMPOSITE TO IMPROVE BLOOD COMPATIBILITY

11:20 - 11:40 S. Le Caer. N. Brodie-Linder, C. Alba-Simionesco, M. Shahdo Alam, C. Chatelain, F. Brunet, T. Charpentier, D. Durand, V. Dauvois and J.P. Renault EFFECT OF THE NATURE OF THE SURFACE ON THE REACTIVITY OF NANOPOROUS SILICA UNDER IRRADIATION

11:40- 12:00 S.D.Isik and O. Güven RADIATION SYNTHESIS OF SIZE-CONTROLLED POLY(N-VlNYL PYRROLIDONE) NANOGELS AND THEIR USE AS ANTIMICROBIAL AGENTS

12:00-12:20 E. Janata EARLY STAGES IN THE GROWTH OF SMALL SILVER CLUSTERS IN AQUEOUS SOLUTION

12:20 - 12:40 V. Cuba. T. Pavel kova, J. Bárta, J. Indrei, T. Gbur, M. Pospisil, V. Múcka, Z.Docekalova, A. Zavadilová and M. Vlk PREPARATION OF INORGANIC CRYSTALLINE COMPOUNDS INDUCED BY IONIZING, UV AND LASER RADIATION 12:40-13:00 M.J.A. Oliveira, D. F. Parra. V.S. Amato and A.B. Lugáo HYBRID HYDROGELS PRODUCED BY IONIZING RADIATION TECHNIQUE FOR DRUG DELIVERY

13:00-14:30 LUNCH BREAK

Radiolysis of Inorganic and Organic Systems Chair: V.I. Feldman Co-chair: N. Grimaldi

14:30-14:50 Y. Du, S. Goldstein and J. Rabani THE CATALYTIC EFFECTS OF COPPER IONS ON PHOTO­ OXIDATION IN TI02 SUSPENSIONS: THE ROLE OF SUPEROXIDE RADICALS

14:50-15:10 S.S. Emmi, S. Caminati, B. Esposito and M. Saracino THE OH YIELD IN THE RADIOLYSIS OF AN AQUEOUS/H2Oz SYSTEM

15:10-15:30 R-M. Musat. A.R. Cook, J-P. Renault and R.A. Crowell THE RADIATION CHEMISTRY OF NANO-CONFINED WATER

15:30-15:50 A.V. Kobzarenko. F.F. Sukhov, A.Y. Orlov, G.V. Kovalev, I.A. Baranova and V.I. Feldman EFFECT OF MOLECULAR STRUCTURE ON FRAGMENTATION OF ISOLATED ORGANIC MOLECULES IN SOLID RARE GAS MATRICES

15:50-16:10 COFFEE BREAK

16:10-18:30 Poster Session (continued) Visit of posters

19:00-20:30 DINNER THURSDAY, SEPTEMBER 1

Food Irradiation and Cultural Heritage Conservation Chair: P.G. Fuochi Co-chair: K. Farah

09:00 - 09:20 A. Alberti, A.E. Chiaravalle, P.G. Fuochi. D. Macciantelli, M. Mangiacotti and G. Marchesani IRRADIATED SEASHELLS: USE OF EPR SPECTROSCOPY FOR IDENTIFICATION AND DOSIMETRY

09:20 - 09:40 M. Mangiacotti. G. Marchesani, F. Floridi, G. Siragusa, A. Alberti, P.G. Fuochi, L.M. Chiesa and A.E. Chiaravalle IDENTIFICATION AND DOSE EVALUATION OF IRRADIATED BEEF CONTAINING BONES

09:40 -10:00 M.R.R. Oliveira, J.M.G. Mandarino and N.L. del Mastro RADIATION INDUCED ELECTRON PARAMAGNETIC RESONANCE SIGNAL AND SOYBEAN ISOFLAVONES CONTENT

10:00 -10:20 M. Cutrubinis, V. Moise. D. Negut, R. Georgescu, R. Suvaila, M. Virgolici and M. Manea FREE RADICALS INDUCED IN ARCHIVE PAPER BY IRRADIATION

10:20 -10:40 COFFEE BREAK

10:40 -11:10 Closing remarks J. Rabani and D. Isik

11:30-13:00 FAREWELL LUNCH

POSTER SESSION

Chair: B. Katusin-Razem Co-chair: D. Mesterházy

TUESDAY, August 30 10:30 11:30

WEDNESDAY, August 31 16:10 18:30 Fundamental Processes in Radiation Chemistry

POl I. Dzeba and B. Mihaljevic REACTION KINETICS OF RESVERATROL WITH THIYL AND ALKOXYL RADICALS

P02 C. Postolache. R. Georgescu, C. Tuta and Gh. Bubueanu EVALUATION OF PRIMARY INTERNAL SELF-RADIOLYTICAL EFFECT IN TRITIUM LABELLED COMPOUNDS USING ESR SPECTROMETRY

Radiation Chemistry of Biological Systems

P03 M. Constantin. M. Manea and I. Ardelean STUDY REGARDING MAGNETOSPIRILLUM GRIPHYSWALDENSES BACTERIA BIOCHEMYCAL CHANGES USING FTIR AND RAMAN SPECTROSCOPY

P04 M. Dumitrascu. V. Meltzer, E. Sima, M. Vírgolici, M. G. Albu, R. Minea, M. Manea, V. I. Moise and C. Vancea CHARACTERIZATION OF ELECTRON BEAM IRRADIATED COLLAGEN- POLYVINYLPYRROLIDONE (PVP) AND COLLAGEN-DEXTRAN (DEX) BLENDS

Radiation Chemistry of Macromolecular Systems

P05 M. Akbulut and O. Giiven DEVELOPMENT OF MOLECULARLY IMPRINTED HEMA-BASED COPOLYMERIC SYSTEMS FOR GLUCOSE RECOGNITION

P06 B. Beiler. M. Veres, L. Himics, M. Koós and Á. Sáfrány RAMAN SPECTROSCOPIC STUDY ON POROUS POLYMER MONOLITHS PREPARED BY RADIATION INITIATED POLYMERIZATION

P07 Y. Buchmüller. G. G. Scherer, A. Wokaun and L. Gubler INTRODUCTION OF FUNCTIONALIZABLE GROUPS VIA RADIATION GRAFTING INTO POLYMER ELECTROLYTE MEMBRANES FOR FUEL CELLS

P08 G. Celik, M. Barsbay and O. Giiven RADIATION INDUCED, RAFT MEDIATED GRAFTING OF STYRENE ONTO POLY(ETHYLENE-/1£ r-TETRAFLUOROETHYLENE) (ETFE)

P09 V. Fugaru, C Postolache, C. Tuta and Gh. Bubueanu RADIOINDUCED ACRYLIC ACID GRAFTING ONTO EXTRUDED POLYSTIRENE SURFACE

PIO C. Dispenza, N. Grimaldi. M-A. Sabatino, D. Bulone, D. Giacomazza, G. Przybytniak, S. Todaro, S. Alessi and G. Spadaro STUDIES OF NETWORK STRUCTURE AND DYNAMICS OF E-BEAM CROSSLINKED PVPs: FROM MACRO TO NANO

P ll Ren Cai, Bo Deng, Yang Yu, Haiqing Jiang and Jineve Li RADIATION INDUCED GRAFT POLYMERIZATION OF A FLUORINATED ACRYLATE ONTO FABRICS

P12 L. Mészáros. T. Bárány and T. Czvikovszky EB-PROMOTED RECYCLING OF WASTE TIRE RUBBER WITH POLYOLEFINS P13 D. Milicevic. D. Milivojevic and E. Suljovrujic THE INFLUENCE OF THE INITIAL PREPARATION AND CRY ST ALLINIT Y ON THE FREE RADICAL EVOLUTION IN GAMMA IRRADIATED POLY(L-LACTIDE)

P14 D.F. Parra. G. Fontana, P.L. Forster, L.G. Marchini and A.B. Lugao GRAFITING ON LUMINESCENT POLYMETHYLMETACRYLATE TO IMPROVEMENT OF LUMINESCENCE

P15 Z. Jelcic and F. Ranogaiec RADIATION MODIFIED HIGH IMPACT POLYSTYRENE (PS-HI)

P16 S.R. Scagliusi. E.L.C. Cardoso and A.B. Lugao EFFECT OF GAMMA RADIATION ON CHLOROBUTYL RUBBER VULCANIZED BY THREE DIFFERENT CROSSLINKING SYSTEMS

P17 B. Secerov. S. Galovic, S. Trifunovic, D. Milicevic and E. Suljovrujic STUDY OF GAMMA IRRADIATED POLYETHYLENES BY TEMPERATURE MODULATED DIFFERENTIAL SCANNING CALORIMETRY

P18 M. Sen and H. Hayrabolulu RADIATION SYNTHESIS AND CHARACTERIZATION OF NETWORK STRUCTURE OF NATURAL/SYNTHETIC DOUBLE-NETWORK SUPERABSORBENT POLYMERS

P19 G. Szebénvi. G. Romhány, B. Vajna and T. Czvikovszky EB TREATMENT OF CARBON NANOTUBE-REINFORCED POLYMER COMPOSITES

P20 E. Takács. L. Wojnárovits, T. Fekete and J. Borsa IMPROVEMENT OF PESTICIDE ADSORPTION CAPACITY OF CELLULOSE FIBRE BY HIGH-ENERGY IRRADIATION-INITIATED GRAFTING OF GLYCIDYL METHACRYLATE

P21 Hongjuan Ma, Side Yao, Jingye Li and Min Wang PRE-IRRADIATION INDUCED PRAPARATION OF AMINE-TYPE ADSORBENTS WITH EMULSION GRAFT POLYMERIZATION OF GLYCIDYL METHACRYLATE ON PE NON­ WOVEN FABRIC

P22 Y. Zhang, L. Xu, L. Zhao, J. Peng, J. Li and M. Zhai RADIATION GRAFTING OF STYRENE ONTO CELLULOSE MICROSPERES AND SUBSEQUENT ACYLATION/AMINATION FOR APPLICATION IN WASTEWATER TREATMENT

P23 Zhou Chengfei. Cao Wei, Guo Jianmei, Zhai Tong and Zeng Xinmiao EFFECTS OF y-IRRADIATION ON CROSSLINKING OF PUI/OVS NANO-COMPOSITE FOAM

P24 Z. Zimek. G. Przybytniak and A. Nowicki OPTIMIZATION OF ELECTRON BEAM CROSSLINKING OF WIRE AND CABLE INSULATION

Dosimetry and Process Control

P25 M. Ignatovvch. M. Fazoli and A. Kelemen SPECTRALLY RESOLVED THERMOLUMINESCENCE OF Cu-Ag AND Mn DOPED LTB SINGLE CRYSTALS AND GLASSES

P26 A. Kelemen. D. Mesterházy, M. Ignatovych and V. Holovey THERMOLUMINESCENCE CHARACTERISATION OF NEWLY DEVELOPED Cu-DOPED LTB MATERIALS Radiation Chemistry of Nanoscale Systems

P27 A. Gopalan. K.R. Ko, Se-Hee Lee S. Komathi, M. Veres and Kwang-Pill Lee RADIATION INDUCED PREPARATION OF NEW MULTIFUNCTIONAL NANOBIOWEBS

P28 S.L. Soto Espinoza, V. Risso, E. Pawlak, E.E. Smolko and M. Grasselli RADIATION SYNTHESIS OF SEROALBUMIN NANOPARTICLES

P29 Kwang-Pill Lee. Se-Hee Lee S. Komathi and A. Gopalan PREPARATION OF CO/PD ALLOY PARTICLES DISPERSED MULTIWALLED CARBON NANOTUBE SUPPORTED NANOCATALYSTS VIA GAMMA IRRADIATION

P30 I. Pucic and T. Jurkin ASSESSMENT OF y-IRRADIATED POLY (ETHYLENE OXIDE) BASED HYDROGELS AND NANOCOMPOSITES

P31 E. Suliovruiic. T. Vukasinovic Milic and M. Micic FABRICATION OF SILVER NANOPARTICLES IN POLY(2-HYDROXYETHYL METHACRYLATE/ITACONIC ACID) HYDROGEL NETWORKS BY GAMMA IRRADIATION

Radiolysis of Inorganic and Organic Systems

P32 D. Abbasova EPR ANALYSIS OF SURAKHANY OIL ASPHALTENES

P33 G. Bubueanu. C Postolache and C. Tuta BEHAVIOUR OF FLUOROPOLYMERS IN PRESENCE OF TRITIATED WATER

P34 D. Dondi, A. Buttafava, A. Zeffiro, S. Bracco, P. Sozzani and A. Faucitano REACTION MECHANISMS IN y IRRADIATED HIGH SURFACE SILICA -ELASTOMER SYSTEMS

P35 T. Kondoh. J. Yang, K. Norizawa, K. Kan, T. Kozawa, A. Ogata, S. Tagawa and Y. Yoshida TIME-DEPENDENT BEHAVIOR OF ELECTRON IN N-DODECANE STUDIED BY FEMTOSECOND PULSE RADIOLYSIS

P36 S.V. Nesterov. O.A. Zakurdaeva and V.I. Feldman LOW TEMPERATURE RADIOLYSIS OF DICYCLOHEXANOCROWN ETHERS AND RELATED COMPOSITIONS

P37 V. Anan’ev and V. Pak PARAMAGNETIC CENTERS FORMATION UNDER RADIOLYSIS OF CRYSTALLINE RbN03 AND CsN03

P38 A.V. Ponomarev. E.M. Holodkova and B.G. Ershov ELECTRON-BEAM SYNTHESIS OF FUEL IN THE GAS PHASE

Food Irradiation and Cultural Heritage Conservation

P39 D. Abbasova APPLICATION OF XRF FOR CHARACTERIZATION OF ICON OF XVIII CENTURY P40 A. Adu-Gvamfi. F.B. Apea Bah, T. Mahami, J. Agyei-Amposah and C. Owulah IMPROVING THE MICROBIOLOGICAL QUALITY OF DRIED MORINGA LEAF PRODUCTS THROUGH GAMMA IRRADIATION

P41 J.C.M. Barreira, A.L. Antonio. Á. Fernandes, T. Günaydi, H. Alkan, A. Bento, M.L. Botelho and I.C.F.R. Ferreira CHEMOMETRIC CHARACTERIZATION OF GAMMA IRRADIATED CHESTNUTS FROM TURKEY

P42 E. Bortolin. S. Della Monaca, R. Gargiulo and C. Boniglia LIMITS OF TL PROTOCOL EN 1788 APPLIED TO HERBS AND SPICES: IDENTIFICATION OF BLENDS CONTAINING IRRADIATED COMPONENTS

P43 M.M. Manea, C.D. Negut, O.H. Barbu, M. Virgolici, I. Stanculescu. M. Cutrubinis, I.V. Moise and C.C. Ponta COMPARATIVE FT-RAMAN, FT-IR AND COLOUR SHIFTS SPECTROSCOPIC EVALUATION OF GAMMA IRRADIATED EXPERIMENTAL MODELS OF OIL PAINTINGS

P44 G. Marchesani. M. Mangiacotti, A. Alberti, P. Fuochi, L.M. Chiesa and A.E. Chiaravalle APPLICATION OF PHOTOSTIMULATED LUMINESCENCE (PSL) TO DETECT IRRADIATED MOLLUSCS

Environmental Protection

P45 M. Chamam. Cs.M. Földváry, A.M. Hosseini, A. Tungler, E. Takács and L. Wojnárovits REMEDIATION OF WASTEWATERS BY HIGH ENERGY IRRADIATION PROCESS

P46 T. Csav. G. Rácz, E. Takács and L. Wojnárovits RADIATION DEGRADATION OF PHARMACEUTICAL RESIDUES IN WATER: CHLORAMPHENICOL

P47 K. Gonter, E. Takács and L. Wojnárovits HIGH-ENERGY IONIZING RADIATION INITIATED DECOMPOSITION OF ACETOVANILLONE

P48 R. Homlok. E. Takács and L. Wojnárovits RADIOLYTIC DEGRADATION OF DICLOFENAC AND 2,6-DICHLOROANILINE IN AQUEOUS IN SOLUTION

P49 V.V. Morgunov. O.L. Fainchtein and A.M. Shkilko NUMERICAL SIMULATION OF FLUE GAS PURIFICATION FROM NO,, S02 BY ELECTRON BEAM

P50 T. Pálfi. R. Homlok, T. Csay, L. Wojnárovits and E. Takács MECHANISM OF AZO DYE DEGRADATION BY IONIZING RADIATION: DEGRADATION OF SULFANILIC ACID AZOCHROMOTROP AND ITS PARENT COMPOUNDS IN AQUEOUS SOLUTION

P51 L. Szabó. T. Tóth, R. Homlok, E. Takács and L. Wojnárovits RADIOL YTIC DEGRADATION OF PARACETAMOL IN DILUTE AQUEOUS SOLUTION

P52 A. Kimura, M. Osawa and M. Taguchi DECOMPOSITION OF PERSISTENT PHARMACEUTICALS IN WASTEWATER BY IONIZING RADIATION Radiation Sterilization

P53 K. Kavkler, A. Demsar, B. Katusin-Razem, I. Pucic, B. Mihaljevic, P. Zalar and N. Gunde-Cimerman GAMMMA IRRADIATION FOR THE PREVENTION OF BIODETERIORATION OF HISTORIC AND MODERN TEXTILES

P54 L. Trandafir. M. Ene, M. Alexandru, M. Constantin, A. Ionifá, F. Zorilá and V. Moise PRACTICAL ASPECTS DURING STERILIZATION VALIDATION FOR MEDICAL DEVICES AT IRASM MICROBIOLOGICAL LABORATORY

P55 F. Zorila. L. Trandafir, M. Alexandru, S. Nisipeanu, M. Haiducu, I.V. Moise and R. Georgescu MICROBIOLOGICAL ASPECTS OF THE IRRADIATION TREATMENTS FOR PRESERVATION OF ARCHIVES

Biomedical Materials

P56 J. Krstic, J. Spasojevic, A. Krklies and Z. Kacarevic-Popovic SWELLING KINETICS AND ANTIMICROBIAL ACTIVITY OF RADIOLYTICALLY SYNTHESIZED NANO-Ag/PVA HYDROGELS

P57 M. Micic and E. Suljovrujic RADIATION-INDUCED SYNTHESIS AND SWELLING PROPERTIES OF P(2- HYDROXYETHYL METHACRYLATE-CO-ITACONIC ACID-CO-OLIGO(ETHYLENE GLYCOL) ACRYLATE) COPOLYMERIC HYDROGELS

P58 C. Dispenza, M.-A Sabatino. A. Niconov, D. Chmieliewska and G. Spadaro E-BEAM CROSSLINKED, BIOCOMPATIBLE FUNCTIONAL HYDROGELS INCORPORATING POLY ANILINE NANOPARTICLES

P59 W. L. Oliani, D.F. Parra. H.G. Riella, L.F.C.P.Lima, A.B. Lugao POLYPROPYLENE NANOGEL “MYTH OR REALITY” ORAL PRESENTATIONS

TRACK EFFECTS IN THE RADIOLYSIS OF AROMATIC LIQUIDS

J.A. LaVerne and A. Baidak Radiation Laboratory, University of Notre Dame Notre Dame, Indiana, USA 46556

The radiolysis of simple aromatic liquids - benzene, pyridine, toluene and aniline - has been examined using gamma and heavy ion radiolysis techniques. Yields of molecular hydrogen and of “dimers” (biphenyl, bibenzyl, and dipyridyl, diphenylamine for benzene, toluene, pyridine, and aniline, respectively) have been compared as a function of the track structure. These products are the most abundant in each of these compounds and they give a good representation of the main pathways for the radiolytic decomposition of each medium. Aromatic liquids are generally thought to be radiation inert because of the low yields of product molecules. However, the yields of molecular hydrogen are shown to increase significantly with increasing linear energy transfer and have limiting values that appear to be nearly the same for all of the media. Such a response strongly suggests that the mechanism is similar for all of these compounds. Hydrogen production at high linear energy transfer is thought to be due to an increased probability of annihilation reactions to produce high energy excited states that decompose to give molecular hydrogen. On the other hand, “dimer” yields from the different aromatic liquids have a variety of dependences on track structure that reflect the many possible pathways to their production. Reactions of radicals and high energy excited states lead to “dimer” formation in these systems. PULSE RADIOLYSIS OF WATER BY ENERGETIC HEAVY ION

M. Taguchil), K. Iwamatsu1,2), Y. Sugo]), S. Kurashima1*, M. Yamaguchi3' and Y. Katsumura2) ’'japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma 370-1292 Japan 2)The University of Tokyo,7-3-1 Hongo, Bunkyo, Tokyo 113-8656, Japan 3)Japan Atomic Energy Agency, 4-33 Muramatsu, Tokai, Naka, Ibaraki 319-1194 Japan

Water radiolysis is a fundamental process governing radiation effects in various aspects. Degree of water molecule decomposition depends on the type and LET (Linear Energy Transfer) value of radiations. However, the degradation of water molecules by a- particle has not been clearly understood. In this study, we aimed to clarify the reaction behavior of the groundwater induced by of a-particles from high-level radioactive waste (HLW) in the geological disposal environment. a-Radiolysis of water was investigated by use of high energy helium ions accelerated by the AVF cyclotron in TIARA facility, JAEA/Takasaki. The pulsed He ion irradiation technique and online time resolved absorbance measurement system was investigated for direct observation of chemical reactions of transient species produced by irradiations [1]. Hydroxyl (OH) radical is the most important species for reactions in aqueous samples because of its high reactivity and formation yield. NaCl was selected as a probe reagent for the OH radical produced by the irradiation with He ion, and dissolved in pure water. Because 50 MeV He ion has the penetration range at 1.5 mm in water, the sample cell has the thickness of 2 mm, and 50 pm glass windows on the top and bottom for preventing energy loss of the incident ions and measuring the absorbance. The transient absorbance was recorded for the aqueous NaCl solutions using semiconductor LASER diode at 375 nm as a probe light source. ClOH' was formed by the reaction of the OH radical with Cl\ The absorbance of ClOH' increased within the irradiation pulse width, and then decreased gradually. The formation yield of ClOH' which was estimated from the peak absorbance value, increased with the solute concentration. Precise analyses of chemical reactions occurred in track will be discussed at the presentation. This study is a part of the project on geological disposal funded by the Ministry of Economy, Trade and Industry, Japan, and a grant from the Ministry of Education, Culture, Sport, Science and Technology of Japan.

Reference

[1] M. Taguchi, et al., Radiat. Phys. Chem., 78, 1169 (2009) FEMTOSECOND PULSE RADIOLYSIS SYSTEM ON PRIMARY PROCESS OF RADIATION CHEMISTRY

Y. Yoshida, J. Yang, T. Kondoh, K. Norizawa, K. Kan, T. Kozawa, T. Toigawa, A. Ogata and S. Tagawa The Institute of Scientific and Industrial Research, Osaka University, Japan

A femtosecond pulse radiolysis system for the absorption spectroscopy was developed by a new type of the accelerator [1], The system for the absorption spectroscopy is composed with a S-band electron linac with a laser photocathode rf gun, the pulse compression system, the optical detection system with a femtosecond laser and the synchronization system. The total time-resolution of the system is about 240 fs. The first femtosecond pulse radiolysis studies were done in water and alcohols. The formation times of pre-hydrated electron and hydrated electron were 200 fs and 540 fs, respectively, which corresponded with the reported values obtained in the laser photochemistry. Also, the formation times of pre-solvated electrons and solvated electrons in several alcohols were obtained. The formation time of pre-solvated electrons were strongly dependent on the OH-groups density, and the formation time of solvated electrons were dominated by the dielectric relaxation time. The experimental data suggested that the formation process of solvated electron in alcohols could be explained by the two states model. The geminate ion recombination process in non-polar liquid has been also studied by the femtosecond pulse radiolysis. The formation process of the cation radical was observed in n-dodecane in picosecond time-region, while the electron showed the typical geminate decay after the pulse. That was caused by the relaxation process from the excited cation radical [2, 3], The relaxation time of 7 ps in n-dodecane was obtained by analyzing the geminate process based on the diffusion theory.

References

[1] J. Yang, et al., Nucl. Instrum. Methods Phys. Res., A 556, 52 (2006) [2] T. Kondoh, et al., Radiat. Phys. Chem., 80, 286 (2011) [3] T. Kondoh, et al., submitted to Radiat. Phys. Chem. SIMILARITIES AND DIFFERENCES IN THE FREE RADICAL GENERATION BY DIFFERENT IRRADIATION METHODS

A. Dombi Institute of Material Sciences and Engineering, University of Szeged, 6720 Szeged, Tisza L.krt. 103, Hungary

The inefficiency of biological treatment methods for water and air purification has been lead to the adaption of Advanced Oxidation Processes (AOPs). The hallmarks of an AOP process is the direct or indirect chemical activation of molecular oxygen ambient temperature in presence of a medium with very low pollutant concentration and this poses numerous challenges. The main characteristic of AOPs is the free radical generation. The energy of radical generation (the oxygen activation) is usually provided by VUV irradiation, radiolysis or an electron beam. Occasionally, moderately active form of oxygen (ozone or hydrogen peroxide) is used for radical generation. One of the remarkable sections of oxygen activation is realized by indirect way, typical pattern is the heterogeneous photocatalysis. The direct chemical methods for radical generation, like the Fenton reaction, rarely occurs. During the radical generation, one of the crucial questions relates to the first step of process, the charge separation and the subsequent transfer to oxygen molecule or to the target molecule. Another aspect in AOP application is the self-propagation process where chain reactions can be enhanced by the presence of peroxy-type radicals. AOP design requires the ratio of chain step rate to radical recombination rate should be increase, where possible. The optimization of self-preservation process requires a good level of understanding of the chemical mechanism of transformations and their reaction kinetic behavior for all of contaminants. Additional influencing factors of the efficiency of AOP treatment facilities include the reactor design and construction. All of these considerations warrant considerable investigation, exploration and case studies. THEORETICAL INTERPRETATION OF THE TEMPERATURE DEPENDENCE OF HYDRATED ELECTRON YIELDS IN LIQUID AND SUPERCRITICAL WATER

R. Schiller Central Research Institute for Physics, Atomic Energy Research Institute 1525 Budapest, P.O.B. 49, Hungary

Recent results on the temperature dependent yields of hydrated electrons by Kratz et al. [Phys. Chem. Chem. Phys., 12, 12169 (2010)] were compared with an earlier theory of us [J. Chem. Phys., 92, 5527 (1990)]. The theory was based on the idea that electrons in the hydrated state are bound to their geminate positive ion and are set free by energy fluctuations. Temperature, T, static relative permittivity, and constant-volume specific heat, Cv, play here the decisive role; the combination Te] -Jc^ is the variable by which the yield can be predicted. The calculations agreed with the radiation chemical results, as discussed in terms of the material properties, reasonably well. REACTIONS OF EXCESS ELECTRONS WITH ORGANIC MOLECULES IN GLASSY MATRICES: MEDIUM EFFECT ON STABILIZATION OF RADICAL ANIONS

V.I. Feldman, E.V. Saenko, D.N. Laikov and I.A. Baranova Department of Chemistry, Moscow State University, Moscow, 119991, Russia

Attachment of excess electrons to organic molecules is one of the key primary events in radiation chemistry and radiobiology. The effect of electron scavenging by carbonyl compounds is well known for several decades. Meanwhile, most of these compounds have no significant gas-phase electron affinity (EA). Thus, the formation of radical anions in condensed phases should by often controlled by intermolecular interactions. Here we present the results of experimental and ab initio study of excess electron attachment to a series of monofunctional and bifimctional compounds upon their irradiation in low-temperature matrices with various polarity and polarizability. The electron capture was monitored by suppression of the yield of trapped electrons and formation of radical anions as revealed by EPR and optical spectroscopy. It was found that molecules with EA > 0.5 eV (e. g., diacetyl) gave rather stable radical anions, independent of the matrix used. Meanwhile, the compounds with nearly zero (or negative) EA show dramatic matrix effect. In particular, acetone and diacetonyl radical anions were not observed in hydrocarbon glasses, although the yield of trapped electron is suppressed markedly. This result may be explained by reversible electron capture. Turning to slightly more polar ether matrices leads to the matrix-induced stabilization of diacetonyl radical anion. The quantum-chemical calculations at the MP2 level provide strong support to this concept. They reveal that coordination of 4 to 6 solvent molecules may increase excess electron binding energy from nearly zero to more than 0.5 eV. An alternative is self-stabilization due to formation of dimers, which probably occurs for acetone at higher concentrations. The interplay between these effects is determined by solute concentration, intermolecular interactions and conformation (in particular, for bifimctional spcies). Preliminary results show that such consideration may be applicable to a wide class of molecules with borderline EA values, including those presenting interest for biology and molecular electronics. This work was supported by the Russian Foundation for Basic Research (grant 09-03- 00848a). SUPEROXIDE RADICALS MEDIATE HEPTATOXICITY INDUCED BY THE HEAT SHOCK PROTEIN 90 INHIBITORS BENZOQUINONE ANSAMYCINS

S. Goldstein Institute of Chemistry, the Hebrew University of Jerusalem, Jerusalem 91904, Israel

Geldanamycin (GM), a benzoquinone ansamycin antibiotic, is a natural product inhibitor of the heat shock protein 90 (Hsp90) with potent and broad anticancer properties. However, its progression to clinical trials was halted due to unacceptable levels of hepatotoxicity. Consequently, numerous less toxic analogs differing only in their 17-substituent have been synthesized including 17-AAG and the water soluble 17- DMAG (Alvespimycin), which have recently entered clinical trials. The different hepatotoxicity induced by GM and its analogs may reflect the redox active properties of the quinone moiety (Q) and possibly the extent of superoxide radical formation, which may stimulate cellular oxidative injury. Q + 0 2 0 2- + Q (1) Eq. 1 is established rapidly, and its actual position is governed by Ej(Q/Q' ) and -£’7(0 2 /0 2 ’"") and the relative concentrations of Q and O2. Using pulse radiolysis, £ 7(Q/Q") f°r 17-DMAG has been determined vs. 0 2,1,4-naphthoquinone or menadione to be -194 ± 6 mV, which is somewhat lower than EjiO ^O i") = -180 mV (1 M O2). Eq. 1 is well to the left in the case of 1,4-benzoquinone and substitution into the ring by electron-donating or -withdrawing groups reduces or increases, respectively, E7(Q/Q'~) in a predictable manner, e.g. linearly related to the Hammett sigma value of the substituents. Hence, Q/Q~) should follow the order GM < 17-AAG < 17-DMAG implying that 0 2 is more readily reduced to O2 _ by GM. It is demonstrated that Ű2 ~ can be efficiently trapped by Tempol during the reduction of GM, 17-AAG and 17-DMAG by NADPH catalyzed by NADPH-cytochrome P450 reductase, and that O2 ~ formation rate, which reflects the rate of NADPH oxidation, follows the order 17-DMAG > GM > 17-AAG. In the absence of 0 2~ scavengers, the rate of NADPH oxidation follows the order 17-DMAG > 17-AAG > GM. The order of the drug cytotoxicity toward rat primary hepatocytes, as determined by their effect on cell viability, follows the order GM > 17-AAG > 17-DMAG. The apparent discrepancy between the order of toxicity and the rate of O2 formation is discussed. DARWIN'S LEFT HAND: ANALYSIS OF CHIROPTICAL PROPERTIES OF UNIRRADIATED AND IRRADIATED L- AND D-AMINO ACIDS

H. Durchschlag, C. Seidl and K.-J. Tiefenbach Institute of Biophysics and Physical Biochemistry, University of Regensburg, Germany

Although normal chemical reactions roughly produce equal mixtures of left-handed and right-handed types, life used some specialized machinery to produce only left- handed forms of amino acids. Origin of life theories must explain how nature could produce the proper mirrored building blocks. There appear, however, to be no established reasons why left-handed amino acids should be favoured in biological systems, and the possible emergence of chiral uniqueness in living processes is still an unresolved riddle [1,2]. In a multitude of experiments, we have tested the sensitivity of all L- and D- amino acids against X-irradiation and UV light exposure, with special emphasis on any differences in degradation, (thermal) stability and ability to act as substrates. Among the techniques tested, the spectroscopic techniques (UV absorption, fluorescence, and in particular far-UV circular dichroism) turned out to be most effective, in addition to crystallisation experiments. In this context, a variety of experimental conditions (pH, gassing conditions etc.) were chosen. For analysing the data of aromatic and non- aromatic amino acids, respectively, appropriate precautions have to be taken. As a result of our investigations, indeed, several significant dissimilarities between different types of amino acids and different enantiomers were established. For example, among the aromatic representatives, L and D forms of tyrosines turned out to show a quite different behaviour, while among the non-aromatics, L and D enantiomers of asparagines and glutamines established distinctly different characteristics. Overall, under definite conditions, D-isomers tend to be more sensitive to radiation than their L- counterparts. If this experimentally observed radiosensitivity of L and D enantiomers is indeed the reason for amino acid homochirality and the 'handedness of life' has to be elucidated in future experiments on earth and in space.

References

[1] RauchfuB, H.: Chemical Evolution and the Origin of Life, Springer, Berlin (2008). [2] Meierhenrich, U.: Amino Acids and the Asymmetry of Life, Springer, Berlin (2008) THE SOLID STATE RADIOLYSIS OF THE H20/DMS0 BINARY SYSTEM: THE ORIGINE OF THE RADIOBIOLOGICAL DAMAGE OF CELLS IN CRYOSTATIC CONDITIONS

D. Dondi1*, A. Buttafava1*, A. Faucitano1*, R. Cherubini2*, V. De Nadal2) and S. Gerardi2) ^Dipartimento di Chimica -Universita’ di Pavia; V.le Taramelli 12, 27100 Pavia; 2)Laboratori Nazionali INFN di Legnaro, Padova, Italy

The cryoconservation method is based on the use of cryogenic fluids which, when mixed with water, partially protect the cells from the segregation of salts. During a long period of storage in the cryogenic state, the radiation dose from the natural background can attain a dose of 0.1 Gy in 25-50 y. which can be the source of significant mutagenic effects. The present work deals with the EPR study of the y-radiolysis at 77 K of the binary system H2O/DMSO which is the most commonly used freezing medium. The free radical yields and decay kinetics were determined for DMSO/H2O frozen mixtures of composition ranging from pure water to pure DMSO, passing through the key 10% DMSO composition. The radical vs dose yield curves were observed to pass through a maximum in correspondence of the DM SO 3 H2O hydrate. Radicals are trapped during the irradiation but are released on warming near the melting temperature; radical attack to cells structures can take place at this stage, provided that the reactants be in the same phase. The attitude of trapped radicals to interact on melting with organic substrates was tested by performing a set of experiments using the 2,2,6,6 tetramethyl piperidinyl oxyl stable radical as a spin trapping agent. An upper limit estimate of the fraction of trapped radicals potentially capable of causing radical damage on melting could thus be determined as a function of the H2O/DMSO ratio. This fraction is 14 % for H2O/DMSO (10%) mixtures. OH radicals instead were found to be non-reactive probably because are trapped in separated ice phases. EPR measurements performed on irradiated H2O/DMSO (10%) frozen samples containing 1.5xl07 cells/ml have shown that almost the totality of the trapped radicals are generated from the components of the freezing medium.

Reference

D. Dondi, A.Buttafava, A.Faucitano, R.Cherubini, V. De Nadal, S. Gerardi: EPR study of the effect of the cryoconservation state on the radiobiological damage of cells (.Proceedings EUCHEM conference on Organic Free Radicals, C. Chatgilialoglu ed., Bologna, June 2010) ELECTRON BEAM WASTEWATER TREATMENT WITH MOBILE ELECTRON ACCELERATOR

B. Han1*, S.-M. Kim1*, W. Kang1*, N. Zommer2’ and U. Sasson2) ^EB TECH Co., Ltd. 550 Yuseong-gu Yongsan-dong, Daejeon 305-500, Korea 2)PELE Technology Inc., 1590 Buckeye Drive, Milpitas CA 95035, USA

Radiation technologists have been applied for treatment of pollutants such as wastewaters, flue gas, and sewage sludge. The major advantage of radiation technology is that the reactive species are generated in-situ during the radiolysis process without addition of any chemicals. The results of practical applications have confirmed that radiation technology can be easily and effectively utilized for treating large quantities of pollutants. Due to the necessity of pilot scale test facility for continuous treatment of wastewater and gases on the spot, a mobile electron beam irradiation system mounted on a trailer has developed in EB TECH Co. Ltd. This mobile electron beam irradiation system is designed for the individual field application with self-shielded structure of steel plate and lead block which will satisfy the required safety figures of ICRP. Design parameters are limited by the allowable total weight and height of the trailer on the road which controlled by National Authorities. Therefore, the output parameter of electron beam is designed for 0.7MeV and 20kW through 600mm window. Shielding of a mobile electron accelerator has been examined by Monte Carlo technique (MCNP code). Calculations using two different versions (version 4c2 and version 5) of MCNP showed agreements within statistical uncertainties, and the highest leakage is far below the tolerable radiation dose limit. This mobile unit will be used for on-site test of liquid waste and gaseous waste in U.S. by PELE Technology Inc. and EB TECH Co. Ltd. This unit could treat up to 500m3 of liquid waste per day or 10,000 Nm3 of gases per day. -1 1 -

ON THE MECHANISM OF DECHLORINATION OF POLYCHLORINATED BIPHENYLS (PCBS) INDUCED BY ELECTRON BEAM IRRADIATION IN AQUEOUS AND AQUEOUS MICELLAR SOLUTIONS, TRANSFORMER OIL, AND SEDIMENT

M. Chaychian, J. Silverman and M. Al-Sheikhly Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742-2115, USA

The widespread release of PCBs into the environment presents a serious problem due to their persistence and toxicity. Ionizing radiation, such as gamma rays and high-energy electron beam, is remarkably effective in dechlorinating PCBs into biphenyls. The kinetics of the reductive dechlorination of PCBs in aqueous and aqueous micellar solutions and in transformer oil is being studied by pulse radiolysis and steady-state radiolysis. In aqueous micellar solutions, dichloro-, tetrachloro-, and decachlorobiphenyl congeners were solubilized in water using a commercially available non-ionic surfactant, Triton X-100, and subsequently pulse irradiated by electron accelerator using optical detection method. The reaction rate constant between dechachlorobiphenyl and aqueous electrons eaq*_, and Triton with eaq*~ in the 2 % Triton solution, were measured as 2.6 x 109 LmoI'V1 and 1.2 x 107 LmolTs’1, respectively. We have also measured in aqueous solutions, the reaction rate constant of eaq*~ with dichlorobiphenyl as 3.8 x 109 Lmol'V1. In aqueous-propanol, the reaction rate constants of eaq*~ with dichlorobiphenyl, tetrachlorobiphenyl, and dechachlorobiphenyl are 2 x 109 Lm of's'1, 3 x 109 Lm of's'1, and 7 x 109 Lmol'V1, respectively. In addition to the presence of PCBs as high-dielectric component, transformer oil contains many aromatic hydrocarbons; the most abundant being biphenyl, fluorine, and phenanthrene. Solvated electrons formed by irradiation of the oil react either with PCB to lead to dechlorination or with the aromatic hydrocarbons present in the oil to form radical anions. These species are shown to transfer an electron to chlorinated biphenyls relative rapidly, leading to dechlorination. The rate constants for several such reactions, determined in 2-propanol solutions, are in the range of 107-108 Lmof’s’1. These rapid reactions explain why PCB can be dechlorinated in oil despite the formation of biphenyl as radiolysis product that reacts rapidly with solvated electrons. Our study has shown that the oxidizing powers of ionizing radiation are of little value in the remediation of PCBs due to the high concentration of other organic species necessarily present. However, radiation-induced reductive reactions are extremely effective for PCB remediation. - 12 -

RADIATION INDUCED DEGRADATION OF KETOPROFEN IN DILUTE AQUEOUS SOLUTION

E. Illés1*, E. Takács2*, A. Dombi1*, K. Gajda-Schrantz1*, K. Gonter2* and L. Wojnárovits2* 1'institute of Material Sciences and Engineering, University of Szeged, Szeged, Hungary 2*Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

Due to the heavy medical use and the high persistence, ketoprofen, a non-steroidal anti­ inflammatory drug is regularly detected in the municipal wastewaters and the usual biological treatment facilities are not effective enough in its removal. More efficient removal can be achieved with the combination of the conventional treatment with Advanced Oxidation Processes (AOPs). These processes are based on the generation of aggressive radicals, mainly *OH radicals, as reactive attacking intermediates.

Ketoprofen

In this work the possibilities of ketoprofen elimination were investigated in dilute aqueous solutions by radiation technology. Special emphases were made on the mechanisms of degradation, intermediates and also on final products. The intermediates of degradation were studied by pulse radiolysis, for end product experiments 60Co y-irradiation facility was used. The irradiated samples were evaluated either by taking UV-Vis spectra or by HPLC with UV or MS detection. The *OH radicals react with the aromatic rings forming ketoprofen molecules hydroxylated at different positions. The eaq_ reacts with the carboxyl group forming an anion and then after protonation ketyl radical. Under photoexcitation decarboxylation from the ketyl radical is observed. In radiolytic experiments there is no decarboxylation. DECOMPOSITION OF ORGANOCHLORINE INSECTICIDES FROM WASTEWATER BY GAMMA IRRADIATION

M. Virgolici1*, P. Bugheanu2*, I.R. Stanculescu1,2*, A.V. Medvedovici3*, M.M. Manea1*, C.D. Negut1*, M. Cutrubinis’*, I.V. Moise1* and C.C. Ponta'* ^"Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), IRASM Centre of Technological Irradiations, 077125, Romania 2)University of Bucharest, Faculty of Chemistry, Department of Physical Chemistry, 030018, Romania 3)University of Bucharest, Faculty of Chemistry, Department of Analytical Chemistry, 050663, Romania

Organochlorine pesticides are a group of toxic compounds, most of them being included in the Stockholm convention list of persistent organic pollutants. They are characterized by high chemical stability and may lead to marked changes in the aquatic ecosystem via bioaccumulation and biomagnification. Gamma radiolytic degradation is thought to be a promising treatment for the decomposition of organochlorine insecticides to environmental friendlier compounds. The radiolytic study was carried out on model wastewater samples spiked with organochlorine insecticides (as lindan, dieldrin, aldrin? or DDT). To identify most convenient irradiation conditions for wastewater treatment, samples were irradiated at different doses and two dose rates: 2 kGy/h and 30 kGy/h. The dependence of organochlorine insecticides concentration of dose and dose rate was monitored with gas chromatography coupled with an electron capture detector (GC-ECD). Same samples were screened with gas chromatography coupled with mass spectrometry (GC/MS), in order to identify radiolysis products which may still be classified as persistent organic pollutants. Compound identification was performed via mass spectra deconvolution and retention index with AMDIS software and spectral matching with NIST 2005 GC/MS library. The results of the GC/MS screening will designate the target compounds for routine quantitative monitoring by GC-ECD. A molecular modelling study was developed to predict the most probable radiolysis products and it was correlated with the GC/MS results to speculate some preferential radiolysis pathways. - 14-

DIESEL EMISSION REMEDIATION USING ELECTRON BEAM

S.A. Hashim", C.S. Wong2), M.R. Abas2) and K.Z. Hj Dahlan0 1’Malaysian Nuclear Agency, Bangi, Kajang, Malaysia ^University of Malaya, Kuala Lumpur, Malaysia

An electron beam (EB) flue gas test rig was tested for the remediation of emission from diesel combustion which contained mainly nitric oxide (NO). In a separate experiment, dielectric barrier discharge reactor was used to remove nitric oxide from a simulated gas mixture. In both systems, energized electrons were used to produce radicals that reacted with the pollutants. The EB system was a laboratory scale test rig used to treat emission from a diesel run generator. At 1.0 MeV, 10 mA more than 90% NO removal from flue gases flowing at 120 Nm3/hr can be achieved. For higher removal percentage, higher beam current was required. In a related effort, a table top, two tubes DBD reactor was used to process bottled gases containing 106 ppm NO. Total removal (>99%) was achieved when the inlet gas contained only NO and N2 . The system was operated with input AC voltage of 35 kV peak to peak. The energy of the electron within the reaction space is estimated to be around 15keV. In the EB treatment system, the amount of NO2 increased at high beam current, showing that the NO was also oxidised in the process. Whereas in the DBD reactor, the amount of NO2 remained insignificant throughout the process. This leads to the conclusion that the DBD reactor is capable of producing total removal of NO. This is highly desirable as post treatment will not be necessary. - 15 -

PLASMA PROCESSES INCLUDING ELECTRON BEAM FOR OFF-GASES PURIFICATION

A.G. Chmielewski1’2’, A. Pawelec1*, J. Licki3’, S. Witman1’2*, Y. Sun1’ and Z. Zimek1* ^Institute of Nuclear Chemistry and Technology, Warsaw, Poland 2)University of Technology, Department of Chemical and Process Engineering Warsaw, Poland 3)Institute of Atomic Energy, Swierk, Poland

Non-thermal plasma technologies based on different methods of plasma generation are being applied for ozone generation for different applications, waste water and off-gases treatment. Plasmas create reactive species, in particular ions, radicals or other reactive compounds, which can decompose pollutant molecules, organic particulate matter or soot. Electron beam flue gas treatment is another plasma-based technology which has been successfully demonstrated on industrial scale coal fired power plants. High efficiency of SO2 (> 95%) and NO x(>70%) has been obtained and industrial plant applying this process has been built in Poland. The further investigations carried out all over the world have illustrated that the process can be applied for poly-aromatic hydrocarbons (PAH) destruction as well, and just recently research laboratories in the US and South Korea have reported in the feasibility of the process for mercury removal from the flue gas [1], The recent studies concern a new type of accelerators implementation in the industrial scale, application of the process in the high sulfur oil fired boilers [2] and Diesel off - gasses purification. The treatment of the flue gases with the high NOx concentration is a special challenge for the technology since the main energy consumption (and applied accelerators power) is related to this pollutant content in the processed off gases. The pulse beams and scavenger application can be a solution to reduce investment and operational costs. The further development of the technology is directly connected with high power accelerators development [3].

Acknowledgment: The R& D activities are supported by the European Regional Development Found in the frame of the project PlasTEP “Dissemination and fostering of plasma based technological innovation for environment protection in the Baltic Sea Region”.

References

[1] J.-C. Kim, K.-H. Kim, A. Armendariz, M. Al-Sheikhly, J. Environ. Eng. 136, 554 (2010) [2] A.A. Basfar, O.I.Fageeha, N. Kunnummal, A.G; Chmielewski, A. Pawelec, J. Licki, Z. Zimek, Fuel, 87, 1446 (2008) [3] Accelerators for America’s Future, US DOE, Washington, 2010, www.acceleratorsamerica.org/files/Report.pdf - 16 -

TAILORING THE STRUCTURE AND PROPERTIES OF AMORPHOUS STARCH BY BLENDING AND EB-RADIATION PROCESSING

D. Khandal1*, P.-Y. Mikus2*, P. Dole2*, C. Bliard1*, S. Baumberger3* and X. Coqueret1* !)ICMR, UMR CNRS 6229,2) FARE, UMR INRA, Université de Reims Champagne Ardenne - 51687 Reims, France 3)Institut J.-P. Bourgin, UMR 1318, AgroParisTech-INRA, 78026 Versailles, France

Starch can be used alone and in combination with other compounds to make biodegradable articles from renewable resources. Lignins and their derivatives are good candidates for limiting the water sensitivity of starch-based materials, but they exhibit poor compatibility in blends with polysaccharides. Electron beam (EB) processing is proposed as an efficient method for inducing covalent linkages between the two constituents. Compared to unirradiated starting materials, the surface and bulk properties of EB-irradiated starch - lignin blends submitted to EB irradiation showed an interesting reduction in hydrophilicity. Radiation induced grafting of lignin models onto starch was shown to impede long-term retrogradation, with limited loss of mechanical properties. The reactivity under radiation of model blends was examined by several analytical methods. Maldi-Tof mass spectrometry allowed us to propose reasonable free radical mechanisms that account for the grafting of various benzyl and cinnamyl alcohols onto maltodextrins. The presence of cinnamyl derivatives was found not only to limit degradation, but also modify the properties of the formulations (improved hydrophobicity, mechanical properties). Size exclusion chromatography and gel fraction measurements confirmed unambiguously the attachment of UV-absorbing chromophores onto the maltodextrin main chain. The combination of the obtained results demonstrates the possibility of altering in a favourable way the tensile properties of plasticized starch by applying high energy radiation to properly formulated blends including aromatic compounds like cinnamyl alcohol. - 17 -

THERMO-MECHANICAL PROPERTIES AND STRUCTURAL FEATURES OF EPOXY RESINS CURED BY ELECTRON BEAM RADIATION

G. Ranoux and X. Coqueret Université de Reims Champagne-Ardenne, CNRS UMR 6229, France Institut de Chimie Moléculaire de Reims, BP 1039, 51687 Reims Cedex 2, France

Radiation induced polymerisation offers many advantages compared to the traditional thermal curing of composites essentially for the fast and out-of-autoclave curing operation as well as for the ability to manufacture complex and large structures at low development costs. However a better control of the elaboration of the network under radiation is still required to reach the specifications of high performance composites. Macroscopic properties such as the glass transition temperature (Tg) as well as the microstructure of the formed network are of central importance in the design of matrices with demanding mechanical properties. In this work we have examined in particular the effect of thermal post cured treatment and of the initiator nature, iodonium or sulfonium salts with various counter ions, on the thermo-mechanical properties and on the microstructure of the formed network. The samples were characterized to determine the relation between the degree of cure, the post-cure treatment and Tg. Network microstructure was investigated by atomic force microscopy (AFM) and NMR relaxometry, bringing information at various dimension scales. The AFM phase images revealed the heterogeneous character of the network that can be interpreted in term of variations of crosslink densities. The decay of transverse magnetization measured by solid state proton T2 NMR relaxation experiments exhibits two kinetic components which can be assigned to the highly cross-linked and the loosely cross-linked phase. The effects of the thermal history on Tg and on monomer conversion in aromatic epoxy materials cured by EB irradiation have been examined in some detail. GAMMA-IRRADIATION OF SOLID, MOLTEN AND DISSOLVED POLYETHYLENE OXIDE) AND ITS NANOCOMPOSITES

T. Jurkin and I. Pucic Laboratory for Radiation Chemistry and Dosimetry, Ruder Boskovic Institute, Zagreb, Bijenicka 54, Croatia

Poly(ethylene oxide), (PEO), is a semicrystalline polymer with a numerous applications (hydrogels, polyelectrolytes, etc.). Its degree of crystallinity can be reduced by both degradation and crosslinking. Gamma irradiation is a suitable method widely used to achieve modification of PEO for specific applications. The outcome can be influenced by different factors like PEO characteristics and irradiation conditions, even though some of them are rarely implicated. Namely, effect of PEO molecular mass, sample form, state of aggregation, total dose and dose rate can be assessed only through systematic approach. A part of the ongoing systematic study on interactions of PEO characteristics (aggregate state, molecular mass, sample form) and irradiation conditions (atmosphere, total dose, dose rate) will be presented. A number of experimental techniques like DSC, WAXD, FTIR etc. were applied, DSC being the most sensitive. It has been found that the y- irradiation dose and the state of aggregation of PEO samples are the most important factors determining the outcome. The influence of atmosphere, molecular mass and form of PEO sample (for those irradiated in the solid state) cannot be neglected. Chain scission dominated in PEO irradiated in the presence of oxygen especially in solid state and resulted in an increase in crystallinity and crystallite size at small doses. The increase in crystallinity did not occur on irradiating PEO at temperatures above its melting point or in aqueous solution. The lowest degree of crystallinity and phase transformation temperatures with preserved mechanical properties were obtained on irradiation of aqueous solution in an inert atmosphere and was probably due to crosslinking. The protective effect of solvent seems to be questionable since also degradation was observed in PEO samples irradiated as aqeous solutions in presence of oxygen. The results of the extensive study help in ongoing optimization of radiation preparation of PEO nanocomposites. - 19 -

CROSSLINKING OF VDF-BASED POLYMERS BY y-RADIATION: IMPROVEMENT OF NETWORK DENSITY

L. Dumas1*, S. Rouif2), D. Portinha1* and E. Fleury1* ^Université de Lyon, INSA-Lyon, CNRS, IMP@INSA, UMR 5223, F-69621, Villeurbanne, France 2,10NIS0S - Parc Dombes Cőtiére Activités, Dagneux, F-01120, France

Poly (vinylidene fluoride) is characterized by high intrinsic properties associated with the presence of a strong CF bond, responsible for its good chemical and thermal stability and its low surface energy. These properties provide a wide range of applications, from the medical field to the energy one. However, for some specific applications, excellent physicochemical affinity with a given liquid medium as well as a conservation of the dimensional integrity is required. These antagonist properties can be insured by crosslinking the material through an irradiation process such as the use of y- ray. Compared to traditional methods which consist in a prior chemical modification of the polymers, this strategy can be applied on materials already processed. The mechanisms of the homopolymer radiolysis [1] are relatively well known and involve free radical species which nature and concentration can be measured by ESR [2], The main scope of this work is to study and improve the crosslinking of PVDF- based polymers induced by y-radiation. The macroscopic behavior of the irradiated material is related to the ability of the polymer to form crosslinks or chain scission. The network formation is revealed by swelling test while crosslinking density can be evaluated from rheological measurements. Finally, a part of the study is focused on the increase of crosslinking efficiency. For this purpose, a chemical crosslinker which is sensitive to free radical reactions was incorporated into the polymer matrix. Thus, a significant improvement in properties is revealed. Moreover, the impact of radiation dose, crosslinker concentration or type of atmosphere during the radiation process is evaluated and their impact on mechanical properties is elucidated.

References

[1] K. Makuuchi, A. Asano, T. Abe, J. Polym. Sci. Pol. Chem, 14, 617 (1976) [2] L. Dumas, B. Albela, L. Bonneviot, D. Portinha, E. Fleury, submitted to J. Phys. Chem. Letters - 20 -

EFFECTS OF SOLVENT POLARITY ON MUTUAL POLYPROPYLENE GRAFTING BY ELECTRON BEAM IRRADIATION

A.B.C. Geraldo, E. Moura, E.S.R. Somessari, C.G. Silveira, H.A. Paes, C.A. Souza, W. Fernandes and J.E. Manzoli Institute de Pesquisas Energéticas e Nucleares - IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2.242 - Cidade Universitária - 05508-000 - Sáo Paulo - SP - Brazil

Copolymerization by grafting is a process largely known and the advantages of modifying polymers by radiation includes superimposition of properties related to the backbone and the grafted chains in the absence of an initiator. This process produces low byproduct levels, costs and hazards. Since polypropylene is applied in many industrial and commercial sectors, the grafting process is an alternative to improve some of its physical and chemical properties. The aim of this work was to verify the effect of distinct organic solvents on polypropylene grafting process by mutual irradiation applying absorbed doses from 30 kGy to 100 kGy at dose rates of 2.2 kGy/s and 22.4 kGy/s. All process were performed in atmosphere air presence. Styrene was the monomer grafted on polymer substrate and some non-polar and polar organic solvents, like toluene, xylene, acetone, methanol and its homologous, were used at distinct concentrations. The grafted samples were evaluated by degree of styrene grafting (gravimetric determination) and the Mid-FTIR spectrophotometery. As a general behavior, the degree of grafting increases when absorbed dose values increase in a specific solvent until a maximum dose value (50-70 kGy), after this, the degree of grafting decreases. Moreover, the grafting process have high yields when protic polar solvents are used. These results suggest the grafting process does not have dependence of substrate swelling, that is expected when a non-polar substrate and a non-polar media are in contact. The grafting, in this case, can be related to the free radical generation at protic polar solvents in a first step of process mechanism; these reactive specimens start the reaction on substrate surface to allow the accessibility of monomer species to active sites. Some reaction mechanisms are proposed.

Corresponding authors: [email protected], [email protected] -21 -

DETERMINATION OF PROPAGATION RATE CONSTANTS IN RADICAL POLYMERIZATION BY ELECTRON PULSE POLYMERIZATION - SIZE EXCLUSION CHROMATOGRAPHY

N. Bartoszek, S. Kadlubowski, J. M. Rosiak and P. Ulanski Institute of Applied Radiation Chemistry, Technical University of Lodz, Wroblewskiego 15, 93-590 Lodz, Poland

Radiation chemistry and in particular pulse radiolysis techniques possess unique capabilities for studying kinetics and mechanism of free-radical polymerization. These include for instance direct, time-resolved observations of early stages in polymerization processes,[l] as well as detailed studies on propagation-depropagation equilibria.[2] In this work a new approach to determination of propagation rate constant, kp, is discussed. Recently most studies on kp employ the IUPAC-recommended Pulsed Laser Polymerization - Size-Exclusion Chromatography (PLP-SEC).[3] The method is based on subjecting a monomer to a series laser pulses, which initiate and terminate polymerization, and subsequently analyzing the product by SEC. Molecular weight data allow to determine kp. PLP-SEC is limited to transparent systems. Replacing laser pulses by pulses of fast electrons one can analyze kp in a broad range of systems, including non-transparent liquids or solids. This idea has been put forward by Luthjens et al.[4] Experimental evidence of its applicability has been so far very limited. In our work we have tested this method on iV-vinylpyrrolidone in water, a system recently studied in detail by PLP- SEC.[5] Pulse irradiation with SEC analysis can precisely reproduce kp values determined by PLP-SEC at various conditions.

References

[1] E. Takacs, L. Wojnárovits, K. Dajka, Macromol. Chem. Phys. 201, 2170 (2000) [2] P. Ulanski, E. Bothe, K. Hildenbrand, C. von Sonntag, Chem. Eur. J. 6, 3922 (2000) [3] S. Beuermann, M. Buback, Prog. Polym. Sci. 27, 191 (2002) [4] A.M. van Herk, H. de Brouwer, B.G. Manders, L.H. Luthjens, M.L. Horn, A. Hummel, Macromolecules, 29, 1027 (1996) [5] M. Stach, I. Lacik, D. Chorvat, Jr., M. Buback, P. Hesse, R.A. Hutchinson, L. Tang, Macromolecules 41, 5174 (2008). CATALYTIC POLY(VINYL ALCOHOL) FUNCTIONALIZED MEMBRANES OBTAINED BY GAMMA IRRADIATION

M.H. Casimiro1*, A.G. Silva1*, J.V. Pinto2*, A.M. Ramos1*, J. Vital1* and L.M. Ferreira3* ^REQUIMTE/CQFB, Departamento de Química, Faculdade de Ciéncias e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal 2*Departamento de Ciéncia dos Materials and CENIMAT/I3N, Faculdade de Ciéncias e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal 3*Unidade de Fisica e Aceleradores, Institute Tecnológico e Nuclear, ITN, 2656-953 Sacavém, Portugal

The use of solid acid catalysts in industrial esterification reactions presents important advantages over homogeneous liquid phase since it allows continuous operation of reactors together with an easy catalyst separation. In this context fimctionalized polymeric membranes have been receiving increased attention. In this work poly(vinyl alcohol) (PVA) membranes have been modified with methanesulfonic acid in order to bear sulfonic acid functionalities, by mutual y irradiation at a 60Co source. The obtained membranes were used as solid acid catalyst under batch conditions of the esterification reaction between acetic acid and isoamylic alcohol to obtain isoamylic acetate (banana flavour). The effect of various synthesis conditions on membranes’ physical-chemical properties and catalytic activity was evaluated. The membranes were characterized by ATR-FTIR, AFM and SEM. Swelling degree and water contact angle determinations were also performed. The obtained results showed that within the range of conditions studied the catalytic activity of the obtained membranes are dependent on its composition, hydrophobic/hydrophilic properties and absorbed dose. The increase in sulfonic acid groups’ content is accompanied by an enhancement in the membranes catalytic activity, while the increase in absorbed dose leads to a catalytic activity diminish. PROTON-EXCHANGE MEMBRANES FOR HIGH TEMPERATURE FUEL CELLS BY RADIATION-INDUCED GRAFTING

L.I. §anh and S.A. Gürsel Faculty of Engineering and Natural Sciences, Sabanci University, 34956 Istanbul, Turkey

The polymer electrolyte membrane fuel cell (PEFC) operated at high temperature is advantageous than the current low temperature PEFC in that high temperature operation promotes electro-catalytic reaction, reduces the carbon monoxide poisoning and gain better water management. However, when current commercial membrane of Nafion® is operated at temperatures of higher than 80 °C, especially more than 100°C, the fuel cell performance degrades dramatically due to the dehydration. Therefore, the aim of this study is to develop alternative proton exchange membranes that will operate at high temperature PEFC conditions. Radiation-induced grafting, a well-known method for the introduction of functional groups into a commodity polymer for design of the polymer architecture, has been proposed as an alternative method for the synthesis of novel proton-exchange membranes. Radiation-induced grafting offers the advantages such as simplicity and control over process without residues of initiators and catalyst as well. Graft copolymers were prepared via pre-irradiation method by 60Co source by employing nitrogen containing monomers, iV-vinyl-2-pyrrolidone, 2-vinyl pyridine, 4-vinyl pyridine, to establish hydrogen bonding between N-H atoms and poly(ethylene-ö//-tetrafluoroethylene) as the base polymer film. Graft copolymer films were doped with phosphoric acid subsequently to obtain proton-exchange membranes. The resultant radiation grafted membranes were characterized ex-situ for ionic conductivity, water uptake and mechanical properties. It was determined that resultant membranes have comparable ex-situ ion-conductivity with Nafion® and promising mechanical properties for fuel cell application. - 2 4 -

CHARACTERIZATION OF PE-g-HEMA FILMS PREPARED BY GAMMA IRRADIATION THROUGH NUCLEAR MICROPROBE TECHNIQUES

L.M. Ferreira1*, J.P. Leal2,3*, P.A. Rodrigues1’, L.C. Alves1'4* and A.N. Falcao1* ’’Unidade de Fisica e Aceleradores (UFA), Institute Tecnológico e Nuclear (ITN), 2656-953 Sacavém, Portugal 2)Unidade de Ciéncias Químicas e Radiofarmacéuticas (UCQR), Institute Tecnológico e Nuclear (ITN), 2686-953 Sacavém, Portugal 3)Departamento de Quimica e Bioquimica e Centro de Quimica e Bioquimica, Faculdade de Ciéncias, Universidade de Lisboa, 1749-016 Lisboa, Portugal 4)CFNUL, Centro de Fisica Nuclear da Universidade de Lisboa, 1949-003 Lisboa, Portugal

The functional success of a copolymer as biomaterial depends fundamentally on their mechanical properties (stemming from the material matrix) and on the characteristics of its surface. For biomedical applications, among all the other important properties, the biocompatibility of the surface acquires extreme importance and can dictate its rejection. One of the issues regarding biocompatibility is cytotoxicity which strongly depends on the contamination level at surface. Ion beam analysis techniques associated to Nuclear Microprobe (PIXE, RBS and STIM) allows a rigorous and precise analysis of the concentration (ppm) and distribution of elements contamination, and may also provide information on its near-surface structure. In this work PE-g-HEMA films with different grafting yields were prepared by mutual gamma irradiation at a 60Co source and were analyzed through nuclear microprobe. Data collected allowed the qualitative and quantitative evaluation of contaminants distribution observed in the different samples as well as the clarification of some processes occurred during the copolymerization reaction. Qualitative analysis showed a random and no homogenous distribution of the contaminant elements, independent of the grafting degree, suggesting the existence of several sources of contamination at different stages of their preparation. Results also suggest that this “phased” contamination occurs simultaneously with mechanisms of agglomeration/entrapment of impurities during the gamma induced copolymerization reaction. Moreover, quantitative data showed that all contaminants found in the copolymeric films are natural contaminants of their reagents of preparation, although at concentrations without toxicological hazard, which points to a low cytotoxic potential. The combined analysis of these data with data from SEM and AFM allowed a better understanding of the surface structure and other properties already observed in these copolymeric films. PRODUCTION AND POSTIRRADIATION RELAESE OF HCL AND H2 IN THE RADIOLYSIS OF PVC

P.I. Pavlova-Schmitz1,2), J.A. LaVerne1* and S.M. PimbIott2,3) ’’Radiation Laboratory, University of Notre Dame, Notre Dame, IN 46556, USA 2)School of Chemistry, University of Manchester, Manchester, Ml 3 9PL, UK 3)Dalton Nuclear Institute, University of Manchester, Manchester Ml 3 9PL, UK

Poly(vinylchloride) (PVC) is a thermoplastic polymer commonly encountered in nuclear waste management, disposition and disposal. Despite this, the effects of ionising radiation on its performance are insufficiently understood and poorly characterised. Our study has focused on the post-irradiation degradation of y and 4He ion irradiated PVC and especially on the release of potentially corrosive and explosive gases, such as hydrogen chloride (HC1) and molecular hydrogen (H2), from deaerated, aerated, and water mixtures of PVC. Experiments were performed with PVC powder samples with number average weight of 22 kDaltons and with unplasticised PVC film. The samples were irradiated with 60Co y- rays and 4He ions at room temperature. The production and post-irradiation release of HC1 and H2 was measured using ion and gas chromatography, respectively. In addition, the post-irradiation evolution of the solid plastic was examined using EPR, FT-IR and UV/VIS spectroscopy. The yield of HC1 from y-radiolysis of the PVC powder is 19.6 molecules/100 eV. Chloride ion is released from the polymer for days following radiolysis. The H2 yield with y-rays is about 0.23 molecule/100 eV and 0.45 molecule/100 eV with 4He ion radiolysis. Visually, irradiated PVC samples change from white to a green-brown colour with the extent of discolouration dependent on the applied dose and irradiation environment. No significant post-irradiation evolution of the chromophores was observed by FT-IR or UV/VIS, but the EPR spectra evolve with time. Various reaction mechanisms and possible products will be discussed.

Acknowledgment: This study was performed under the auspices of the Dalton Cumbrian Facility Project, which is a joint initiative of the Dalton Nuclear Institute of The University of Manchester and the U.K. Nuclear Decommissioning Authority. Work at the Notre Dame Radiation Laboratory was supported by the Office of Basic Energy Science of the U.S. Department of Energy. - 26 -

ULTRAVIOLET-RADIATION CURING OF AN ORGANICALLY MODIFIED SILICATE-BASED MATERIAL SYSTEM WITH EPOXY FUNCTIONALITY, AND THE ROLE OF TITANIUM

M. (^opuroglu and M. §ien Hacettepe University, Department of Chemistry, Polymer Chemistry Division, Beytepe, 06800, Ankara, Turkey

Inorganic-organic hybrid material systems, particularly organically modified silicates, offer significant opportunities in the context of development of materials for applications such as dental restoration, photonic interconnection/optical waveguiding, abrasion-resistant coating, etc. To obtain materials of this type, the sol-gel synthesis method, which enable increased control over the chemical composition, microstructure, phase stability, and hence the final properties, can be used. In this study, an inorganic- organic hybrid material system was synthesised by the sol-gel method using (3- glycidyloxypropyl)trimethoxysilane, tetraethoxysilane, dimethyldi-ethoxysilane, and titanium(IV) zso-propoxide. The resultant material system was processed with ultraviolet (UV)-radiation. Influences of certain synthesis and process parameters, including Ti content, sol ageing time, and UV-radiation time, on various properties of the system were detailed. Overall results demonstrated that Ti-based precursors and UV-radiation could be employed to modify the microstructure, and that the final properties of the system might be tuned by an optimal combination of these two parameters. This technique therefore provides a new process regime to obtain materials of this type with desired properties. - 27 -

ACCOMPANYING OF PARAMETERS OF COLOR, BRIGHTNESS AND HARDNESS ON POLYMERIC FILMS COATED WITH PIGMENTED INKS CURED BY DIFFERENT RADIATION DOSES OF ULTRAVIOLET LIGHT

M.A.G. Bardi and L.D.B. Machado Institute de Pesquisas Energéticas e Nucleares, Comissáo Nációnál de Energia Nuclear (IPEN/CNEN-SP), Avenida Professor Lineu Prestes, 2242, Cidade Universitária, SP 05505-000, Brasil

In the search for alternatives to traditional paint systems containing solvents, the curing process of polymer coatings by ultraviolet (UV) light has been widely studied and discussed, specially because of their high content of solids and null emission of VOCs. Radiation curing is defined as the conversion of a reactive liquid into a solid through polymerization and crosslinking reactions between the species, promoted by the interaction of the chemical system with the incident ionizing radiation. The appearance of the coated object (e.g., color, gloss) is a complex function of the light incident on the object, the optical scattering characteristic of the material, and human perception. Pigments are very fine powders being nearly insoluble in binders and solvents, but provide color and the ability to hide the underlying surface. In this context, this paper aims to investigate variations on color, brightness and hardness of UV-cured pigmeted coatings by different doses. When it comes to irradiation exposition, the incorporation of pigments can preferentially cause its reflection or absorption of the incident radiation. Reflection usually occurs at the pigment surfaces within the resin so that the radiation has to pass through the top layers twice. Some degradation can, therefore, occur at the surface, and this is why materials frequently lose gloss on exposure. -28 -

Y-RAY INDUCED GRAFTING POLYMERIZATION FROM A PA-66 REINFORCED PVDF MICROPOROUS ORGANIC MEMBRANE: ARE BOTH POLYMERS CHEMICALLY MODIFIED?

N. Fortin1*, S. Rouif 2\ D. Portinha1* and E. Fleury1* ^Université de Lyon, INSA-Lyon, CNRS, IMP@INSA, UMR 5223, F-69621, Villeurbanne, France. 2*IONISOS - Parc Dombes Cőtiére Activités, Dagneux, F-01120, France

Synthetic polymeric membranes have gained interest in separation science, engineering and technology. Fluoropolymers and especially poly(vinylidene fluoride) (PVDF) are used for such applications. Indeed they are well-known for their good properties in terms of chemical, thermal and electrical stabilities, inertness to acids, solvents and oils, and high resistance to ageing and oxidation. However, the high hydrophobicity of the PVDF membrane could limit its application when the fluid phases to be treated are dispersed in an aqueous medium. Therefore there is a need for the development of new surface modification processes, which renders the membrane more hydrophilic and which are clean and robust enough to be used in industrial field. This work focuses on the y-ray induced grafting of different hydrophilic monomers onto a PA-reinforced PVDF membrane. These polymers are known to be radio-sensitive, and radicals can be generated on both components and their relative proportion determined by ESR [1]. The influence of various parameters was evaluated, related either to the radiation process or the polymerization step, and a global methodology based on thermal properties, viscosimetry and spectroscopic techniques was used to point out the highly selective modification of the PVDF component of the membrane only [2], Finally, the surface properties of the membrane were evaluated and confirmed the membrane modification.

References

[1] N. Fortin, B. Albela, L. Bonneviot, S. Rouif, J.-Y. Sanchez, D. Portinha, E. Fleury, submitted to Polym. Degrad. Stab. 2010 [2] N. Fortin, S. Rouif, D. Portinha, E. Fleury, submitted to Polymer, 2011 - 2 9 -

RADIATION INDUCED CROSSLINKING OF POLYACRYLONITRILE FIBER AND AN ESR STUDY

W. Liu1’2*, M. Wang1*, Z. Xing1’2* and G. Wu" '^Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China 2) Graduate University of the Chinese Academy of Sciences, Beijing 100049, China

Polyacrylonitrile (PAN) fiber was irradiated both in vacuum and air atmospheres at room temperature by gamma rays. Gel fraction determination indicated that gamma irradiation led to the crosslinking of PAN fiber in both cases. However, oxidative degradation resulted in a reduction in gel content at higher dose for the irradiation in air. Electron spin resonance (ESR) was used to trace the evolution of free radicals produced by irradiation in order to study the crosslinking mechanism. The G-value of radical formation was 2.1 (per 100 ev) at room temperature after correction using 1,1- Diphenyl-2-picrylhydrazyl (DPPH). The radicals were found to be rather stable in vacuum, but decayed in air (half life: one week) at room temperature. The most of radicals might be trapped in the crystal part of PAN fibers. By thermal treatment of irradiated PAN fibers in air and vacuum, the trapped radicals decayed with increasing temperature and the radical concentration decreased sharply around the glass transition temperature (100 °C). STUDY OF PDMS CONFORMATION IN PDMS-BASED HYBRID MATERIALS PREPARED BY GAMMA IRRADIATION

J.J.H. Lancastre1*, N. Fernandes1*, F.M.A. Marga^a1*, I.M. Miranda Salvado2), L.M. Ferreira1*, M.H. Casimiro3* and M.C. Corvo3* '*Unidade de Fisica e Aceleradores (UFA), Institute Tecnológico e Nuclear (ITN), 2656-953 Sacavém, Portugal 2)CICECO & Departamento de Engenharia Cerámica e do Vidro, Universidade de Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal 3*REQUIMTE/CQFB, Departamento de Quimica, Faculdade de Ciéncias e Tecnologia, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal

High flexibility, low elastic modulus and high mechanical strength are some of the enhanced properties shown by polydimethylsiloxane-silicate based hybrid materials. These materials are currently being developed for many different applications including biomedical as for instance, to substitute bone tissue. The hybrids materials are usually prepared by sol-gel. However, those reported in the present study were prepared using a 60Co source by gamma irradiation of a mixture of polydimethylsiloxane (PDMS) with tetraethylorthosilicate (TEOS) and zirconium propoxide (PrZr) without addition of any solvent or other product. The obtained materials are homogeneous, transparent, monolithic and flexible. The porosity of these materials have been previously characterised by small angle neutron scattering and other more conventional techniques. The present work aims to further investigate these materials as to their structure dependence on the variation of the precursors contents. A combination of X-ray diffraction, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) and 29Si NMR techniques was used. The results revealed that there are ordered polymer chains both in the irradiated pure polymer as well as in the hybrids, besides amorphous silica. The content of PrZr was found to play an important role on the polymer conformation in the hybrid materials even when it is added in small contents. The results will be presented in detail and discussed. RADIATION-INDUCED GRAFTING OF STYRENE ONTO POLY(VINYLIDENE FLUORIDE) FILM BY SIMULTANEOUS METHOD WITH TWO DIFFERENT SOLVENTS

H.P. Ferreira, D.F. Parra and A.B. Lugao Nuclear and Energy Research Institute - IPEN-CNÉN/SP, Av. Professor Lineu Prestes, 2242, 05508-000, Sao Paulo - SP - Brazil

Radiation-induced grafting to create membranes with ion exchange capacity in fiuorinated polymers has been studied for applications such as fuel cells, filtration and waste treatment and polymeric actuators due to their good physical and chemical properties. In this work, radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses of 1 and 2.5 kGy in the presence of a styrene/N,N- dimethylformamide (DMF) solution (1:1, v/v) and at doses of 20, 40 and 80 kGy in presence of a styrene/toluene solution (1:1, v/v) at dose rate of 5 kGy h-i was carried out by simultaneous method under nitrogen atmosphere and at room temperature, using gamma rays from a Co-60. The films were characterized before and after modification by the grafting yield (GY),infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). GY results shows that grafting increases with dose, and it was possible to confirm the grafting of styrene by FT-IR due to the new characteristics peaks and by the TG and DSC due to changes in thermal behavior of the grafted material. Results showed that the system allows the homogeneous grafting of styrene into PVDF using gamma irradiation at doses as low as 1 kGy when DMF is used and heterogeneous grafting when toluene is used, showing the importance of the solvent nature during the simultaneous method. - 3 2 -

CHALLENGES IN VALIDATING RADIATION STERILIZATION WITH LOW ENERGY ELECTRON IRRADIATION

A. Miller and J. Helt-Hansen Radiation Research Department, Riso DTU Technical University of Denmark, DK-4000 Roskilde, Denmark

Low energy electron irradiation (80 - 300 keV) is used increasingly for sterilization or decontamination in connection with isolators for aseptic filling lines in the pharmaceutical industry. It is not defined how validation for this process shall be carried out. A method can be derived from the medical device standard for radiation sterilization, ISO 11137, because the principles described in this standard can be applied to almost any industrial irradiation process.

The validations elements are: Process definition, concerning specification of the dose required for the process and the maximum acceptable dose for the product. Installation qualification, concerning acceptance the irradiation facility. Operational qualification, concerning characterization of the facility. Performance qualification, concerning setting up the process. Process control, concerning routine monitoring.

The limited penetration of the low energy electrons leads to problems with respect to executing these validation steps. This paper discusses these problems, and show with examples how they can be solved. THE EFFECT OF TIME AND DOSE FRACTIONATION ON THE RESPONSE OF HARWELL GAMMACHROME YR PMMA DOSIMETERS

K. Farah1*, A. Kovács2*, A. Mejri1* and F. Hosni1* ’’Unité de recherche: Maitrise et développement des techniques nucléaires á caractére pacifique. Centre National des Sciences et Technologie Nucléaires. 2020, Sidi-Thabet. Tunisia ^Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

In some irradiation facilities, dosimeters may receive their total absorbed dose in two or more absorbed-dose increments. Some interruptions may be planned, for example multiple irradiations may be used to ovoid increasing of irradiation temperature in electron beam accelerators. Other interruptions may be the result of unplanned irradiator shutdowns. Dose fractionation effects from both planned and unplanned interruptions should be quantified by determining the effect for different dose fractions and interruption times between successive irradiations. This work describes experiments carried out on the response of Gammachrome YR PMMA dosimeters to both single fractions and fractionated doses (two absorbed-dose increments separated by different intervals of time: 0.5, 1, 2, 15 and 24 hours) were measured. Specific absorbance measurements were carried out as a function of post-irradiation time (time between the completion of irradiation and spectrophotometry) from 20 minutes to 4 hours. For measurements taken 3 hours after irradiation, (optimal time to read out Gammachrome dosimeter) it was found that response variations due to dose fractionation were between 1-5%. - 3 4 -

ACCIDENTAL AND RETROSPECTIVE DOSIMETRY USING TL METHOD

D. Mesterházy, M. Osvay, A. Kovács and A. Kelemen Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

The possible risk of an unexpected nuclear accident or violent terror attack necessitates different methods and processes potentially applicable in emergency. After the event fast and reliable dose assassments should be given so that arrangements and intervention could start as soon as possible. Retrospective dosimetry is one of the most important tool of accidental dosimetry for dose estimation when dose measurement was not planned and there is no dose data available as a result of a nuclear accident. Luminescenct materials are suitable for retrospective dosimetry using TL and/or OSL analysis. Several materials have luminescence properties in the evironment, but in the situation mentioned it is suggested to use not just natural substances, but also personal belongings carried by victims, who received the dose. In our environment many objects can be applied as natural dosimeters, having suitable thermoluminescent (TL) and optically stimulated luminescent (OSL) properties. The paper discusses the recent developments, the analysis of luminesence and the dose response curves of various electronic components and the common (table) salt (NaCl) using Daybreak TL reader for retrospective dosimetry purposes. Basic TL properties of these materials (e.g. fading and reproductibility) have also been investigated and will be shown in this study. -35 -

DOPED LITHIUM TETRABORATE AS ADVANCED PHOTOLUMINESCENT AND THERMOLUMINESCENT MATERIALS

M . Ignatovych1* and A. Kelemen2* ^Chuiko Institute of Surface Chemistry, NASU, 17 Gen. Naumov Str.. Kyiv 03164, Ukraine Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

In the presentation it is proposed a review on systematic and comprehensive spectral study o f transition and rare-earth doped tetraborates. It w ill be considered the spectral characterization of Cu-, Eu-, Mn- and Ag-doped LTB, in dependence on dopant content and host modifications: single crystal or glass [1, 2 ]. The presentation w ill include the following items: i) Steady-state and time-resolved photoluminescence (PhL), radioluminescence (RL) and optical absorption (OA) spectra of all above mentioned materials. Kinetic data of PhL and RL (decay curves and life times of emissions). ii) Effect o f high-dose irradiation on the state of the dopants and LTB host - lattices. iii) Thermoluminescence (TL) spectra and dosimetric properties of Cu-doped LTB samples. The main results obtained in the study are that the oxidation state of dopants and hence the emitting properties of these materials such as the luminescence spectra, light-output and lifetimes data are strongly dependent on LTB host- lattice modification. Change in the valence state o f the dopant was observed for the glassy samples in comparison with the relevant single crystals for Cu-, Eu- and Mn- dopted LTB. High-dose (1.0xl03Gy and 1.2xl04Gy), high-energy (4 MeV) irradiation by accelerated electrons o f LTB:Mn and LTB:Ag single crystasl revealed the changes in the oxidation states of dopants. Recharging of dopants Mn2+ —>-Mn3+ and Ag+I—>Ag° were registrated. Ionization processes Mn2+ —>Mn3+ + e and creation of Ag° - nanoparticles were revealed. Thermoluminescence study of non-doped LTB and LTB:Cu single crystals confirmed that TL sensitivity to y doses in the range of 10mGy-200Gy of LTB:Cu was 5 times larger than for well-known,commercially produced dosimeters TLD-100 and TLD-700. High TL sensitivity o f non-doped LTB to thermal neutrons makes the use of pair LTB:Cu and non-doped LTB very promising for mixed-field dosimetry.

References

[1] M. Ignatovych, V. Holovey, A. Watterich, T. Vidoczy, P. Baranyai, A. Kelemen,V. Ogenko, O. Chuiko, Radiat. Phys. Chem., 67, 587 (2003) [2] M. Ignatovych, V. Holovey, A. Watterich, T. Vidoczy, P. Baranyai, A. Kelemen, V. Ogenko, O. Chuiko, Radiat. Measur. 38, 567 (2004) - 3 6 -

MEDICAL DOSIMETRY IN HUNGARY

O. Túrák1*, M. Osvay2’ and L. Ballay1’ Frédéric Joliot-Curie” National Research Institute for Radiobiology and Radiohygiene, Budapest, Hungary 2 ) Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

The widespread development and application of X-ray and of nuclear energy resulted in the problem of ionozing radiation dosimetry in Hungary in the 50’s. The individual monitoring started in 1955 using film dosimeter and ionizing chambers (pen dosimeters) to determine the external photon radiation dose. Since 1966 the film badge has been accepted as the official personal dosimeter system in Hungary. The personal monitoring for 16,000 occupational exposed workers (Nuclear Power Plant, Research Reactors, Isotope Production Laboratories, Hospitals, Industrial Radiographers, etc.) is conducted by the National National Research Institute for Radiobiology and Radiohygiene with Kodak film badges. As for distribution of customers, the 55% o f the dosimeters are used in medicine. Both of medical staff and patient dose (diagnostic and therapy procedures) measurements need control measurements in the dose range of 5 |j.Gy - 50 Gy. In Hungary the film dosimeters (as authorized dosimetry system) are used for the assessment of staffs effective dose. In case o f patient dose measurement most of the manufacturers use ion chamber, and TLD systems at experimental measurements. At dose optimization in the wide spectrum o f medical applications we have to focus only procedures that bear the highest dose and procedure number from all of the humandiagnostic procedures as interventional radiology. Nowadays in Hungary the occupational dose measured only by one dosemeter worn under the lead apron that be used for the estimation o f staffs effective dose. In interventional radiology and cardiology procedures we need another dosemeter next to the film dosemeter to measure the dose o f the eye lens, gonads, fingers, wrist, chest and knees. For this purpose we need a smaller and energy independent dosemeter. Due to the small volume, wide dose range and the energy independence, the LiF TLD is a proper choice for these measurements. The paper discusses the dosimetry methods and recent developments for radiation protection during interventional radiology procedures in Hungary. RADIATION-ENGINEERED NANOMATERIALS: THE ROLE OF THE IAEA IN COORDINATING RESEARCH

M. Haji-Saeid, A. Sáfrány, M.H. de O. Sampa and N. Ramamoorthy International Atomic Energy Agency, Vienna International Centre, A-1400 Vienna, Austria

Radiation technologies, already established in materials processing, have properties uniquely suited for the creation of new functional materials on the nanoscale, both in “top-to-bottom” and “bottom-up” approaches. For example, controlled radiation degradation may be used for fabrication of nanoporous and nanostructured surfaces and membranes; while radiation polymerization, crosslinking and grafting could produce functional polymeric, metallic and semiconductor nanoparticles, functional nanostructured surfaces and nanocomposites. Applications for such nanostructured materials are manifold, from 3D structures, templates for nano wire fabrication, supports for purification, and proton exchange membranes, to imaging, diagnostics, targeted drug and gene delivery, wound healing and cell sheet engineering. Considering the significant potential as well as the already demonstrated successful applications in using radiation methods for synthesis and characterization of nano-sized materials as well as the interdisciplinary nature of nanotechnology, and in order to facilitate the coordination between radiation-based research groups and nanotechnology centres, the IAEA has organized a number of consultantcy meetings, training courses and workshops. Additionally, a coordinated research project entitled “Nanoscale Radiation Engineering of Advanced Materials for Potential Biomedical applications” in progress, under which 17 IA EA Member States institutions work together to develop radiolytic methodologies for synthesis of nanoparticles and nanoporous membranes; polymeric, inorganic and hybrid nanocarriers for various healthcare applications.

This presentation will describe the present activities of the IAEA and plans for future supports for fostering development and application of radiation-engineered functional nanomaterials. - 3 8 -

RADIATION ENGINEERED MULTI-FUNCTIONAL NANOGELS AS NANOSCALE BUILDING BLOCKS OF USEFUL BIOMEDICAL DEVICES

C. Dispenza Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Universitá degli Studi di Palermo, Viale delle Seienze 90128 Palermo. Italy.

Nanogels, or small particles formed by physically or chemically crosslinked polymer networks, represent a niche in the development of “smart” nanoparticles for drug delivery and diagnostics. They offer unique advantages over other systems, including a large and flexible surface for multivalent bio-conjugation; an internal 3D aqueous environment for incorporation and protection of (bio)molecular drugs; the possibility to entrap active metal or mineral cores for imaging or phototherapeutic purposes; stimuli- responsiveness to achieve temporal and/or site control o f the release function and biocompatibility. Moreover, conformability and flexibility make these nanoparticles able to penetrate through small pores and channels through shape modification. Major synthetic strategies for the preparation of nanogels belong to either micro-fabrication methodologies (photolithography, microfluidic, micromoulding) or to self-assembly approaches that exploit ionic, hydrophobic or covalent interactions. When dimensional control has been achieved through the recourse to “soft templates”, such as the internal aqueous phase droplets o f inverse microemulsions, the use o f surfactants, initiators and catalysts often require complex purification procedures. On the other hand, micro­ fabrication methods, such as nanomoulding, are limited by the need of costly equipments. The availability o f inexpensive and robust preparation methodologies is at the basis o f the development o f effective nanogel-based theragnostic devices. High energy radiation processing already demonstrated its potential for the production o f nanogels in the late ‘90s, owing to the pioneeristic work of Rosiak and collaborators, but since no adequate efforts have been spent in developing a viable and robust technology to produce multi-functional nanogels for the benefit of several different nanotechnology application fields, such as sensing, medicine and multiple others. The design rules for mass fabrication of nanoscale hydrogel particles with the recourse to industrial-type accelerators w ill be discussed. Radiation engineered nanogels may become base building blocks of higher order structures with designed properties, through the integration o f heterogeneous components of different sizes and compositions, including biomolecules. - 3 9 -

APPLICATION OF IONIZING RADITION FOR METAL NANOCLUTERS SYNTHESIS

D.K. Smietanko-Chmielewska1* and A.G. Chmielewskilr2) ’’institute of Nuclear Chemistry and Technology, Warsaw, Poland 2)Warsaw University of Technology, Department of Process and Chemical Engineering Warsaw, Poland

Possibility of ionizing radiation application in nanotechnology has been observed from very beginning when this field of science and technology was named. The lithography is based on electron and ion beam applications, and metal clusters synthesis by radiation induced radicals was reported many years ago [1]. International Atomic Energy Agency was the first organization which has started coordinated programs on radiation applications in nanotechnology [2 ] which are being continued in the frame of regional cooperation project RER8014. Some of applications led to patented technical solutions [3], Then review papers [4, 5] and chapters in the books have been published. The main applications beside of lithography deal with metal nanoclusters and nano­ composites synthesis. Polymer composites containing metal nanoparticles have attracted a great interest due to their unique chemical and physical properties. “Green” chemistry promotes application o f natural fibers in such structures, among them cellulose is one of the most frequently used. However, cellulose fabric have ability to absorb moisture, so under certain conditions o f humidity and temperature they can be subjected to microbial attack. One of the most popular and best known antibacterial agents is silver, which serves as a potential antibacterial material acting against an exceptionally broad spectrum o f bacteria including activity against antibiotic-resistant bacteria. Silver nanoparticles (Ag NPs) were grown at the cellulose fibers surface by direct reduction of AgN 0 3 with electron beam (EB) application [6 ], The big field of development concerns nano composites, possibility of e/X units application enlarge this possibility to industrial scale product manufacturing.

Acknowledgment: This work was supported by the IAEA, regional project RER/8/014 and by the Ministry of Science and Higher Education, project DPN/W14/IAEA/2009.

References

[1] J. Belloni, Radiat. Res., 150(5) S9 (1998) [2 ] Emerging applications of radiation in nanotechnology, TECDOC-1438, IAEA, Vienna, (2005) [3] D.K. Chmielewska, U. Gryczka, W. Migdal, Rec. Pat. Nanotech., 2(3), 8201 (2009) [4] A.G. Chmielewski, J. Michalik, M. Buczkowski, D.K. Chmielewska, Nuc. Inst. Meth. Phys. Res. B, 236, 329 (2005) [5] A. G. Chmielewski, D. K. Chmielewska, J.Michalik, M. H. Sampa, Nuc. Inst. Meth. Phys. Res. B, 265, 339 (2007) [6 ] D.K. Chmielewska, B. Sartowska, W. Starosta, M. Walo, Nukleonika, 55(3), 345 (2010) - 40 -

LAYER BY LAYER ASSEMBLY OF POLYANILINE/CHLORINATED POLYMER FILMS AND THEIR RESPONSE TO RADIATION

B. Yarar and O. Giiven Department of Chemistry, Hacettepe University, 06800 Beytepe, Ankara, Turkey

Development of radiation-induced conductivity in blends and composites of polyaniline with polymers that release acid upon irradiation has been shown in previous works from this laboratory. Films casted from mixed solutions, pellets prepared from mechanically mixed and pressed samples, composites, etc. all gave very stable binary systems that showed significant increase in conductivity upon gamma and EB irradiations up to several hundreds of kGy absorbed dose. In this study we have tried to prepare very thin films of binary polymers by layer-by-layer deposition technique. Bilayers of emaraldine base polyaniline(PANI) and cholorosulfonated polyethylene(CSPE) were carefully deposited onto ITO surface. The layer-by-layer deposition of polymers from DMAA/water solutions were followed by UV-vis spectroscopy as shown in Fig. 1 below. Fig 2 shows the spectra of 10 bilayer deposited films treated with NH 3 vapors to make sure that PANI is in its fully nonconductive form and the same film treated with HC1 vapors to convert PANI into its fully conductive form and the nonductive film form irradiated to 15 kGy absorbed dose. Polaron and exciton bands observed in acid doped and gamma irradiated films are almost the same. Film properties before and after irradiation were investigated by ellipsometry, contact angle measurements, AFM and ATR-FTIR and by measuring changes in conductivity.

deposited on ITO surface

doped 10 bilayers of PANI/Chlorosulfonated PE -41 -

PLASMA SURFACE MODIFICATION OF POSS-PCU NANOCOMPOSITE TO IMPROVE BLOOD COMPATIBILITY

M. Solouk1’, H. Mirzadeh1’ and A.M. Seifalian2,3* ’’Polymer Engineering Department, Amirkabir University of Technology (Tehran Polytechnic), Tehran, Iran. 2)Centre for Nanotechnology & Regenerative Medicine, Division of Surgery & Interventional Science, University College London (UCL), London, U. K; 3)Royal Free Hampstead NHS Trust Hospital, London, U. K.

By considering the surface properties as a key factor in blood compatibility and biostability o f a synthetic vessel, in the present study, the surface modification of a hybrid nanocomposite polyhedral oligomeric silsesquioxane (POSS) in to poly (carbonate-urea) urethane (PCU), POSS- PCU, was done. Computer based modelling through response surface methodology (RSM) and central composite design (CCD) was used to optimise the processing conditions relating to plasma power output (30, 60 and 90 W), and (b) the duration of plasma exposure time (30, 75 and 120 sec) on the treatment process. It was found that optimal WCA (9) for endothelial cells (EC) adhesion and retention which was reported 55° from supporting literature (equivalent to (ys = 51 mN/m), was easily achievable using the following experimental conditions: (I) power output at 30 W for 75 sec, (II) 90 W for 40 sec, and (III) 90 W for 55 sec in O 2. The effect o f plasma treatment on the film of POSS- PCU was studied through water contact angle (W CA), surface energy, ATR-FTIR, SEM and AFM. A comparison between platelet adhesion, hemolysis ratio and EC adhesion and MTT assays for cell assessment to both plasma treated and untreated samples were done and evaluated. This study showed that by developing a model, it is possible to investigate key experimental parameters to achieve reproducible and optimal wettability and surface energy (ys) values and hence modify the interfacial properties of biomaterials used in the design o f vascular bypass grafts to enhance the endothelial cells (EC) response to biomaterials.

References

[1] Desmet, T., Morent, R., Geyter, N. D., Leys, C., Schacht, E., Dubruel, P. A Review, Biomacromolecules, 10, 2351 (2009) [2] J. Solouk, A., Cousins, B.G., Mirzadeh, H., Hashtjin, M.S., Najarian, S., Seifalian, A.M., Biotech. Appl Biochem., in the press (2011) - 42 -

EFFECT OF THE NATURE OF THE SURFACE ON THE REACTIVITY OF NANOPOROUS SILICA UNDER IRRADIATION

S. Le Caer1’, N. Brodie-Linder2’, C. AIba-Simionesco2), M.S. Álam1’, C. Chatelain1’, F. Brunet1’, T. Charpentier1’, D. Durand3’, V. Dauvois3’ and J.-P. Renault1’ ” SIS2M U M R 3299, CEA Saclay DSM /IRAM IS, 91191 Gif-sur-Yvette Cedex, France 2)Laboratoire Léon Brillouin, CEA Saclay, Bátiment 563, 91191 Gif-sur-Yvette Cedex, France 3)CEA Saclay, DEN/DANS/DPC/SECR/LSRM, 91191 Gif-sur-Yvette Cedex, France

Materials such as concrete, clays and zeolites which embed radioactive wastes adsorb in their pores significant amounts of water that can be decomposed under ionizing radiation leading to the formation of H2 which is potentially explosive. It is well established that the H 2 production arises from chemi- or physi-sorbed OH groups at the surface o f oxides. In this context, we have studied the behaviour of water confined in nanoporous silica [1,2]. To distinguish the behavior of the two kinds o f OH, we have performed different thermal treatments on SBA-15 materials prior to their irradiation. The IR analysis and H 2 measurements have proven that in the radiolysis o f SBA-15 materials, silanol groups are only attacked when they are in the majority with respect to adsorbed water. However they are much less efficient at producing H2. The comparison between water content before and after electron irradiation and the corresponding H 2 production indicates that water desorption is the main route to adsorbed water loss. On the other hand, surface silanol groups are more susceptible to attack, leading to H 2 production when SBA-15 samples have undergone extensive thermal treatment [3]. The surface o f nanoporous glasses were then grafted using chloroalkyldimethylsilane. The effect of irradiation on these grafted surfaces was studied by means of mass spectrometry and N M R experiments. These different techniques reveal an original reactivity o f the surface under irradiation.

References

[1] S. Le Caer, P. Rotureau, F. Brunet, T. Charpentier, G. Blain, J. P. Renault, J.- C. Mialocq, Chem. Phys. Chem, 6 , 2585 (2005) [2] F. Brunet, T. Charpentier, S. Le Caer, J.P. Renault, Solid State Nucl. Magn. Reson., 33, 1 (2008) [3] N. Brodie-Linder, S. Le Caer, M.S. Alam, J.P. Renault, C. Alba-Simionesco, Phys. Chem. Chem. Phys, 12, 14188 (2010). RADIATION SYNTHESIS OF SIZE-CONTROLLED POLY(N-VINYL PYRROLIDONE) NANOGELS AND THEIR USE AS ANTIMICROBIAL AGENTS

S.D. I§ik and O. Giiven Department of Chemistry, Hacettepe University, 06800, Ankara, Turkey

Nanogels are swollen networks of hydrophilic polymers generally developed to carry drugs, proteins and biologically active substances for biomedical applications. They can be prepared by 1) physical assembling of interactive polymers, 2 ) polymerization of monomers in micro or nanoscale environment, 3) crosslinking of preformed polymers, 4) template-assisted nanofabrication of nanogel particles [1], Among these methods crosslinking of preformed polymer chains provide excellent applications, especially when ionizing radiation is used as the tool to induce crosslinking. Due to its low cytotoxicity, excellent biocompatibility and non-carcinogenic and non- allergic properties, poly(N-vinyl pyrrolidone) (PVP) has been widely used in biomedical applications, hence the main reason for its selection in this work for the synthesis o f its nanogels. PVP nanogels were prepared by gamma irradiation of its dilute aqueous solutions up to 15 kGy. The coil sizes o f PVP chains were initially controlled by using acetone/water mixture as the solvent and further irradiations fixed the sizes by intramolecular crosslinking. By changing the concentration o f PVP solutions, solvent composition and dose it was possible to prepare nanogels within 40- 230 nm sizes. The nanogels were characterized by dynamic light scattering, scanning electron microscopy and atomic force microscopy. GPC has also been used to follow the changes in the coil sizes and distributions upon irradiations [2 ], The PVP nanogels thus synthesized were complexed with iodine in aqueous KI-I2 solutions. Nanogels comprised of typical PVP-iodine complexes were tested for their antiseptic properties.

References

[1] A.V. Kabanov, S.V. Vinogradov, Angew Chem. Int. Ed., 48 5418 (2009) [2] S.D. I§ik, Master o f Science Thesis, Hacettepe University, Ankara, Turkey (2011). - 4 4 -

EARLY STAGES IN THE GROWTH OF SMALL SILVER CLUSTERS IN AQUEOUS SOLUTION

E. Janata Helmholtz Zentrum Berlin furMaterialien und Energie GmbH Hahn-Meitner-Platz 1, 14109 Berlin, Germany

One of the challenging contributions of radiation chemistry and the method of pulse radiolysis is the ability of producing and characterizing metal and semiconductor colloids on the nanometer scale, experiments which started as early as in the 1970’, i.e., in the early days o f nanotechnology. Since then, metal clusters and nanomaterials have attracted an immense attention due to their unique properties. Here, as a review of the work carried out at the Hahn-Meitner-Institut Berlin/ Helmholtz Zentrum Berlin, the results o f the reduction o f silver ions in aqueous solution by products o f the water radiolysis is presented. Attention focuses in general on silver clusters as a model because the monopositivecation Ag+ is the only noble cation that forms mononuclear species with appreciable stability in aqueous solution.While hydrated electrons simply reduce silver ions, the reduction by hydrogen atoms occurs via the intermediate complex of silver hydride ions. The reduced silver ion, i.e., a free silver atom, reacts further with bulk silver ions thus starting the growth of small silver clusters. Even the early stages of that growth result in interesting structures which gives insight into the valence states o f the silver species being involved. Also, the influence of aliphatic alcohol radicals on these processes is discussed for medium and low bulk silver concentrations. Aliphatic alcohols are present in solution in basically all these experiments in order to simplify the redox system by scavenging oxidizing radicals. Aliphatic alcohol radicals obviously form some kind of complex with small silver clusters thus participating in the growth of silver clusters and determining their properties to some extend. -45 -

PREPARATION OF INORGANIC CRYSTALLINE COMPOUNDS INDUCED BY IONIZING, UV AND LASER RADIATION

V. Cuba, T. Pavelková, J. Bárta, J. Indrei, T. Gbur, M. Pospísil, V. Múcka, Z. Docekalová, A. Zavadilová and M. Vlk Czech Technical University in Prague, FNSPE, Brehová street 7 Prague 1, 115 19 Czech Republic

Radiation methods represent powerful tool for synthesis of various inorganic materials. Study of solid particles formation from solutions in the field of UV or ionizing radiation is one o f the very promising and long term pursued trends in photochemistry and radiation chemistry. The motivation may be various, either preparation of new materials or removal of hazardous contaminants (e.g. heavy metals) from wastewater. This work deals with preparation of some metal oxides, synthetic garnets and spinel structures via irradiation o f aqueous solutions containing precursors, i.e. soluble metal salts, radical scavengers and/or macromolecular stabilizers. Namely, results on radiation induced preparation of nickel, zinc, yttrium and aluminium oxides are summarized, as well as zinc peroxide, yttrium / lutetium - aluminium garnets and cobalt(II) aluminate. 60Co irradiator, linear electron accelerator, medium pressure UV lamp and solid state laser were used as the sources o f radiation. Aside from preparation, various physico­ chemical and structural properties of compounds prepared were also studied. A ll used modifications of radiation method are rather convenient and simple, and yield (nano)powder materials with interesting characteristics. Prepared materials generally have high chemical purity, high specific surface area and narrow distribution of particles size (ranging in tens of nm). Generally, all types of irradiation result in materials with comparable properties and structural characteristics; but in the case of synthetic garnets and spinels, preparation using UV-radiation seems to be the most convenient for their preparation. Among compounds discussed, only zinc oxide and zinc peroxide were prepared directly via irradiation. For preparation o f other crystalline compounds, additional heat treatment (at low temperature) o f amorphous solid phase formed under irradiation was necessary. - 46 -

HYBRID HYDROGELS PRODUCED BY IONIZING RADIATION TECHNIQUE FOR DRUG DELIVERY

M.J.A. Oliveira1’, D.F. Parra1’, V.S. Amato2) and A.B. Lugao’’ ’’Nuclear and Energy Research Institute-IPEN-CNEN/SP. Av. Professor Lineu Prestes, 2242, - Cidade Universitária 05508-000, Sao Paulo-SP Brazil 2)Division of Infectious and Parasitic Diseases at the Hospital of Clinics, School of Medicine, University. Avenida Dr. Enéas de Carvalho Aguiar, 255, CEP: 05403-000 Sao Paulo - SP Brazil

Interest in the preparation of biocompatible hydrogels with various properties has increased considerably in recent years due to their versatile applications in biomedicine, biotechnology, pharmacy, agriculture and controlled release of drugs. The use of hydrogels matrices for particular drug-release applications has been investigated with the synthesis of modified polymeric hydrogel of PVA1, PEG and 0.5, 1.0 and 1.5 % nano-clay. They were processed using gamma radiation from Cobalt-60 source at 25 kGy dose. The characterization of the hydrogels was conducted and toxicity was evaluated. The dried hydrogel was analyzed for thermogravimetry analysis (TGA), infrared spectroscopic analysis (FTIR), swelling in solutions of different pH and gel determinations. The membranes have no toxicity and the gel content reveals the reticulation. The nano-clay influences directly the equilibrium swelling.

Acknowledgment: Support by FAPESP 09/50926-1, FAPESP Process n° 2009/18627-4 CNPq Process n° 310849/2009-8, CAPES, IPEN/CNEN. - 47 -

THE CATALYTIC EFFECTS OF COPPER IONS ON PHOTO­ OXIDATION IN TI02 SUSPENSIONS: THE ROLE OF SUPEROXIDE RADICALS

Y. Du, S. Goldstein and J. Rabani The Accelerator Laboratory and Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

UV photolysis of aerated aqueous suspensions of TÍO2 (Degussa P25) containing CH 3OH at pH 8.5 produces HCHO. Addition of CuSC>4 affects the rate of HCHO formation (í? h c h o ) in two opposite ways. Below 2 pM, í? h c h o increases with increasing [CUSO4)] while at higher concentrations it slows down. At very low [CUSO4)], catalytic dismutation of O 2"' forming H 2O 2 and O 2 results in an enhancement of Rhcho- At higher [CuS04], Rucho decreases due to removal o f mobile holes by cupric ions. Square root dependency of HCHO yield on the absorbed light density is observed in the entire [CUSO4] range used. The square root dependency is generally attributed to competition between second-order electron-hole recombination and first-order trapping, although the lifetime o f both electrons and holes is too short to enable the accumulation of more than one pair in the same nano-volume. It is shown here that the electron-hole recombination path involves reaction o f the mobile holes with adsorbed superoxide. The experimental results provide indirect evidence that adsorbed O 2’" radicals, produced by O 2 reaction with the TÍO2 electrons, are important for the well known square root dependency. Unlike the mobile and trapped electrons, O 2*’ has a relatively long lifetime and its accumulation in the nano-volume upon successive absorptions of photons is feasible. Reaction between the accumulated O2'" radicals and mobile holes is responsible for the square root law. The decrease of Ka, which has been suggested as a standard parameter for the nature of TÍO2, by added Cu2+ implies an apparent improvement o f the T i0 2 quality as a photocatalyst. -48 -

THE OH YIELD IN THE RADIOLYSIS OF AN AQUE0US/H202 SYSTEM

S.S. Emmi, S. Caminati, B. Esposito and M. Saracino ISOF-CNR, Via P. Gobetti, 101, 40129, Bologna, Italy

A number of Advanced Oxidation Processes have been proposed to remediate polluted water and waste water. They are commonly based on the exploitation of the thermodynamic and kinetic properties of the OH radical, which can attack most organic pollutants leading, eventually, to a complete mineralization of organics. In aerated atmosphere at room temperature, OH starts a complex oxidative process through the mediation of various reactive oxygen species (ROS), which go from the simplest well known superoxide radicals (HO 2’, O 2*”) to any intermediate peroxyl radicals originated by the fragmentation of the pollutant molecules. Commonly, OH attacks the organic molecules on n bonds and/or abstracts weakly- bonded H atoms; also, although rarely, it may enter an electron transfer reaction. A very basic and well known AOP is set up by irradiating water containing H2O 2 by means of UV mercury lamps emitting at 254 nm. The energy absorbed by H2O2 is high enough to break the 0-0 bond to form OH. Radiolysis, as well, may profit of the scavenging power of H2O 2 to convert eaq" to OH. The addition of H 2O 2 to an aerated aqueous system constitutes in fact an highly efficient AOP. To this purpose an advantage over the H 2O/N 2O system is represented by the presence o f O 2 which plays an active role in the bulk of the overall oxidation process. Nevertheless literature does not report the optimal conditions for this system. This work describes the conditions for which an aerated aqueous/H2 0 2 system can achieve the same OH yield o f an aqueous N 2O saturated system. Measurements o f the extent of eaq conversion have been done in pulse radiolysis, following the increase of thiocyanate radical anion by increasing H2O 2 concentration. - 4 9 -

THE RADIATION CHEMISTRY OF NANO-CONFINED WATER

R.M. Musat1*, A.R. Cook1*, J.-P. Renault2* and R.A. Crowell1* ^Department of Chemistry, Brookhaven National Laboratory, Upton, NY 11793, USA 2*CEA/Saclay, DSM/IRAMIS/SCM URA331 CNRS, 91191 G if sur Yvette Cedex, France

The need to understand the radiolysis of nano-confined/interfacial water in nuclear related fields has become abundantly clear during the recent events at the Fukushima Daiichi nuclear power plant where an explosion occurred that was a result of hydrogen primarily produced at the water/zirconia interface. Although the generation of hydrogen was expected, the mechanism and prevention of its formation remains questionable. In this contribution we address the role of heterogeneous boundaries, the inhomogeneous dose distribution and the physical confinement itself which may hinder or promote the formation of spurs, and are believed to strongly influence the radiolytical processes, which are well known in bulk phase. The confining system which we have chosen to investigate water radiolysis is controlled pore glasses (CPGs), a system that exhibits a high porosity, well-defined pore size, excellent mechanical properties, high thermal stability and resistance to acids. CPGs o f pore diameters 1 and 50 nm were used for this study and the evolution and optical absorption spectrum o f the hydrated electron was followed by means o f ultrafast pulsed radiolysis. Little to no difference is exhibited in the absorption spectrum, but the confinement of water drastically impacts the reaction kinetics of the aqueous electron.

Acknowledgement: This work was supported by the U. S. DOE Office o f Basic Energy Sciences under contract # DE-AC02-98CH10886. - 50 -

EFFECT OF MOLECULAR STRUCTURE ON FRAGMENTATION OF ISOLATED ORGANIC MOLECULES IN SOLID RARE GAS MATRICES

A.V. Kobzarenko, F.F. Sukhov, A.Yu. Orlov, G.V. Kovalev, LA. Baranova and V.I. Feldman Department of Chemistry, Moscow State University, 119991 Moscow, Russia

Elucidation of high-energy reaction pathways in the condensed phase is an important issue for basic understanding of the radiation stability of complex organic molecules. As was shown previously, organic radical cations (RC) may undergo fragmentation or rearrangement in solid matrices due to excess energy [1], The probability o f this process depends on both ionization potential (IP) of the molecule and molecular structure. In the present work we have studied the role of “hot” ionic reaction channels for RC of some bifunctional compounds and alkynes. The effect o f excess energy was simulated by matrix isolation method as described in detail earlier [1, 2]. The formation of fragmentation products was monitored by EPR and FTIR spectroscopy. In the present work it was shown that the RC of bifunctional compounds (CH 3OCH 2COCH 3, CH 3CO(CH 2)nCOCH 3, n = 0^2) dissociated efficiently producing 'CH 3 radicals upon irradiation in solid argon matrix at T < 16 K. The probability of fragmentation decreases with decrease of excess energy by switching from Ar to Xe. It is worth noting that acetone RC does not show fragmentation under these conditions [1]. Thus, bifunctional molecules were found to be less stable to “hot” ionic fragmentation in low-temperature siolids in comparison with simple prototype carbonyl compounds. In the case o f alkynes o f the R-C=CH type, a noticeable yield of fragmentation products was observed when R = -C(CH3)3, but it was negligible for R= - CH 3. It means that the presence of triple bond stabilizes the molecular skeleton of linear alkynes toward “hot” fragmentation, similarly as it was shown for alkenes [2]. The mechanisms o f “hot” reactions and excess energy relaxation are discussed. This work was supported by the Russian Foundation for Basic Research (project 09-03- 00848a).

References

[1] V.I. Feldman et al., Phys. Chem. Chem. Phys., 5, 1769 (2003) [2] V.I. Feldman et al., Radiat. Phys. Chem., 75, 106 (2006) -51 -

IRRADIATED SEASHELLS: USE OF EPR SPECTROSCOPY FOR IDENTIFICATION AND DOSIMETRY

A. Alberti1*, E. Chiaravalle2*, P.G. Fuochi1*, D. Macciantelli1*, M. Mangiacotti2* and G. Marchesani2* ’’iSOF-CNR, Area della Ricerca, Via P. Gobetti 101,1-40129 Bologna, Italy. 2)Istituto Zooprofilattico Sperimentale della Puglia e della Basilicata, Via Manfredonia 20,1-71100 Foggia, Italy

Treatment o f foodstuff for microbial control and shelf-life extension is being used in many countries. However, for consumer protection and information, the European Union has adopted the Directives 1999/2/EC and 1999/3/EC to harmonized the rules concerning the treatment and trade of irradiated foods in EU countries. Among the validated methods to detect irradiated foods the Directives include Electron Paramagnetic Resonance (ESR/EPR) spectroscopy (CEN, 1997,200, 2002). We describe here the use of EPR for identification and dosimetry of seashells irradiated with 60Co y-rays. We examined four species of molluscan bivalvian, i.e. brown venus shells (callista chione), mussels {pinna nobilis), clams (venerutis decussatus), and oysters (ostrea edulis). EPR could definitely identify irradiated seashells due to the presence of long-lived free radicals, primarily CO 2 radical anions. The presence o f other radical ions (e.g, SO 3") as well as of some organic free radical was also ascertained. The administered dose was successfully reconstructed in the case of oysters, but similar attempts failed with the other seashells due to the lack of appropriate EPR signals. IDENTIFICATION AND DOSE EVALUATION OF IRRADIATED BEEF CONTAINING BONES

M. Mangiacottil,2), G. Marchesani1*, F. Floridi1), G. Siragusa1*, A. Alberti3’, P.G. Fuochi3), L.M. Chiesa2) and A.E. Chiaravalle1* ’’istituto Zooprofilattico Sperimentale della Puglia e della Basilicata - Centro di Referenza Nazionale per la Ricerca della Radioattivitá nel Settore Zootecnico- Veterinario, Via Manfredonia 20,1-71121 Foggia, Italy 2)Universita degli Studi di Milano - Facoltá di Medicina Veterinaria - Dipartimento di Scienze e Tecnologie Veterinarie per la Sicurezza Alimentare - Laboratorio di Ispezione degli Alimenti di Origine Animale, Via Celoria 10,1-20133 Milano, Italy 3)ISOF-CNR, Area della Ricerca, Via P. Gobetti 101,1-40129 Bologna, Italy

Food irradiation is a is a well-established technique to extend the food shelf life and to reduce the food-related health hazards caused by pathogenic micro-organisms. At present, radiation treatment is permitted for various categories o f food and food ingredients in many countries. At the European level, irradiation o f food is regulated by the European Directives 1999/2/EC and 1999/3/EC. Community legislation states that any food or food ingredients, authorised in the European Union, must be labelled with the word “irradiated” and that every year each Member State has to carry out checks at the product marketing stage to enforce correct labelling. The present work aimed at identifying irradiated beef meat by using a reliable and sensitive detection of DNA comets as screening biological method and performing an Electron Spin Resonance (ESR) spectrometry as confirmatory qualitative standard. The influence of storage conditions and time after irradiation on DNA degradation was also investigated. Furthermore the application o f ESR technique as a quantitative method was successfully applied to beef bones, using the approach o f calibration curve. Results, although the limited statistics, proved for reliability of the dose reconstruction method and blind tests were carried out resulting in very satisfactory difference between actual treatment dose and reconstructed dose. -53 -

RADIATION-INDUCED ELECTRON PARAMAGNETIC RESONANCE SIGNAL AND SOYBEAN ISOFLAVONES CONTENT

M.R.R. de Oliveira1’, J.M.G. Mandarino2’ and N.L. del Mastro1’ ^Nuclear and Energy Research Institute, IPEN - CNEN/SP Sao Paulo, SP, Brazil 2)Embrapa Soybean, Londrina, PR, Brazil

The isoflavones from soybean are known to have a number of beneficial health effects and can act as antioxidants. Electron Paramagnetic Resonance (EPR) is a well-known spectroscopic technique that can detect free radicals with high sensitivity. In food, free radicals can be generated by several commonly used industrial processes, such as irradiation or heat treatments. Upon gamma-ray irradiation, a new EPR signal was detectable in the vicinity of g = 2 .0 region, ascribed to stable cellulose-derivative components and is a good indicator in the identification of irradiated plant samples. In this work the relation between EPR signals induce by gamma irradiation treatment and soybean isoflavones content was investigated. Present results did not show correlation between total isoflavones content and the EPR signal. Nevertheless, some isoflavone contents had a negative correlation with the radiation-induced EPR signal. - 54 -

FREE RADICALS INDUCED IN ARCHIVE PAPER BY IRRADIATION

M. Cutrubinis, I.V. Moise, C.D. Negut, R. Georgescu, R. Suvaila, M. Virgolici and M.M. Manea "Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), 30 Reactorului St., 077125, Magurele, Ilfov County, Romania

Irradiation of archive paper (document archives of institutions, companies etc. and library or museum collections o f books and documents) can solve the problems related to the bio-deterioration and bio-contamination of paper and sometimes save valuable cultural heritage paper items. For valuable paper items care should be taken to the degradation induced instantly by the ionising radiation to the cellulosic support and also to the long term post-irradiation effects. The free radicals formed due to the irradiation treatment could contribute to instant degradation of paper. Part of them are also trapped for months and years after irradiation and they could be related to the post-irradiation effects in paper items. In this study, different sorts of cellulosic support samples (soft wood and hard wood cellulose, contemporary paper, paper from archives and from collections etc.) have been irradiated with dosis up to 100 kGy and the radiation induced free radicals have been measured by ESR spectrometry. The ESR signals have shown the type and quantity o f radiation induced free radicals. Their study can be used for a reallistic estimation o f the degradative effect of the ionising radiation treatment of archive paper. POSTERS

- 55 -

REACTION KINETICS OF RESVERATROL WITH THIYL AND ALKOXYL RADICALS

I. Dzeba and B. Mihaljevic Radiation Chemistry and Dosimetry Laboratory, Ruder Boskovic Institute, Zagreb, Croatia

Plant derived resveratrol (/ram-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties [1], Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis o f competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1- octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. 7er/-butoxyl radicals were generated directly by peroxide bond cleavage from di-/er/-butyl peroxide in acetonitrile by light pulses of NdrYAG at 355 nm [2], and ruby at 347 nm [3], Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions o f resveratrol and other radicals generated by pulse radiolysis.

References

[1] Y. Shang, Y. Qian, X. Liu, F. Dai, X. Shang, W. Jia, Q. Liu, J. Fang, B. Zhou, J. Org. Chem. 74 5025 (2009) [2] S. Petralia, C. Spatafora, C. Tringali, M.C. Fóti, S. Sortino, New J. Chem. 28 1484 (2004) [3] B. Mihaljevic, D. Razem, Rad. Chem Phys. 67 269 (2003) - 56 -

EVALUATION OF PRIMARY INTERNAL SELF-RADIOLYTICAL EFFECT IN TRITIUM LABELLED COMPOUNDS USING ESR SPECTROMETRY

C. Postolache, R. Georgescu, C. Tuta and Gh. Bubueanu "Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), Atomistilor street, 407, 077125 Magurele Ilfov, Romania

By every Primary Internal self-Radiolytical Effect (PIRE) in tritium labelled molecules is induced a free radical. The PIRE mechanism implies three steps: (a) disintegration of tritium atom with one electron release and formation of an unstable cationic structure; (b) decomposition of the cationic structure with emission of 3He and formation o f a new cationic structure; (c) capture o f one electron from the medium and formation of one free radical. The structure o f resulted free radical is determined by the position of tritium in molecule.

In accordance with this model, the analysis of free radicals accumulation using ESR spectrometry permits the identification of tritium distribution in molecules. Because the free radicals accumulation is correlated with number of tritium atoms in samples, this method can be used for detection and evaluation of tritium activity. For development o f the study we used the following labelled compounds: HTO, polyacrylic acid labeled with tritium at carboxylic groups, polyacrylic acid-a-T, [5-T] Uridine, and [5-T] uracil oxabicyclo [3.3.0] octanic one. Tritiated compounds with 37...370 MBq activities were stored in liq. nitrogen for 1-3 days. The analysis of free radicals was performed using an EPR spectrometer Miniscope type. - 5 7 -

STUDY REGARDING MAGNETOSPIRILLUM GRIPHYSWALDENSES BACTERIA BIOCHEMYCAL CHANGES USING FTIR AND RAMAN SPECTROSCOPY

C. MihaiU), M. Mihaela0 and A. Ioan2J) ’’"Hóna Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), IRASM Multipurpose Irradiation Facility, Microbiology Laboratory ^Institute of Biology Bucharest, Department of Microbiology 3) "Ovidius" University of Constanta, The Faculty of Natural Sciences, Romania

Spectroscopy using Fourier transform and Raman spectroscopy can be used to enlighten functional groups that belong to different biomolecules that are specific to cells (proteins, lipids, carbohydrates, nucleic acids), thus obtaining valuable information regarding bacteria's biochemical composition. Since microorganisms react very promptly to the culture medium changes, the apparition of a stress agent produces a modification of the cellular enzymatic print in order to compensate for the effect of those factors, thus the bacteria self adapting to those changes. These methods can be used to highlight the metabolically modifications in cells which respond to stress factors. The biochemical modification are important in bioremediation processes like biosorbtion of metal contaminated waste water from metallurgical baths or even from irradiator pool, heavy water from nuclear power plant. The main targets are to analyze the biochemical modification appeared in presence or absence of two metals, Fe and Co. The presence of Fe is benefic for bacteria because she can absorb iron and deposit as magnetite inside the cell. The presence of Co determines changes in metabolism with the loss of many polar bindings but the growth was not inhibited even in concentration like 100 mM. - 58-

CHARACTERIZATION OF ELECTRON BEAM IRRADIATED COLLAGEN-POLYVINYLPYRROLIDONE (PVP) AND COLLAGEN-DEXTRAN (DEX) BLENDS

M. Dumitra§cu’’, V. Meltze2’, E. Sima1’, M. Virgolici3’, M.G. Albu4’, R. Minea1’, M.M. Manea3’, I.V. Moise3’ and C. Vancea1’ ' ’National Institute for Lasers Plasma and Radiation Physics, 409 Atomi§tilor Street, 077125, Mágurele, Romania 2’University of Bucharest, Faculty of Chemistry, 4-12 B-dul Regina Elisabeta, 030018, Bucharest, Romania 3’ "Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), 407 Atomi§tilor Street, 077125, Mágurele, Romania 4)Leather and Footwear Research Institute - INCDTP, Collagen Department, 93 Ion Minulescu Street, 031215, Bucharest, Romania

The aim of the present study was to investigate the influence o f electron beam irradiation on some blends o f collagen-polyvinylpyrrolidone (PVP) and collagen- dextran (DEX). The blends were prepared by mixing different quantities of collagen, PVP and DEX in distilled water. After irradiation the obtained hydrogels were processed by controlled drying and freeze-drying. Both types of materials were characterized by FT-IR, FT-Raman, TG, DSC, water uptake and SEM. The intensity of the characteristic bands, in the range 2800-3600 cm' 1 from FT-IR spectra, varied considerably as function of absorbed radiation dose. Raman spectra revealed the absence o f the characteristic peak at 2700 cm' 1 for irradiated blends at 30 kGy. Kinetic parameters were calculated from the TG, DTG and DSC data by means of isoconversion methods at different heating rates. Thereby a relation between absorbed radiation dose and activation energy was established. Water uptake studies were carried out in PBS solution (phosphate buffer saline) at 37°C and pH = 7.4 and the results revealed a decrease o f the water uptake with increasing of absorbed radiation dose. - 5 9 -

DEVELOPMENT OF MOLECULARLY IMPRINTED HEMA-BASED COPOLYMERIC SYSTEMS FOR GLUCOSE RECOGNITION

M. Akbulut and O. Giiven Department of Chemistry, Hacettepe University, 06800 Beytepe, Ankara, Turkey

Molecularly imprinted copolymeric systems can be tailored by using one or more functional monomers with a crosslinker in the presence o f a molecule behaving as the template [1], After polymerization/crosslinking template molecule is removed by solvent extraction thus leaving behind specific recognition sites and moieties in the crosslinked matrix [2 ], In this study, 2-hydroxyethyl methacrylate (HEMA) was used as functional monomer and diethylene glycol diacrylate (DEGDA) and polyethylene glycol (200) diacrylate (PEG(200)DA) were employed as crosslinking agents to imprint D(+)glucose. Molecular imprinting o f D(+)Glucose onto HEMA matrix was prepared byradiation induced crosslinkingin the presence of dimethyl sulfoxide(DMSO)/isopropyl alcohol(IPA) (3/l,v/v) at room temperature. Control matrices were synthesized through the same procedure in the absence o f D(+)Glucose. In order to evaluate the recognition and separation properties o f imprinted systems,HPLC experiments were performed. For this purpose P(-)lactose, D(+)glucose and glycerol were used as analytes and separation has been shown to be achieved successfully (Figure 1). Furthermore, to determine the size of the cavities in the imprinted polymeric networks the positron annihilation lifetime spectroscopy (PALS) was employed.

Figurel. Chromatograms o f P(-)lactose, D(+)glucose and glycerol on imprinted polymer column prepared with PEG(200)DA. Mobile phase, acetonitrile/water(5/l, v/v); flow rate, 0.3 m L.m in'1.

The radius of cavities for imprinted polymers prepared with PEG(200)DA which were swollen in water and mixture of acetonitrile/water (1/5, by volume) followed by freeze drying, were determined as 0.25 and 0.28 nm, respectively.

References

[1] H. Bodugöz, O. Güven, N.A. Peppas, JAppl. Polym. Sci, 103, 432 (2007) [2] N. Diourelov, Z. Ate§, O. Güven, M. Misheva, T. Suzuki, Polymer, 48, 2692 (2007) - 60 -

RAMAN SPECTROSCOPIC STUDY ON POROUS POLYMER MONOLITHS PREPARED BY RADIATION INITIATED POLYMERIZATION

B. Beiler'*, M. Veres2*, L. Himics2), M. Koós2) and Á. Sáfrány'* '’institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary 2*Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences, Budapest, Hungary

Due to their advantageous properties porous polymer monoliths are widely used in many areas o f modem technology. The possibility o f simple modification of the porous structure, surface chemistry and other properties allows preparing materials with the required characteristics easily. The use of gamma radiation initiation for monolith preparation has several advantages over the traditional thermal or UV-initiation methods: the process is independent of the temperature, no need for initiators and other additives and molds of almost any shape and size can be used. In order to exploit the possibilities o f the method, the effect of the preparation conditions on the properties of the formed monoliths has to be studied in detail. In this work Raman spectroscopy was used to investigate the formation and structure of monoliths prepared by gamma-radiation initiated polymerization. Measurements were performed on sample series prepared from diethylene glycol dimethacrylate monomer and different solvents that were irradiated with doses up to 40 kGy. The evolution of the bonding configuration of monomers with dose and composition of the monomer mixture was investigated. The conversion rate determined from the change in the intensity o f the C=C double bond was found to be in good agreement with the conversion determined from mass measurements. Both methods showed that the conversion is almost 100% even at as low as 16 kGy. Monoliths prepared with higher doses, however, have better mechanical properties, which, according to the Raman spectra, are related to the increasing crosslinking o f the polymer framework and incorporation of the partially polymerized monomers into the structure. -61 -

INTRODUCTION OF FUNCTIONALIZABLE GROUPS VIA RADIATION GRAFTING INTO POLYMER ELECTROLYTE MEMBRANES FOR FUEL CELLS

Y. Buchmiiller, G.G. Scherer, A. Wokaun and L. Gubler Electrochemistry Laboratory, Paul Scherrer Institut, CH 5232 PSI Villigen, Switzerland

Our work is focused on the introduction of functionalizable groups, so called linkers, to polymer electrolyte membranes. The aim is to attach antioxidant groups to the linkers to enhance the durability o f the proton conducting membrane in a fuel cell. The synthetic route we chose is radiation cografting of functionalizable monomers and precursor monomers o f a protogenic group into ETFE base film (thickness 25 jam) with subsequent animation. Typically, we performed cografting of styrene with different linkers, such as acryloyl chloride, vinylbenzyl chloride, and glycidyl methacrylate. Styrene is readily sulfonated to introduce proton conductivity. The cografting behavior of the linkers and styrene was investigated to target the desired molar fraction of the monomers in the grafted polymer. A ll films were characterized by Fourier transform infrared (FTIR) spectroscopy and elemental analysis. Using these data the graft polymerization kinetics of these systems have been determined. The cografted films were first functionalized with amines, such as thyramine and dopamine, and then sulfonated or vice-versa, depending on the stability of the compounds in acidic environment. The synthesized membranes were characterized for conductivity and ion exchange capacity (IEC). Promising membranes were tested in a fuel cell. - 6 2 -

RADIATION INDUCED, RAFT MEDIATED GRAFTING OF STYRENE ONTO POLY(ETHYLENE->4Z.T-TETRAFLUOROETHYLENE) (ETFE)

G. £elik, M. Barsbay and O. Giiven Department o f Chemistry, Hacettepe University, 06800 Beytepe, Ankara, Turkey

The development o f cost-effective proton exchange membranes to replace the state-of- the-art and expensive perfluorinated membranes such as Nafion, Flemion, and Aciplex is one of the main challenges for commercialization of polymer electrolyte fuel cell technology. Recently, partially fluorinated poly(ethylene-ű/Metrafluoroethylene) (ETFE) has been identified as a promising alternative base polymer film to prepare low- cost polymer electrolyte membranes because of its advantageous characters like superior mechanical properties and high resistance to radiation-induced damage. 1,2 The radiation-induced grafting technique, based on the utilization of a polymer material such as ETFE in combination with further chemical modification steps (sulfonation) allows the functionalization of the base material and the introduction of the desired property (proton conductivity) for preparing a fuel cell membrane.3 However this simple conventional method suffers from one simple flaw: The molecular weight and the polydispersity o f the grafted chains cannot be controlled. Predetermined molecular weights and low dispersities as well as homogeneous composition and desired architecture can be achieved by grafting of monomer onto base polymer under living/controlled free radical polymerization (CRP) conditions.4 Among the CRP methods, Reversible Addition Fragmentation-Chain Transfer (RAFT) is of particular interest as a very wide range o f functional monomers can be polymerized in a controlled manner under non-demanding reaction conditions (e.g., tolerance to oxygen and low temperatures) . 5 The present study deals with the RAFT mediated radiation-induced (0.032 kGyh'1, 60Co) grafting o f styrene on ETFE films followed by the sulfonation of the polystyrene grafts. The effect o f monomer concentration, absorbed dose and RAFT agent concentration on the grafting were investigated. The synthesized films were characterized by ATR-FTIR, XPS, DSC and TGA methods. Cross-sections of these films were investigated by SEM- EDS and Confocal Raman Spectroscopy to evaluate the grafting profile. These films have potential use as a fuel cell membrane and we believe that the method applied will present an advance in the ability o f preparing fuel cell membranes with predefined graft architecture.

References

[1] S.A. Gürsel, L. Gubler, B. Gupta, G.G Scherer., Adv. Polym. Sci., 215, 157 (2008) [2] L. Gubler, S.A. Gürsel, G.G. Schere, Fuel Cells, 5, 317 (2005) [3] M.M. Nasef, E.S.A. Hegazy, Prog. Polym. Sci., 29, 499 (2004) [4] M. Barsbay, O. Güven, MH. Stenzel, C. Bamer-Kowollik, T.P. Davis, L. Barner, Macromolecules, 40, 7140 (2007) [5] G. Moad, E. Rizzardo, S.H. Thang, Aust. J. Chem., 58, 379 (2005) -63 -

RADIOINDUCED ACRYLIC ACID GRAFTING ONTO EXTRUDED POLYSTIRENE SURFACE

V. Fugaru, C. Postolache, C. Tuta and Gh. Bubueanu "Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), Atomistilor street, 407, 077125, Magurele Ilfov, Romania

Removable surface contamination (RSC) represents the main risk factor for radiochemical laboratories workers. In case of low P energy radionuclides (3H and 14C) RSC is determined by wiping of RSC with absorbed materials smears and measuring of radioactivity at liquid scintillation device. The polystyrene materials are recommended for this applied because have a good solubility in liquid scintillation cocktails. But hydrophobic polystyrene properties implied a low sampling factor. In this paper were analyzed radioinduced hydrophilic acrylic groups onto extruded polystyrene foils. The study followed superficially grafting of individually acrylic fragments on extruded polystyrene surface. Two protocols are used:

Exposing of extruded polystyrene foils immersed in acrylic acid aqueous solution, at y radiation field emitted by 60Co source; Exposing of extruded polystyrene foils at a tritium P sources followed by immersion in acrylic acid aqueous solution.

The acrylic fragments insertion was evaluated by FTIR ATR spectrometer. The grafting yields were determined by radiometrical methods using [a-T] acrylic acid. The acrylic grafted polystyrene foils were used in made of tritium RSC smears. - 64 -

STUDIES OF NETWORK STRUCTURE AND DYNAMICS OF E- BEAM CROSSLINKED PVPs: FROM MACRO TO NANO

C. Dispenza1*, N. Grimaldi1*, M.-A. Sabatino1, D. Bulone2), D. Giacomazza2, G. Przybytniak3, S. Todaro1*, S. Alessi1* and G. Spadaro1* ^Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Universitá degli Studi di Palermo, Viale delle Scienze Ed. 6 , 90128 Palermo, Italy 2)CNR - Istituto di Biofisica (Palermo unit), Via U. La Malfa 153, 90146 Palermo, Italy 3*Centre for Radiation Research and Technology. Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland

Much interest has been paid to develop a variety of radiation-crosslinked hydrated polymeric materials, which swell in water but do not dissolve, as biocompatible materials used for wound healing, drug delivery system, surface-coating material for medically used devices, etc. With the aim of establishing design rules to produce hydrogels of controlled size at the nanoscale and desired internal network structure using conventional electron accelerators and set-ups, here we attempt a description in terms o f structural and dynamic properties of polymer networks generated through e- beam irradiation of aqueous solutions of the same model polymer, a commercial grade poly(N-vinyl-pyrrolidone), subjected to e-beam irradiation with a 12 MeV Linac accelerator, at same dose (40kGy) and dose-rate (100 kGy/h) and at the variance of polymer concentration in water. Concentration has been systematically varied from above (10, 8 , 6 , 4, 2 % w) to below (1, 0.5, 0.25, 0.1, 0.05 % w) the critical chain overlap concentration value (~l%w) of the chosen polymer in water, as estimated by intrinsic viscosity measurements. The transition between macroscopic gelation and micro-/nanogels formation is observed just below the critical overlap concentration (0.5 %w), whereas the net prevalence of intra-molecular over inter-molecular crosslinking occurs at a polymer concentration below 0.25 % w, as revealed by both dynamic and static laser light scattering measurements. Significant structural differences between nanoscalar “finite” crosslinked networks and macrogels are evidenced by both FTIR and solid state N M R spectra. Polymeric segments mobility of the formed networks, at the different scales, has been assessed through stress-rheometry, solid-state cross­ polarization times and nuclear relaxation time N M R studies of the freeze-dried residues. - 65 -

RADIATION INDUCED GRAFT POLYMERIZATION OF A FLUORINATED ACRYLATE ONTO FABRICS

R. Cai, B. Deng, Y. Yu, H. Jiang and J. Li Shanghai Institute of Applied Physics, Chinese Academy of Sciences, 201800, Shanghai, P.R.China

A fluorinated acrylate monomer, 1H,1H,2H,2H-nonafluorohexyl-1-acrylate, is grafted onto fabrics such as cotton and nylon fabrics, under simultaneous radiation-induced graft polymerization. The degree of grafting (DG) has been determined as a function of different reaction parameters such as absorbed dose and monomer concentrations. A plausible mechanism has been suggested to explain the behavior of grafting reaction. The chemical structure and morphology o f these grafted fabric samples are characterized by means of infrared spectroscopy (FT-IR), X-ray Photoelectron Spectroscopy (XPS), Scanning electron microscope (SEM). These results demonstrated that the fluoride polyacrylate are introduced onto the fabrics successfully and the morphology o f the fabrics is unchanged. Meanwhile, the contact angles of modified fabrics are measured. The result o f contact angle measurement shows the grafted fabric samples hold excellent hydrophobic property.

9

8 T

7 -

6 - i

0 4- D

3 -

Absorbe dose=30 KGy Dose rate=1.765 kGy/h 1 - [Cu(CH3COO)2]=2mmol/L

-1 o 2 4 6 8 10 12 14 16 18 (Vol.%)

Figure. Effect of fluorinated acrylate's concentrations on graft polymerization. - 6 6 -

EB-PROMOTED RECYCLING OF WASTE TIRE RUBBER WITH POLYOLEFINS

L. Mészáros, T. Bárány and T. Czvikovszky Department o f Polymer Engineering, Budapest University of Technology and Economics, H-l 111, Budapest, Műegyetemrkp. 3., Hungary

One of the principal problems of common recycling of technical polymers is the thermodynamical incompatibility. The change of the Gibbs “free energy” during the mixing - determined by the changes of enthalpy and entropy - should be directed towards the miscibility [1]. In most of cases, even between closely related polymers, the compatibility is on low level which leads to phase separation and weak adhesion between the phases. Radiation treatment may help in this problem making the polymers more compatible by creating covalent bonds between the polymer phases. Such problem arises at the recycling o f ground tire rubbers (GTR). The rubber properties of GTR could be utilized by mixing the GTR with thermoplastic olefins. With the aid of radiation treatment the rubber-like properties of these types o f thermoplastic elastomers can be increased. In this study polyethylene (PE) (50-70 wt%) as thermoplastic olefin, 30 wt% o f GTR and ethylene vinyl acetate (EVA) (0-20 wt%) as rubber-like compatiblizing material were used for preparation of a recycled rubber containing blend, processable by thermoplastic processes. The melt-mixing o f the samples was made by extrusion and then the test specimens were injection molded. The injection molded samples were than treated by high energy electron beam. On the specimens tensile tests, hysteresis, falling weight impact tests, hardness measurements, and dynamic mechanical thermal analysis (DMA) were carried out. The results proved the benefit of the electron beam treatment.

Reference

[1] J. Brandrup, M. Bittner, W. Michaeli, G. Menges: Recycling and recovery of plastics, Hanser, Munich (1996) -67 -

THE INFLUENCE OF THE INITIAL PREPARATION AND CRYSTALLINITY ON THE FREE RADICAL EVOLUTION IN GAMMA IRRADIATED POLY(L-LACTIDE)

D. Milicevic, D. Milivojevic and E. Suljovrujic The Vinca Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia

Poly-L-lactide (PLLA) is a well-known biodegradable and biocompatible semi­ crystalline polymer used in a wide variety of applications, from implantable medical devices and drug release matrices to environmentally friendly packaging materials; the diversity in initial preparation, morphology and crystallinity plays a significant role in most o f these applications. On the other hand, gamma radiation as a processing tool has often been used for the sterilization of sensitive PLLA products; depending on initial polymer state the radiation-induced evolution in structure and properties can differ significantly. This study presents the influence of initial preparation and crystallinity on the evolution of free radicals in PLLA induced by gamma irradiation. For this purpose, a set o f PLLA samples with different crystallinities, between 20% and over 70%, was prepared by varying the preparation conditions and exposed to gamma radiation in the air to the absorbed dose o f 25, 50 and 100 kGy. Additionally, the annealing treatment at 80°C was applied on the part of the samples. The presence and evolution o f free radicals were followed using electron spin resonance (ESR) spectroscopy during the period of 1 month. The further characterization was conducted by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and wide angle X-ray scattering (W AXS) measurements. Presented results show that damaging long-lived residual free radicals in the irradiated PLLA are formed in the core o f the crystalline region suggesting that the degree of crystallinity, crystalline size and perfection are the main factors which govern the lifetime of these radicals. Furthermore, annealing treatment can substantially reduce the concentration o f free radicals and it looks necessary to apply this treatment for irradiated PLLA samples with large crystallinity. - 6 8 -

GRAFITING ON LUMINESCENT POLYMETHYLMETACRYLATE TO IMPROVEMENT OF LUMINESCENCE

D.F. Parra, G. Fontana, P.L Forster, L.G. Marchini, A.B. Lugao Nuclear and Energy Research Institute-IPEN-CNEN/SP. Av. Professor Lineu Prestes, 2242, - Cidade Universitária 05508-000, Sao Paulo-SP Brazil

Due o f advantages in photoluminescent (PL) properties to promissor applications, rare earths ions (RE3+) are being studied in the last years. Rare earths complexes have unique spectroscopic characteristics as very narrow emission lines, high fluorescence emission efficiency due to absorption coefficient of ligands, and energy transfer to the central ion, making then potential candidates to high-tech applications. Luminescent polymers use this strategy and in the majority of the cases need improvement of stability as that of polymethylmetacrylate doped with Eu(tta)3 (H 2 0 )2. In this sense grafting of fluormonomers are developed on the films surface to improve the stability of the luminescent films.

Acknowledgment: Support by CNPQ, FAPESP Process n° 2009/18627-4, CNPq Process n° 310849/2009-8, IPEN/CNEN. - 6 9 -

RADIATION MODIFIED HIGH IMPACT POLYSTYRENE (PS-HI)

Z. Jeleié1* and F. Ranogajec2* ^PLIVA Croatia Ltd., TAPI Research and Development, Zagreb, Croatia 2)Ruder Boskovic Institute, Zagreb, Croatia

The purpose of applying the high-energy gamma-ionizing radiation with doses up to 1000 kGy was to enable controllable change of mechanical properties o f high impact polystyrene (PS-HI) and, at the same time, to investigate the possibility of using reprocessed irradiated polymeric material. Dielectric relaxation of a radiation modified high impact polystyrene (PS-HI) has been investigated below the polystyrene glass transition temperature (Tg) by the direct current (dc) charging/discharging transient method. Time dependence of charging/ discharging current has been well described for the PS-HI by the power function of the logarithm of time. The relationship between the dc conductivity and the dielectric relaxation time (x) has been approximated by the fractal dimension. The dc transient current method is considered to be a practical tool for analyzing the dielectric relaxation process of the radiation modified PS-HI. It was also shown that yield strength and tensile strength increase while elongation at break decreases with increasing radiation dose. The specimen prepared by a post-irradiation moulding gave higher melt flow rate than those o f specimen formed before irradiation. These results indicate that after radiation the system of PS-HI is reprocessable. It is concluded that an oxygen environment at the beginning of irradiation leads to enhanced chain scission at the expense of crosslinks via peroxide formation and causes oxidative degradation of the main polymer chain of irradiated PS-HI at a low dose. However, at higher absorbed doses the quasi-inert environment has been established and crosslinking, due to recombination of macroradicals, is dominant. - 70 -

EFFECT OF GAMMA RADIATION ON CHLOROBUTYL RUBBER VULCANIZED BY THREE DIFFERENT CROSSLINKING SYSTEMS

S.R. Scagliusi, E.L.C. Cardoso and A.B. Lugao Nuclear and Energy Research Institute, Center of Chemistry and Environment (CQMA), Av. Prof. Lineu Prestes, 2242 - Cidade Universitária - 05508-900, Sáo Paulo/SP - Brazil

The development of halogenated butyl rubber (chlorobutyl) in the 1950's and 1960's greatly extended the usefulness of butyl. These properties permitted development of more durable tubeless tires with the air retaining innerliner chemically bonded to the body o f the tire. Tire innerliners are by far the largest application for halobutyl. When polymers are subjected to high energy radiation, a variety of chemical reactions may occur subsequent to the initial ionization and excitation events. These reactions lead to changes in the molecular weight of the polymer through scission (S) and crosslinking (X) o f the molecules and affect the physical and mechanical properties. In the halobutyl rubbers the chain scission may predominate. This work aims to show effects of gamma radiation in properties o f clorobutyl rubbers vulcanized with sulfur, using sulfur donators and phenolic resin. The butyl rubber was studied in index. The samples were characterized before and after irradiation. Gamma radiation doses used were: 25 kGy, 50 kGy, 100 KGy, 150 kGy and 200 KGy, in order to identify whether cure system is the most stable under irradiation. Was observed that the chorobutyl rubber cured by phenolic resin, are less sensitive to gamma radiation. -71 -

STUDY OF GAMMA IRRADIATED POLYETHYLENES BY TEMPERATURE MODULATED DIFFERENTIAL SCANNING CALORIMETRY

B. Secerov, S. Galovic, S. Trifunovic, D. Milicevic and E. Suljovrujic The Vinca Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia

The various polyethylenes (PEs) and effects of high energy radiation on theirs structures were widely studied in the past using conventional Differential Scanning Calorimetry (DSC) measurements. In this work, we applied the Temperature Modulated Differential Scanning Calorimetry (TMDSC) technique in order to obtain more information about the influence of initial structural differences and gamma radiation on the evolution in structure and thermal properties of different polyethylenes. For this reason, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) samples were exposed to gamma radiation, in air, to a wide range of absorbed doses (up to 2400 kGy). The separation of the total heat flow TMDSC signal into a reversing and nonreversing part enabled to observe the low temperature enthalpy relaxation (related to the existence o f the “rigid amorphous phase”) and recrystallization processes as well as to follow their and/or radiation-induced evolution of melting in a more revealing manner compared to the case of the conventional DSC. Consequently, our results indicate that TMDSC could improve the understanding of radiation-induced effects in polymers. RADIATION SYNTHESIS AND CHARACTERIZATION OF NETWORK STRUCTURE OF NATURAL/SYNTHETIC DOUBLE­ NETWORK SUPERABSORBENT POLYMERS

M. §en and H. Hayrabolulu Hacettepe University, Department of Chemistry, Polymer Chemistry Division, Beytepe, 06800, Ankara, Turkey

Superabsorbent polymers (SAPs) are moderately cross linked, 3-D, hydrophilic network polymers that can absorb and conserve considerable amounts of aqueous fluids even under certain heat or pressure. Because o f the unique properties superior to conventional absorbents, SAPs have found potential application in many fields such as hygienic products, disposable diapers, horticulture, gel actuators, drug-delivery systems, as well as water-blocking tapes coal dewatering, water managing materials for the renewal of arid and desert environment, etc. In recent years, naturally available resources, such as polysaccharides have drawn considerable attention for the preparation of SAPs. Since the mechanical properties of polysaccharide based natural polymers are low, researchers have mostly focused on natural/synthetic polymer/monomer mixtures to obtain novel SAPs. The aim o f this study is to synthesize and characterization of network structure of novel double-network (DN) hydrogels as a SAP. Hydrogels with high mechanical strength have been prepared by radiation induced polymerization and crosslink of acrylic acid sodium salt in the presence of natural polymer locust bean gum. Liquid retention capacities and absorbency under load (AUL) analysis of synthesized SAPs was performed at different temperatures in water and synthetic urine solution, in order to determine their SAP character. For the characterization of network structure of the semi-IPN hydrogels, the average molecular weight between cross links (Me) were evaluated by using uniaxial compression and oscillatory dynamical mechanical analyses and the advantage and disadvantage of these two techniques for the characterization of network structures were compared. EB TREATMENT OF CARBON NANOTUBE-REINFORCED POLYMER COMPOSITES

G. Szebényi1’, G. Romhány1’, B. Vajna2’ and T. Czvikovszky1’ 1’Department of Polymer Engineering, 2)Department of Organic Chemistry and Technology Budapest University o f Technology and Economics, H-1111 Budapest, Hungary

A small amount - less than 0.5% - carbon nanotube reinforcement may improve significantly the mechanical properties of epoxy based composite materials. The basic technical problem is on one side the dispersion o f the nanotubes into the viscous matrix resin. Namely the fine, powder-like - less than 100 nanometer diameter - nanotubes are prone to form aggregates. On the other side, the good connection between the nanofiber and matrix, - which is determining the success o f the reinforcement, - requires some efficient adhesion promoting treatment. After an elaborate masterbatch mixing technology we applied Electron Beam treatment of epoxy-matrix polymer composites containing carbon nanotubes in presence of vinylester resins. The Raman spectra o f vinylester-epoxy mixtures treated by an 8 MeV EB showed the advantage o f the electron treatment. Even in the case of partially immiscible epoxy and vinylester resins, the anchorage of carbon nanotubes reflects improvement if a reasonable 25 kGy EB dose is applied. Atomic Force Microscopy as well as mechanical tests on flexural and impact properties confirm the benefits o f EB treatment. Simultaneous application of multiwall carbon nanotubes and „conventional” carbon fibers as reinforcement in vinylester modified epoxies results in new types of hybrid nanocomposites as engineering materials. The bending- and interlaminar properties of such hybrid systems showed the beneficial effect of the EB treatment.

Acknowledgment: This work has been supported by the New Hungary Development Plan (Project ID: TÁMÖP-4.2.1/B-09/1/KMR-2010-0002).

References

[1] Szebényi G., Romhány G.: Materials Science Forum, 659, 91, (2010) [2] Szebényi G.: PhD Thesis, Budapest University of Technology (2011) - 74 -

IMPROVEMENT OF PESTICIDE ADSORPTION CAPACITY OF CELLULOSE FIBRE BY HIGH-ENERGY IRRADIATION- INITIATED GRAFTING OF GLYCIDYL METHACRYLATE

^E. Takács, ^L. Wojnárovits, l,2)T. Fekete and 2)J. Borsa ^Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary 2)Budapest University of Technology and Economics, Budapest, Hungary

Sustainable development needs renewable raw materials applied wherever possible. Cellulose is the most abundant biopolymer on earth; various modifications of its properties for special uses are important issues of the research. Some contaminations in wastewaters, e. g. pesticides, are hydrophobic materials; their adsorption on hydrophilic cellulose substrates is very limited. Cotton cellulose was grafted by glycidyl methacrylate in simultaneous grafting using gamma irradiation initiation. Water uptake of cellulose significantly decreased while adsorption of phenol and a pesticide molecule (2,4- dichlorophenoxyacetic acid: 2,4-D) increased upon grafting. As the figure shows on untreated sample even negative 2,4-D adsorption occured, due to the selective adsorption o f water from the solution; the adsorption did not approache its saturation value even in a 30 hours time period investigated. - Saturation o f phenol adsorption was achived after 5-6 hours; adsorption Time, hours equilibrium data of phenol fitted the Langmuir isotherm. - 75 -

PRE-IRRADIATION INDUCED PRAPARATION OF AMINE-TYPE ADSORBENTS WITH EMULSION GRAFT POLYMERIZATION OF GLYCIDYL METHACRYLATE ON PE NON-WOVEN FABRIC

H. Ma, S. Yao, J. Li and M. Wang Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P. 0 . Box 800-204, Shanghai 201800, P. R. China

A m ild pre-irradiation method was used to graft glycidyl methacrylate (GMA) onto polyethylene (PE) non-woven fabric. The polymer was irradiated by electron beam at a voltage o f 1.8 MeV and a current of 2 mA in air atmosphere at room temperature. The degree of grafting (Dg) was determined as a function of reaction time, irradiation dose, monomer concentration and temperature. After 30 kGy irradiation, with 5% GMA, the surfactant Tw-20 of 0.5% at 55 °C for 15 min, the trunk polymer was made grafted at a D g of 150%. Selected PE-g-PGMA of different D gs was modified with such compounds as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). The obtained amine-type adsorbents were prepared specialty for the further removal o f copper and uranium from solution. It was shown that at least 90% 1 ppm copper and 60% uranium with the initial concentration from 3 to 1 0 0 0 ppb can be removed from water.

U /ppb Removal Rate / % uranyl nitrate pure uranyl Solution solution with nitrate solution NaHC03 Adsorbents- EDA TETA EDA TETA type J 91.5 87.6 42.9 48.7 10 96.4 96.1 74.0 69.3 100 90.5 89.2 65.2 61.1 1000 77.5 71.9 64.2 60.1

Time (min)

Fig. Time course of GM A grafting on PE Table. Removal Rate of U ions in two non-woven fabrics. solutions with two adsorbents. Dose: 30 kGy, GMA concentration: 5%, Temperature: 55°C.

Reference

[1] N. Seko, N. Thi Yen Ninh, M. Tamada, Rad. Phys. Chem. 79, 22 (2010)

Corresponding author, [email protected] RADIATION GRAFTING OF STYRENE ONTO CELLULOSE MICROSPERES AND SUBSEQUENT ACYLATION/AMINATION FOR APPLICATION IN WASTEWATER TREATMENT

Y. Zhangl), L. Xu2), L. Zhao3), J. Peng1*, J. Li1* and M. Zhai1* ^Beijing National Laboratory for Molecular Sciences, Department of Applied Chemistry and the Key Laboratory of Polymer Chemistry and Physics of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China 2*Department o f Energy and Resources Engineering, College of Engineering, Peking University, Beijing 100871, China 3*R & D Laboratories, Advanced Materials Research Center, Nissin Electric Co. Ltd., Japan

Nowdays, ion-exchange adsorbents are increasingly used in the removal of metal ions due to their regeneration. In this study, an anion-exchange adsorbent was prepared by radiation-induced grafting o f styrene onto the surface of cellulose microspheres, followed by acylation and animation processes. The structure o f the prepared adsorbent was confirmed by FTIR and elemental analyses. The grafting yield was adjusted by the total absorbed dose, dose rate and the concentration of styrene. The resultant adsorbents with 3.2% nitrogen content possessed high ion exchange capacity and adsorption performance toward Cr(VI) ions. These features suggested that the adsorbent has potential for application in wastewater treatment.

G mic

c o c h 2c i O Scheme 1. Synthesis route for the preparation of anion exchange adsorbent. - 7 7 -

EFFECTS OF y-IRRADIATION ON CROSSLINKING OF PUI/OVS NANO-COMPOSITE FOAM

C. Zhou, W. Cao, J. Guo, T. Zhai and X. Zeng Beijing Research Center for Radiation Application, Key Laboratory of Radiation Technology and Advanced Materials of Beijing Academy of Science and Technology, Beijing, China, 100012

The effect o f absorbed dose on the properties of the polyurethane-imide PUI/octavinyloctasilasesquioxane (OVS) nano-composite foam containing 2- hydrooxyethyl methylacrylate was investigated by using y-ray irradiation. The thermal analysis experiment indicated that the thermo stability of radiation crosslinking PUI/OVS nano-composite foam was the best when the absorbed dose was 50kGy. The dynamic study also testified the elastic modulus (E ) of glassy zone of radiation crosslinking PUI/OVS nano-composite foam was the best when the absorbed dose was 50kGy, while the loss modulus (E) o f glassy zone o f composite foam was the best when the absorbed dose was 75kGy. The compressive strength, fire retardance and acoustic property o f nano-composite foam increased with the increase o f the absorbed dose.

References

[1] V.N. Bliznyuk, T.A. Tereshchenko, MA. Gumenna et al., Polymer, 49(9) 2298 (2008) [2] T.F. Baumann, T.V. Jones., J. Polymer Sci.Part A, 47 2589 (2009) - 78 -

OPTIMIZATION OF ELECTRON BEAM CROSSLINKING OF WIRE AND CABLE INSULATION

Z. Zimek, G. Przybytniak and A. Nowicki Center for Radiation Research and Technology Institute of Nuclear Chemistry and Technology, Warsaw, Poland

The computer simulations based on Monte Carlo method and the ModeCEB software program were carried out in connection with EB radiation set-up for crosslinking of electrical wire and cable insulation, located at the Center for Radiation Research and Technology of the Institute o f Nuclear Chemistry and Technology [1]. The theoretical predictions for absorbed dose distribution in irradiated electrical wire and cable insulation caused by scanned EB were compared to the experimental results of irradiation which were carried out in the experimental set-up based on ILU 6 electron accelerator, which is characterized by the following parameters: • Electron energy 0.5-2.0 MeV, Average beam current 40-10 mA, pulse duration 400 jis, • Width of scanning up to 80 cm, • Scan frequency up to 50 Hz. The computer simulation o f the dose distributions in two-sided irradiation system by a scanned electron beam in multilayer circular objects was performed for different process parameters: electrical wire and cable geometry (thickness o f insulation layers and cupper wire diameter), type of polymer isolation, electron energy, energy spread, geometry o f electron beam and electrical wire and cable distribution at irradiation zone. The geometry of electron beam distribution in irradiation zone was measured using TVA and PVC foil dosimeters for electron energy range available in ILU 6 accelerator. The temperature rise o f irradiated electrical wire and irradiation homogeneity were evaluated for different experimental conditions to optimize process parameters. The obtained results o f computer simulation were supported by experimental data of dose distribution based on gel-fraction measurements. Such agreement indicates that computer simulation ModeCEB is correct and sufficient for modeling o f absorbed dose distribution in multi-layer circular objects irradiated with scanned electron beams [2 ].

Acknowledgement: The R& D activities are supported by the European Regional Development Found in the frame of the project UDA-POIG.Ol .03.01-14-052/09

References

[1] V.T. Lazurik, V.M. Lazurik, G. Popov, Yu. Rogov, Z. Zimek, “Information System and Software for Quality Control of Radiation Processing”, Warsaw, Poland, 2011 (in print) [2] I. Kaluska, V.T. Lazurik, V.M. Lazurik, G. Popov, Yu. Rogov, Z. Zimek, Radiat. Phys. Chem., 76, 1815 (2007) - 7 9 -

SPECTRALLY RESOLVED THERMOLUMINESCENCE OF Cu-Ag AND Mn DOPED LTB SINGLE CRYSTALS AND GLASSES

M . Ignatovych'*, M . Fazoli2) and A. Kelemen3* ^O.Chuiko Institute of Surface Chemistry, NASU, 17 Gen. Naumov Str., Kyiv 03164, Ukraine 2)Deapartment of Material Science, University of Milan-Bicoca, via Cozzi 53, Milan 20125, Italy 3)Institute o f Isotopes, P.O. Box 77, Budapest 1525, Hungary

Doped lithium tetraborate (LTB) are well-known polyfunctional materials that are widely used during many years as X-ray phosphors, scinitillators and termoluminescent (TL) detectors. They received very successful applications in personal and clinical dosimetry as tissue-equivalent TL dosimetric materials. However up to now the mechanism of their TL performance is still under discussion. There is no consensus concerning the nature of charge traps and recombination TL luminescence centers even for most widely used and commercially produced LTB: Cu phosphors. There are different opinions in the literature as to the role o f dopant ions - either being directly involved in TL emission or only „improving”, enhancing TL sensitivity of intrinsic centers of LTB host that are common for different doped samples. It is worth to note that these statements were made on the base o f traditional TL technique from measuring the dependence of TL response o f doped LTB samples only versus temperature. But during last years it was developed advanced thermoluminescence technique - spectrally resolved - that permits the measurement of TL response simultaneously from temperature and TL emission wavelength. Here we present the results of using just spectrally resolved thermoluminescence technique for study of Cu-Ag and Mn doped LTB single crystals and glasses. Obtained results allow to conclude: 1. TL emission bands for LTB:Cu, LTB.Mn and LTB: Ag proved to be at different wavelength: 370 nm, 608 nm and 272 nm, respectively. Comparison with their photoluminescence (PL) spectra revealed the perfect agreement between the wavelength o f the TL and PL emission bands. It strongly points that the dopants are directly involved as recombination centres in the TL process. 2. Comparison of TL glow curves o f non-doped and doped LTB single crystals and the corresponding glassy samples showed that: a) structure and shape o f the TL glow curves are different. Single crystals containing charge carrier traps with definite activation energy displayed distinct peaks in the TL glow curves while the corresponding glassy samples exhibited broad TL curves without individual TL peaks, b) TL intensity of the glassy samples is substantially lower as compared to the corresponding single crystals. This may be caused by the poor energy storage o f the ionizing radiation. - 8 0 -

THERMOLUMINESCENCE CHARACTERISATION OF NEWLY DEVELOPED Cu-DOPED LTB MATERIALS

A. Kelemen1*, D. Mesterházy'*, M. Ignatovych2* and V. Holovey3* '’institute of Isotopes, HAS, P.O. Box 77, Budapest 1525, Hungary 2*O.Chuiko Institute of Surface Chemistry, NASU, 17 Gen. Naumov Str., Kyiv 03164, Ukraine, 3*Institute of Electron Physics, NASU, 88000 Uzhgorod,Ukraine

Cu-doped lithium tetraborate (LTB:Cu) is a tissue-equivalent thermoluminescent material that can be successfully applied in the fields of personal and clinical dosimetry. Different methods of preparing this material have been developed giving rather different TL characteristics. In the near past years single crystals and glassy samples were synthesized in the Institute of Electron Physics. This new material, mainly the single crystal, shows promising dosimetric properties. The 380 nm wavelength of its emission makes it suitable in using with standard commercially available TL readers. The structure o f its glow curve is not complicated and suitable for a simple evaluation procedure. The TL sensitivity o f the single crystals is high enough for detecting small dose values (0.1 mGy). The dose response linearity o f the material was investigated for a large dose region and was found to be linear starting from 0.1 mGy to several kGy-s. The fading characteristics of the LTB:Cu samples were analyzed under two different experimental conditions of storage: dark (thermal fading) and light (optical fading). Both properties are good, especially the low light sensitivity is favorable as compared to other LTB materials. -81 -

RADIATION INDUCED PREPARATION OF NEW MULTIFUNCTIONAL NANOBIOWEBS

A. Gopalan1’2*, K.R. Ko1*, S.-H. Lee1*, S. Komathi2*, M. Veres3* and K.-P. Lee1’2* ^Department of Nano-Science & Technology, Kyungpook National University, Daegu, Korea 2)Department Chemistry Graduate School, Kyungpook National University, Daegu, Korea 3*Research Institue of solid state physics and optics, Hungary

New poly(vinylidene fluoride) based multi-functional (electroconductive, bioactive and catalytic) nano-biowebs were prepared. In a typical approach, a mixture of poly (vinylidene fluoride) and silica was electrospun to fabricate PVdF-silica nanofibers (PVdF-Si NFs). Gold nanoseed particles were then loaded into the PVdF-Si NFs by gamma radation induced reduction method. The morphology o f PVdF-Si NFs/Au was examined by field emission scanning electron microscopy. The presence o f Au seed particles on the surface of PVdF-Si NFs/Au was confirmed by EDA X measurements. The crystal structure o f the formed Au particles and the formation of Si were confirmed by X-ray diffraction analysis. The thermal stability o f the PVdF-Si NFs/Au was evaluated by thermogravimetry. The mulifunctionalities (electroconductive, bioactive and catalytic) of the nanowebs were evaluated by cyclic voltammetry and the cyt c immobilized onto nano-bioweb (PVdF-Si NFs/Au/cyt c NBW) exhibited amperometric response to o f nitrite ions. - 82 -

RADIATION SYNTHESIS OF SEROALBUMIN NANOPARTICLES

S.L. Soto Espinoza1’, V. Risso1’, E. Pawlak2), E.E. Smolko2’ and M. Grasselli1’ ’’Dpto. LaMaBio, Dpto. de Ciencia y Tecnología, Universidad Nációnál de Quilmes, Bemal, Buenos Aires, Argentina 2)Centro Atómico Ezeiza, Comisión Nációnál de Energia Atómica, Buenos Aires, Argentína

Ionizing radiation has been industrially used for many years in polymer processing. The two main streams of applications belong to crosslinking and degradation reactions. More sophisticated commercial products are achieved under development such as wound-dressing hydrogels, membranes and sensors. Radiation technology can be used to generate polymer microparticles by precipitation polymerization with a very narrow particle size distribution. Additive-free initiation and easy process control are the main advantage of this technology. In this way, methacrylate-based microspheres can be prepared by radiation-induced polymerization of diethyleneglycol dimethacrylate (DEGDMA) and others cross linkers in organic solvent. Particle diameter can be achieved, from the range 0.8 to 8 pm, by selection of the appropriate organic solvent. Tailor-made microspheres were further developed by copolymerization of DEG DM A with reactive monomers, such as glycidyl methacrylate, or particular monomers to rich functional microspheres, however lower-diameter particles still have not been achieved by this technique. Small polymeric particles can be also reached by ionizing radiation technology, but via another strategy. Soluble synthetic polymers can be intramolecularly cross linked by quantum-ray, creating nanogels, which was first reported by Ulanski el al.. Authors managed irradiation conditions to generate intramolecular crosslinking onto soluble polymer molecules in random coil conformation. Many proteins are also soluble macromolecules; however, most of them have a very compact and defined three dimensional structure, which are known as globular proteins. Radiation effect onto globular proteins, fragmentation and aggregation process has been described by many authors. Modification o f primary, secondary and ternary structure of seroalbumin has also been reported. In this work, a soluble and globular protein such as seroalbumin was used as basic unit to build nanoparticles. Detectable protein nanoparticles in the range o f 20 to 50 nm were reached after gamma irradiation of aqueous protein solution in the presence of polar organic solvents. Nanoparticles were characterized by Dynamic Light Scatering, SEM and TEM. Spectroscopic data from Circular Dicroism and fourth derivative UV-vis spectroscopy showed protein molecules keep its general three-dimensional structure into the created nanoparticles.

Acknowledgement: The authors thank to CONICET, MINCyT of Argentina and IAEA for grants. PREPARATION OF CO/PD ALLOY PARTICLES DISPERSED MULTIWALLED CARBON NANOTUBE SUPPORTED NANOCATALYSTS VIA GAMMA IRRADIATION

K.-P. Lee 1,2), S.-H. Lee1’, S. Komathi2’and A. Gopalan1,2’ ' ’Department of Nano-Science & Technology, Kyungpook National University, Daegu, Korea 2)Department Chemistry Graduate School, Kyungpook National University, Daegu, Korea

New multiwalled carbon nanotube/ silica supported cobalt-palladium bimetallic nanocatalysts (MWNT@silica/Co-Pd NPs) were prepared by a simple one step gamma irradiation method. The method involves the in-situ surface modification of MWNT with silica (MWNT@silica) and simultaneous formation of Co-Pd bimetallic NPs using gamma irradiation. The bimetallic NPs were stabilized by silica particles formed over the surface o f MWNT. An extensive characterization o f MWNT@silica/Co-Pd NPs on structural, morphological. and electrochemical. aspects is described. MWNT@silica/Co-Pd NPs were characterized by field emission scanning microscopy (FESEM), UV-visible spectroscopy, X-ray diffraction (XRD) thermogravimetric analysis (TGA), and Raman spectroscopy. The stabilizing effect of silica particles and irradiation dosage levels on the composition of Pd to Co were analyzed. The electroatalytic activities of the MWNT@silica/Co-Pd NPs were investigated by cyclic voltammetry. ASSESSMENT OF y-IRRADIATED POLYETHYLENE OXIDE) BASED HYDROGELS AND NANOCOMPOSITES

I. Pucic and T. Jurkin Laboratory for Radiation Chemistry and Dosimetry, Ruder Boskovic Institute, Zagreb, Bijenicka 54 Croatia

Preparation of poly(ethylene oxide) (PEO) based hydrogels and nanocomposites by ionizing radiation may ease development of new materials with desired properties like sterile hydrogels or polyelectrolytes with enhanced conductivity. Due to its chemical nature if PEO is irradiated dry, its chains are directly affected and in presence of oxygen it generally degrades, while in the inert atmosphere partial crosslinking is observed. In aqueous solution radiation produces reactive species in water and the reaction of these species with PEO chains is supposed to lead mostly to crosslinking. The degree of crystallinity of PEO decrease both on degradation and crosslinking. We prepared and irradiated by y-radiation to various doses aqueous solutions of PEO with nano-silica and without it. The solutions were irradiated in presence o f oxygen and in the inert atmosphere. The dried samples were investigated by a number of experimental techniques. To observe all changes corresponding to radiation effects the FTIR spectra were recorded as melt and then as films obtained by in-situ crystallization. In all samples changes were observed in vibrations characteristic of crystalline PEO at 1342 cm' 1 and 1360 cm’ 1 that merged into a single absorption indicating amorphization. In samples irradiated in the inert atmosphere and without nano-silica, changes in the shape and intensities of -C-O-C- triplet at around 1100 cm' 1 suggest crosslinking. On the other hand, the addition o f nano-silica led to increase in intensities of -C-O-C- triplet what is more consistent degradation. The changes in selected FTIR absorptions were correlated to DSC results. The concentration o f aqueous solution was significant for the outcome while the molecular mass of PEO had minor influence. In the presence o f oxygen the protective effect of sol vent seems to be questionable. - 8 5 -

FABRICATION OF SILVER NANOPARTICLES IN POLY(2-HYDROXYETHYL METHACRYLATE/ITACONIC ACID) HYDROGEL NETWORKS BY GAMMA IRRADIATION

E. Suljovrujic, T.V. Milic and M. Micic Vinca Institute of Nuclear Sciences, P.O. Box 522, 11001 Belgrade, Serbia

The silver nanoparticles were fabricated via in situ reduction of silver nitrate embedded in swollen hydrogel using gamma radiolysis method. Copolymeric hydrogels based on 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) previously synthesized by gamma radiation were used as a carrier and a stabilizing agent, while ethyl alcohol was used as a free radical scavenger. The influence o f different contents of IA and metal ion concentrations on the size and distribution of nanoparticles was investigated. The Ag/P(HEMA-co-IA) nanocomposites were characterized by high resolution scanning electron microscopy (SEM), wide-angle X-ray diffraction (W AXD), UV-vis spectroscopy and swelling measurements. Escherichia coli was used as test bacteria, to prove the antimicrobial properties of Ag/P(HEMA/IA) nanocomposite. Inhibition kinetics o f bacteria growth was investigated by measuring the colony-forming unit (CFU). The antibacterial effectiveness o f the Ag/P(HEMA-co-IA) hydrogel nanocomposite was demonstrated even at small silver concentrations. - 8 6 -

EPR ANALYSIS OF SURAKHANY OIL ASPHALTENES

D. Abbasova Institute of Radiation Problems of AzNAS, Azerbaijan

In this work EPR of Surakhany oil resins were investigated. From the analysis of the main characteristics of the EPR spectra due to paramagnetic defects in the conjugated chain formed by a system of delocalized 71-electron structure of the petroleum resins found that the inhomogeneous broadening o f EPR lines because o f interaction o f paramagnetic centers (PC) with oxygen atoms distributed randomly on areas of delocalization of spin. Based on the temperature dependence of the concentration o f the PC found that along with thermally activated paramagnetism in the samples of resin, there are also so- called biographical free radicals initially present in the samples. Change o f EPR line shape with temperature increasing to pure Lorentzian indicating a strengthening o f the role o f exchange interactions indicative of a deviation from random distribution o f the PC uniform. Have been shown that the differences in spectral characteristics o f the EPR of oil resins can be used to diagnose and identify the origin of oils from different oilfields. - 87 -

BEHAVIOUR OF FLUOROPLYMERS IN PRESENCE OF TRITIATED WATER

Gh. Bubueanu, C. Postolache and C. Tuta "Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), Atomistilor street, 407, 077125, Magurele Ilfov, Romania

One o f the most used methods for tritium recovery from tritiated water relies on combined electrolysis with catalytic isotope exchange techniques. The electrolytic cell converts the tritiated water or tritiated heavy water into a hydrogen, deuterium and tritium mixture. The mixture is purified and then tritium is recovered by catalytic isotopic separation techniques. Tritium presence in the system induces an intense radiation field especially at aqueous solution interface. This can generate significant structural modifications with potentially negative effects. In this paper work it is followed the study of radiolytic phenomena in Pt/C/PTFE isotopic exchange catalyst, NAFION membranes and VITON fluoroelastomer in presence of trititated water with high radioactive concentration. Radiolytical processes were analyzed by: - Exposure of fluorop6 lymers samples immersed in H2O at gamma radiation field (60- Co source) in vacuum, at liq. Nitrogen temperature and at ambient temperature respectively. - Immersing of NAFION, Pt/C/PTFE catalyst and VITON samples in tritiated water with high activity (3.7 and 37 TBq/L) for different time period. In both cases the samples were characterized by FT IR ATR, and fluoride ions emission from polymeric matrix. Experimental results were correlated with quantum-chemical simulations. - 8 8 -

REACTION MECHANISMS IN y IRRADIATED HIGH SURFACE SILICA -ELASTOMER SYSTEMS

D. Dondi1*, A. Buttafava1*, A. Zeffiro1’, S. Bracco2), P. Sozzani2) and A. Faucitano1' ’'Department of Chemistry, University of Pavia,.V.le Taramelli 12, 27100 Pavia; 2)Department of Material Science, University of Milano-Bicocca, Italy

In this work the mechanism o f the y-ray induced vulcanization o f the binary systems consisting of styrene butadiene rubber (SBR; 30 % styrene, 25 % vinyl units) and high surface silica (160-1000 m 2/g) are investigated by matrix EPR spectroscopy, ATR-FTIR and by measuring the crosslinking kinetics. The experiments have dealt with pristine silica, silica modified by radiation grafting of polybutadiene olygomers (SÍO2/PB) and the SBR compounds containing 30-40 % of pristine or modified silica. The irradiation under vacuum of the pristine silica gives rise to thermally unstable species which decay at very low temperature, below 180 K. When the SBR/silica compounds are irradiated, in addition to the SBR radicals, also SBR chain radicals chemically linked to the silica surface are detected. The yield o f such grafted radicals is greatly enhanced when using silica coated with polybutadiene olygomers bearing high (25-45 %) vinyl double bond content. The rationale of such observation is that the species generated within the bulk o f the silica particles migrate to the surface where are scavenged by the vinyl double bonds o f the absorbed chains. It is thus assessed that the direct radiolysis of silica plays an active role in the radiation vulcanization process by promoting the formation of silica-rubber chemical links which are of key importance in the reinforcement mechanism. The crosslinking kinetics were found to be coherent with the above observation showing that the crosslinks yield vs dose ratios increase in the order: pure SBR< SBR/pristine Si0 2

Bibliography

[1] D. Dondi, A. Buttafava, C. Palamini, F. Pepori, A. Lostritto. L. Giannini, M. Nahmias, L. Conzatti, A. Faucitano, Macromol. Symp., 301, 98 (2011) - 89 -

TIME-DEPENDENT BEHAVIOR OF ELECTRON IN N-DODECANE STUDIED BY FEMTOSECOND PULSE RADIOLYSIS

T. Kondoh, J. Yang, K. Norizawa, K. Kan, T. Kozawa, A. Ogata, S. Tagawa and Y. Yoshida The Institute of Scientific and Industrial Research, Osaka University, Japan

The geminate ion recombination was studied by the femtosecond pulse radiolysis system which was developed by using a photocathode RF gun LIN AC in Osaka University. We found the excited radical cation as the precursor of the radical cation in the femtosecond pulse radiolysis study of n-dodecane [1], previously. The lifetime of the excited radical cation was very short (e.g. 7 ps in n-dodecane), and the charge transfer reaction rate constant from the excited radical cation to biphenyl was 10 times higher than that of the radical cation. That suggested that the excited radical cation affects the primary decomposition process and scavenging reaction [2], To confirm the excited radical cation, the time-dependent behaviors of the electron in n- dodecane were investigated by the femtosecond pulse radiolysis in this study. The geminate decay of the electron monitored at 1200 nm agreed with that of the radical cation monitored at 800 nm after 100 ps, which means the electron recombined with the radical cation geminately. While the electron showed the typical geminate behavior even within 100 ps, which disagreed with that of the radical cation, because of the formation process of the radical cation from the excited radical cation. Moreover, the scavenging effect on the electron was studied by the femtosecond pulse radiolysis. The initial yields of the electron were decreased by increasing of the scavenger (CCI4) concentration and the geminate decays were changed. That means that the pre-thermalized electron was captured by CCI4 and the initial distributions of the geminate pairs were changed.

References

[1] T. Kondoh, J. Yang, K. Norizawa, K. Kan, Y. Yoshida, Radial Phys. Chem., 80, 286(2011) [2] T. Kondoh, J. Yang, K. Norizawa, K. Kan, T. Kozawa, A. Ogata, S. Tagawa, Y. Yoshida, Radiat. Phys. Chem., submitted. LOW TEMPERATURE RADIOLYSIS OF DICYCLOHEXANOCROWN ETHERS AND RELATED COMPOSITIONS

S.V. Nesterov1’, O.A. Zakurdaeva1’ and V.I. Feldman2’ l)Enikolopov Institute of Synthetic Polymer Materials of RAS, ul. Profsoyuznaya 70, Moscow, 117393, Russia 2)Department of Chemistry, Moscow State University, Moscow, 119991, Russia

Safe reprocessing the spent nuclear fuel and utilization of liquid radioactive wastes are challenging tasks from scientific, applied and environmental points of view. The tasks can be significantly simplified by preliminary separation of the dangerous fission products, in particular Sr9 . As shown in numerous radiochemical tests, dicyclohexano- substituted crown ethers were very promising agents being able to bind Sr90 selectively. Accordingly, the data on radiolysis mechanism and radiation stability of the crown ether are of great importance. Herein, we report a review of our recent results on intermediate radiolytic products of dicyclohexanosubstituted crown ethers and some of crown-based systems, which were irradiated at 77K. Paramagnetic intermediate products were studied by ESR spectroscopy. Dicyclohexano-18-crown-6 (DCH18C6), di-tert-butylcyclohexano-18- crown-6 (DtBuCH18C6), their aqueous and 1-octanol solutions as well as complexes of DCH18C6 with nitrates and chlorides of alkali earth metals were chosen as the objects of investigation. Both macrocyclic radicals and acyclic intermediates resulted from polyether ring cleavage were found in the "free" crown ethers irradiated at 77K. The non-additive yields of macrocyclic radicals in irradiated aqueous solutions of DCH18C6 were attributed to interaction of macrocycle with OH radicals resulted from water radiolysis. Observed superadditive accumulation of stabilized macrocyclic radicals upon irradiation of DtBuCH18C6 solutions in 1-octanol may be also explained by reactions of the polyether ring with products of solvent radiolysis. The anion nature was found to have a pronounced effect on the mechanism of radiation-chemical transformation in crown ether complexes with alkaline earth metal salts. Namely, NO32' radicals were identified as principal intermediate species in nitrate complexes irradiated at 77K, while C-centered radicals resulted from the transformation of macrocycle were stabilized in the case of chloride complexes. The results obtained may be used for an assessment of radiation stability of the crown-based systems in practical nuclear applications. This work was supported by the Russian Foundation for Basic Research (no. 09-03- 00877a) and programme no.8 of the Division of Chemistry of Russian Academy of Sciences. -91 -

PARAMAGNETIC CENTERS FORMATION UNDER RADIOLYSIS OF CRYSTALLINE RbN03 AND CsN03

V. Anan’ev and V. Pak Kemerovo State University, Krasnaya 6, Kemerovo, 650043, Russia

The goal of the present paper is to study the paramagnetic centers formation under y- radiolysis of crystalline RbNOs and CsNC>3 at 300 K and their decay under the heating to develop the mechanism for radiolysis products formation. The RbN03 and CSNO3 crystals were irradiated with 60Co y-rays at ~ 310 K. The irradiated RbNC>3 and CSNO3 crystals were thermal annealed at 393 K and 423 K, respectively. O - and N 02* centers are registered in ESR spectra of irradiated crystals. The kinetics of 0*“ accumulation has a nonlinear character, when for N 0 2* it is linear. The values of 0 * initial radiation chemical yield - G(0~) are equal to 0.01 and 0.14 (100 eV)'] for RbNC>3 and CSNO3, respectively, when G(N02*) - 0.03 (100 eV)'1 for studied nitrates. The thermal annealing of irradiated samples results in the drop of the initial centers with simultaneously appearance of the Oi*. but not 0 2»“. The initial product of radiolysis of the nitrates is the complex [xN02~ ...0x]. Because C>3*_ formation from 0 * under thermal annealing is possible if the molecular oxygen formed under irradiation only, then x = 2. Therefore O formation is not due to the localization of the electron on the atomic oxygen of the complex. The complex [N 02v ..0 “] may be formed under the dissociation of the excited nitrate ion formed under irradiation. Hence, the formation of that complex in crystalline nitrates is at variance to the fact that G(0~) disagree with G(N02»). The mechanism for the paramagnetic centres formation under the radiolysis of RbNC>3 and CsNC>3 crystals and the heating can be written as follows. Under irradiation: NC>3~+e—»N03»2~->[N0 2~...(>~]; 2N03~+h—» (N 03)2»~—» [N 02*...0 2...N 0 2 ] Under the heating: [N02* ...0 2...N 0 2_]^[N 02* ...N0 2~]+02; 0 2 +[N 02'. . . 0 ”]-> [N 02“...0 3*1

Acknowledgements: This research was conducted with financial support from Federal Target Programme “Scientific&Scientific-Pedagogic Manpower of Innovation Russia” 2009-2013 years. - 9 2 -

ELECTRON-BEAM SYNTHESIS OF FUEL IN THE GAS PHASE

A.V. Ponomarev, E.M. Holodkova and B.G. Ershov A.N. Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, Leninsky Prospect, 31, 119991 Moscow, Russia

Tendencies of world development focus attention on a vegetative biomass as on the major raw resource for future chemistry and a fuel industry. The significant potential for perfection of biomass conversion processes is concentrated in the field of radiation- chemical methods. Both the mode of post-radiation distillation and mode of electron- beam distillation of biomass have been investigated as well as the mode of gas-phase synthesis of liquid engine fuel from of biomass distillation products. Synergistic action of radiation and temperature has been analyzed at use of the accelerated electron beams allowing to combine radiolysis with effective radiation heating of a material without use of additional heaters. At dose rate above 1 kGy/s the electron-beam irradiation results in intensive decomposition of a biomass and evaporation of formed fragments with obtaining of a liquid condensate (~ 60 wt %), CO2 and CO gases (13-18 wt %) and charcoal in the residue. Biomass distillation at radiation heating allows to increase almost three times an organic liquid yield in comparison with pyrolysis. The majority of liquid products from cellulose is represented by the furan derivatives considered among the very perspective components for alternative engine fuels. Distilled-off gases and vapors are diluted with gaseous C1-C5 alkanes and again are exposed to an irradiation to produce liquid fuel from a biomass. This transformation is based on a method of electron-beam circulation conversion of gaseous C 1-C5 alkanes (Ponomarev, A.V., Radiat. Phys. Chem., 78, 48, 2009) which consists in formation and removal of liquid products with high degree of carbon skeleton branching. The isomers ratio in a liquid may be controlled by means of change of an irradiation condition and initial gas composition. The irradiation of gaseous alkanes together with vaporous products of biomass destruction allows to synthesize the fuel enriched by conventional liquid alkanes, tetrahydrofuran derivatives, stable alcohols and ethers. Fractional composition and knock value of an obtained liquid corresponds to the requirements assigned to standard engine fuel. The described method has been supplemented by the modifications aimed at production of alternative types of liquid engine fuel from a various auxiliary feedstock - synthesis gas, cracked gas, heavy oil fractions and native bitumens. These modifications are characterized by synergetic gain in yield of feedstock conversion. -93 -

APPLICATION OF XRF FOR CHARACTERIZATION OF ICON OF XVIII CENTURY

D. Abbasova Institute of Radiation Problems of AzNAS, Azerbaijan

Application of XRF for cultural heritage characterization is well known. This method is non­ destructive and non-invasive method and can be apply for archeological samples and cultural heritage objectives analysis. In this work element content of icon of XVIII century was given by using of XRF Omega 4000. Were identified that red color fragments of icon have different element contents from yellow and green colored parts. All red colored fragments have the same content. It means that author was used different dyes for illustration. Results of analysis were given in % and shown in table.

Icon Ti V Fe Zr Sn Ta W Re Au Pb LE Yellow color 0.1619 0.0589 0.5995 0.0088 ND ND 0.1637 ND ND 0.0818 98.9255 Green color 0.1214 0.0753 0.5486 0.0062 ND ND 0.0619 ND ND 1.2402 97.9465 Red color 0.1194 0.0914 0.2173 ND 0.2165 0.3625 ND 22.2558 3.0181 8.2978 65.4211 - 9 4 -

IMPROVING THE MICROBIOLOGICAL QUALITY OF DRIED MORINGA LEAF PRODUCTS THROUGH GAMMA IRRADIATION

A. Adu-Gyamfi, F.B. Apea-Bah, T. Mahami, J. Agyei-Amposah and C. Owulah Department of Food Science and radiation Processing, Biotechnology and Nuclear Agriculture Research Institute, Ghana Atomic Energy Commission, P. O. Box LG 80, Legon, Ghana

Moringa products obtained from the plant Moringa oleifera have several nutritional and medicinal uses in most developing countries. Until recently in Ghana, there were no national standards regulating its quality. The objectives of this study were to assess the microbiological quality of dried moringa leaf products and to investigate how it is affected by gamma irradiation. Samples of dried moringa leaf powder were obtained from various retail outlets in Accra and analysed for total viable cells, colifoms, moulds and yeast, Escherichia coli and Salmonella by using methods of serial dilution and pour plating. Additionally, samples of mechanical-, solar- and room-dried moringa leaves were irradiated at doses of 0, 2.5, 5.0, 7.5, 10.0 kGy with gamma radiation from a Co- 60 source. The samples were subsequently analysed for total viable cells, coliforms, moulds and yeasts, Salmonella spp. and Pseudomonas spp. by using the methods of serial dilution and pour plating. Results indicated the range of the counts of total viable cells in the samples of moringa leaf powder was 5.92 - 8.44 (logio cfu/g). In the case of coliforms, the range of the counts was 4.85 - 7.25. The counts of moulds and yeast cells was in the range of 1.65 - 3.69. The range of the counts of E. coli in the samples was 3.71 - 4.78. Salmonella was present in some of the MLP samples analysed. The results also show that samples of room-dried moringa leaves had higher counts of total viable cells (6.20 logiocfu/g); coliforms (6.83); moulds and yeasts (2.99); and Pseudomonas spp. (3.52) compared to samples dried by mechanical or solar methods. Salmonella spp was not detected in all the samples. No microorganisms were detected in all the samples of moringa leaves after gamma irradiation at doses of 5, 7.5 and 10 kGy. Irradiation at 2.5 kGy reduced the counts of microorganisms to 3.57 (logiocfu/g) and below. Prolonged drying periods of the moringa leaves in shady environments of high humidity could promote microbial growth and negatively impact the microbiological quality. Temperatures of mechanical drying (50-55°C) and solar drying (35-55°C) were higher than that of room drying; thus reducing the moisture content and available moisture that could have supported microbial growth. Gamma irradiation significantly improved the microbiological quality of dried moringa leaves products. The process should be integrated into the processing protocol of dried moringa leaves in order to enhance their quality of for the domestic and export markets. -95 -

CHEMOMETRIC CHARACTERIZATION OF GAMMA IRRADIATED CHESTNUTS FROM TURKEY

J.C.M. Barreiraa,d), A.L. Antonioa,b,e), A. Fernandesa), T. Giinaydie), H. Alkane), A. Bentoa), M.L. BoteIhob) and I.C.F.R. Ferreiraa) a)CIMO/Escola Superior Agrária, IPB, Portugal; b)GTRPP/UFA, Instituto Tecnológico e Nuclear, Portugal; c)Dep. de Fisica Fundamental, Univ. de Salamanca, Spain; d)REQUIMTE/Faculdade Farmácia, Univ. Porto, R. Anibal Cunha, Portugal; e)Gamma-Pak Sterilizasyon, 59500 £erkezköy-Terkirdag, Turkey

Chestnut (Castanea sativa Miller) is a valuable natural resource, with high exportation levels. Due to their water content, chestnuts are susceptible to storage problems like dehydration or development of insects and microorganisms. Irradiation has been revealing promising features to be considered as an alternative conservation technology, for Portugese cultivars. Hence, the assessment of irradiation effects in foreign cultivars might act as an important indicator of the versatility of this technology. In this work, the effects of gamma irradiation (0.0, 0.5 and 3.0 kGy) on proximate composition, sugars, fatty acids and tocopherols composition of Turkish chestnuts stored at 4 °C for different periods (0, 15 and 30 days) was evaluated. Regarding proximate composition, the storage time (ST) had higher influence than irradiation dose (ID), especially on fat, ash, carbohydrates and energetic value. Sucrose exhibited similar behavior in response to the assayed ST and ID. The prevalence of ST influence was also verified for fatty acids (FA), tocopherols and sucrose. Laurie, palmitoleic and linolenic acids, were the only FA that undergone some differences with ID. Saturated, monounsaturated and polyunsaturated fatty acids levels were not affected neither by storage nor irradiation, a- Tocopherol was the only vitamer with significant differences among the assayed ST and ID. Overall, our results confirm that gamma irradiation is a promising conservation methodology, without inducing changes in chestnut chemical and nutritional composition. - 96 -

LIMITS OF TL PROTOCOL EN 1788 APPLIED TO HERBS AND SPICES: IDENTIFICATION OF BLENDS CONTAINING IRRADIATED COMPONENTS

E. Bortolin, S.D. Monaca, R. Gargiulo and C. Boniglia Istituto Superiore di Sanitá, Rome, Italy

The European Standard EN1788, based on thermoluminescent technique, has been validated for the identification of herbs and spices through international trials. The method requires a double TL measurement on silicates extracted from the foods. The first TL readout (Glowl) is performed right after the extraction whereas the second one (Glow2) is earned out after laboratory irradiation with a dose comparable to those used for the treatment. Irradiated samples provide glow curves Glowl and Glow2 showing a peak at about 200 °C similar in shape and intensity, whereas in the curves of untreated samples only a weak signal due to natural radiation (geological signal) is observed at about 300 °C. On these basis, the minimum threshold of 0.1 has been established for the Glowl/Glow2 ratio to identify irradiated samples. The method can be applied also to detect an irradiated component in blends containing different ingredients such as, for example, dietary herbal supplements. In this case, the intensity of Glowl peak can be extremely low depending on the percentage of irradiated product present in the blend. Therefore, as reported in the EN1788 Standard, a glow ratio below the fixed threshold can be obtained for these samples. In these situations the shape of Glowl and, in particular, the presence of a peak at T<250 °C, helps to correctly identify the sample. Unfortunately, weak TL signal in that region of the glow curve (Glowl) might also be observed as a consequence of fortuitous artificially low doses irradiation, such as those provided from the X ray scanners used to control the product content (manufacture checks, customs checks at ports, airports,...). This work investigates the possibility that such events can lead to incorrect classifications during the analyses of the official controls. Preliminary tests performed on samples of herbs and spices passed through the X scanner of an airport seems to confirm this hypothesis. - 9 7 -

COMPARATIVE FT-RAMAN, FT-IR AND COLOUR SHIFTS SPECTROSCOPIC EVALUATION OF GAMMA IRRADIATED EXPERIMENTAL MODELS OF OIL PAINTINGS

M.M. Manea1’, C.D. Negut1’2’, O.H. Barbu3’4*, M. Virgolici1’, I.R. Stanculescu1’5’, M. Cutrubinis1’, I.V. Moise1’ and C.C. Ponta1’ ’’"Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), IRASM Centre of Technological Irradiations, 077125, Romania 2)University of Bucharest, Department of Atomic and Nuclear Physics, 077125 3)National University of Arts Bucharest, Department of Conservation-Restoration, 010773, Romania 4’National Museum of Romanian History (MNIR), Centre of Research and Scientific Investigations, 030026, Romania 5)University of Bucharest, Faculty of Chemistry, Department of Physical Chemistry, 030018, Romania

The present study follows the changes of gamma irradiated historic pigments and experimental models of oil paintings with non-destructive and non-contact spectroscopic analytical techniques which are the only ones accepted by the conservators/restorers community. Molecular structure characterization was performed by F T -IR / Raman spectroscopy using a Bruker Vertex 70 class equipped with two mobile probes: a MIR fibre module for MIR probes (with LN2 cooled detector) and a Raman RAM II module (LN2 Ge detector) with a RAMPROBE fibre. Colour was measured by a portable reflectance spectrophotometer (Miniscan XE Plus, HunterLab) in diffuse/8 ° geometry with a beam diameter of 4 mm and specular component included. Correlations between colour shifts and changes in molecular structure induced by gamma irradiation were further investigated. - 98 -

APPLICATION OF PHOTOSTIMULATED LUMINESCENCE (PSL) TO DETECT IRRADIATED MOLLUSCS

G. Marchesani1', M. Mangiacotti1’2', A. Alberti3', P.G. Fuochi3', L.M. Chiesa2) and A.E. Chiaravalle1' ''istituto Zooprofilattico Sperimentale della Puglia e della Basilicata - Centro di Referenza Nazionale per la Ricerca della Radioattivitá nel Settore Zootecnico- Veterinario, Via Manfredonia 20,1-71121 Foggia, Italy 2)Universitá degli Studi di Milano - Facoltá di Medicina Veterinaria - Dipartimento di Scienze e Tecnologie Veterinarie per la Sicurezza Alimentare - Laboratorio di Ispezione degli Alimenti di Origine Animale, Via Celoria 10,1-20133 Milano, Italy 3)ISOF-CNR, Area della Ricerca, Via P. Gobetti 101,1-40129 Bologna, Italy

In contrast to thermally processed foods, irradiation is a cold treatment both to reduce microbiological contamination and to increase the shelf-life of raw seafood. According to the list of States’ authorizations molluscs can be irradiated in a range of 0.5 ^ 3 kGy only in authorized countries (e.g. UK, Belgium and Czech Republic). Therefore the aim of this study is to identify, at different dose levels (0.5, 1, 1.5, 2, 3 kGy), irradiated oysters, clams and mussels using luminescence materials from different sites (shells and pulps) and to determine sample sensitivity for previous screening result confirmation. A total number of 10 samples for each species were analyzed by both procedures: screening and calibrated PSL. Samples were irradiated using a low energy X-ray irradiator (RS-2400, Radsource Inc.) with the following operational settings: 150 kV and 45 mA. Whole pulps were simply dispensed into a clean Petri-dish whereas shells powder required to be fixed as a thick layer with silicone grease. Results obtained showed that screening analysis can be used to identify correctly all irradiated and non irradiated samples. Particularly untreated sample exhibited a sensitivity index from 2 to 4 order of magnitude greater than the exposed sample one, while for exposed specimen calibrated PSL signals, after re-irradiation at defined dose, were of the same order of the first measurement (initial PSL counts). In conclusion mineral debris contaminating pulps and biocarbonates from shells can be considered reliable radioinduced markers and PSL techniques can be easily applied for rapid and simple analysis to identify irradiated molluscs in official controls. - 9 9 -

REMEDIATION OF WASTEWATERS BY HIGH ENERGY IRRADIATION PROCESS

M. Chamam, Cs.M. Földváry, A.M. Hosseini, A. Tungler, E. Takács and L. Wojnárovits Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

The y-ray and electron beam induced oxidation of Na-phenolate solutions were studied by varying the oxygen concentration and the absorbed dose. The experiments were made in a stainless steel high pressure autoclave equipped with a magnetic stirrer. The oxygen pressure in the autoclave was varied up to 20 bars. The rate of oxidation was followed by measuring the Chemical Oxygen Demand (COD) and the Total Organic Carbon content (TOC) of the solutions.

Phenol O, normal pressure 2200 - r 800

„ 2000 600 O E O T3 _o CT E 1800- 400 O p ci O 3 O (Q 1600 200 | . 0 „ 20 bar 2 mmol dm 1400 0 To 20 30 40~ 50 Dose, kGy

The figure shows the COD values of phenol solution measured before and after irradiation. The starting concentrations were 10 mmol dm-3, and 2 mol dm-3. Samples were irradiated in O2 atmosphere, at normal pressure (square) or at 20 bar (triangle) and also in N2O/O2 5/1 mixture (open circle). In the figure the TOC values are also shown (open square). The COD and TOC values change nearly linearly with the dose. The increase in oxygen pressure results in increasing mineralization rate. - 100 -

RADIATION DEGRADATION OF PHARMACEUTICAL RESIDUES IN WATER: CHLORAMPHENICOL

T. Csay, G. Rácz, E. Takács and L. Wojnárovits Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

Traditional wastewater treatment systems primarily rely upon physical, chemical and biological processes. The conventional techniques cannot efficiently remove badly biodegradable pollutants like pesticides, herbicides and drugs from influents. Leaving “polluted” water flowing freely out to environment may cause unwanted and sometimes unpredictable effects. Degradation or removal of residual organic contaminations from wastewater is an important task both for science and engineering to preserve environment and drinking water. Ionizing radiation treatment of liquid wastes is one of the so called advanced oxidation processes (AOP) leading to decomposition of pharmaceuticals in aqueous solutions. The radiolysis of chloramphenicol (CPL) a broad spectrum antibiotic was investigated under different conditions. Steady-state gamma radiolysis were used to generate various reactive species (’H, ’OH and e~ ). Reactions were followed by steady state and time resolved UV-Vis spectrometry. Several degradation products were separated and identified by LC-MS/MS. Mineralization was followed by measuring chemical oxygen demand (COD) and total organic carbon content (TOC). The change in toxicity was followed by Microtox, a luminescent bacteria test. Results indicate that ionizing radiation is very effective in degradation of CPL. After irradiating 0.1 mM CPL solutions with 5.0-7.5 kGy doses, no products could be observed indicating that irradiation resulted in complete mineralization. - 101 -

HIGH-ENERGY IONIZING RADIATION INITIATED DECOMPOSITION OF ACETOVANILLONE

K. Gonter, E. Takács and L. Wojnárovits Institute of Isotopes, Hungarian Academy of Sciences, Budapest, H-l 121, Hungary

Acetovanillone (AV) i.e. l-(4-hydroxy-3-methoxyphenyl)ethanone) with other name Apocynin, a derivative of vanillin, is known for its anti-inflammatory capabilities which is attributed to its radical scavenging ability. AV is one of the main phenolyc pollutants which is present in the wastewater produced during the boiling process in cork industry. It is a biorecalcitrant compound which blocks the biodegradation. Advanced oxidation processes, among them irradiation induced degradation may help to solve this problem.

Acetovanillone (AV)

As the experiments show AV readily degrades under the effect of ionizing radiation; at a concentration of 0.1 mmol dm'3 a dose of 5 kGy is sufficient for complete degradation of AV and its main decomposition products. In neutral solution the *OH radicals take part in radical addition reaction to the aromatic ring with a diffusion limited rate coefficient. In the reaction hydroxycyclohexadienyl type radical forms. This radical within a c.a. 15 \is transforms to phenoxy radical. The phenoxy radical decays on the ms timescale. These intermediates are characterised and a degradation mechanism is suggested. - 102 -

RADIOLYTIC DEGRADATION OF DICLOFENAC AND 2,6- DICHLOROANILINE IN AQUEOUS IN SOLUTION

R. Homlok, E. Takács and L. Wojnárovits Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

The pharmaceutical companies in designing new molecules pay attention to the environmental toxicity of the drug; from the different variants they try to choose the less toxic one. However, metabolites, degradation products may also be toxic for the fauna and flora. For instance, diclofenac (DCF), a non steroid type anti inflammatory drug, is a moderately toxic compound. During its degradation 2,6-dichloroaniline (DCA) forms which is much more toxic than the initial molecule. In this work the radiation induced degradation of DCF and DCA is reported. The purpose of the work is the elimination of these compounds from water.

Diclofenac (DCF) 2,6-Dichloroaniline (DCA) The intermediates are studied using pulse radiolysis, while the degradation is followed by UV-VIS spectroscopy, separation by HPLC and products identification by diode array and MS-MS detection. The effect of dose, irradiation atmosphere, and additives are investigated. The change in chemical oxygen demand, in total organic carbon content and in toxicity of the solutions are also followed as a function of dose. The *OH radicals at both molecules add to the ring and this reaction initiates the degradation. In the case of DCF hydroxylated molecules, DCA, and quinone type compounds form. In the presence of oxygen there is an increase in the hydroxylated product yield. Ring opening and mineralization is suggested to proceed through peroxy intermediates. In the case of DCA the hydroxy radical reaction is accompanied by chlorine atom elimination.

Reference

R. Homlok, E. Takács, L. Wojnárovits: Elimination of diclofenac from water using irradiation technology. Chemosphere, doi: 10.1016/j.chemosphere.2011.06.101 - 103 -

NUMERICAL SIMULATION OF FLUE GAS PURIFICATION FROM NOx, S 02 BY ELECTRON BEAM

V.V. Morgunov1*, O.L. Fainchtein2* and A.M. Shkilko1* ''Ukrainian engineer pedagogics academy, Kharkov, Ukraine 2)USSTC “Energostal”, Kharkov, Ukraine

The paper is devoted to numerical simulation of radiation-chemical processes in gas phase, which are take place during electron beam (EB) treatment of flue gases. A mathematical model of EB processes in gas phase was created. Also, a computer code which numerically simulates radiation-chemical processes during EB treatment of flue gases was created. The needed data such as chemical species, radiation-chemical yields and rate constants of the chemical reactions were collected and putted into database. The computer code allows do following:

1. The following technological parameters: irradiation dose, temperature, initial composition of the flue gases, time of irradiation (time which flue gases spend in an irradiation zone), one- or two- stage irradiation can be defined by the user in the code shell; 2. In accordance with the initial composition of flue gases selects chemical species from database of the chemical species (total amount of species in database is 522) which took part in simulation taking into account species that are formed due to irradiation.; 3. In accordance with the selected chemical species selects chemical and radiation- chemical reactions from the database of reactions (total amount of chemical and radiation-chemical reaction is 2275) which are took part in the simulation; 4. Creates a stiff system of ordinary differential equations (ODEs) which describes chemical and radiation-chemical reactions; 5. Solves the received system of ODEs by backward differentiation formula (Gear’s method); 6. Creates plots of dependencies: concentrations of chemical species versus time of irradiation under different parameters of modeled EB-processes.

The received results. For the following technological parameters: irradiation dose is 8.0 kGy; two stage irradiation; initial temperature is 353°K; time of the irradiation - 4 s; initial composition of the flue gases - typical for power plant, following removal efficiencies were received: NO - 99.97%, NO2 - -17.53% (the concentration growth was observed), SO2 - 77.32% (without taking into consideration direct reaction SO2 and NH3); amount of selected species -111; amount of selected reactions - 941. Elaborated computer code can be used for optimization of the EB flue gases purification technology, modeling kinetic mechanism of radiation-chemical processes in the flue gases, carry out numerical experiments. - 104 -

MECHANISM OF AZO DYE DEGRADATION BY IONIZING RADIATION: DEGRADATION OF SULFANILIC ACID AZOCHROMOTROP AND ITS PARENT COMPOUNDS IN AQUEOUS SOLUTION

T. Pálfi, R. Homlok, T. Csay, L. Wojnárovits and E. Takács Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary

Mechanistic studies were made on *OH radical and hydrated electron reaction with Sulfanilic Acid Azochromotrop (SPADNS) as model azo dye. SPADNS contains 4,5- dihydroxynaphthalene 2,7-disulfonic acid part and 4-sulfophenylazo group. To establish the details of the reaction mechanism the reactions of two simpler molecules without 4- sulfophenylazo part were also studied: one of them contained one (in position 4, II), the other two (in positions 4 and 5, III) -OH groups. *OH radicals react with these molecules with radical addition to the naphthalene 2,7-disulfonic acid part. The adduct cyclohexadienyl type radical may decay in radical-radical reactions, or undergoes a (pH dependent) water elimination to naphthoxy radical, radical decay takes place on the ms timescale. *OH radical addition on the azo bond in dyes has low importance. Degradation efficiencies are 0.6-0.8. The hydrated electron in the case of the two simpler molecules reacts with the rings, while in the case of dye with the azo bond. Electron scavenging is followed by protonation, this reaction in the case of II and III yields cyclohexadienyl, while with the dye hydrazo radical. The efficiency of degradation with II and III is 0.2-0.6, while for the dye it is close to 1.

o \\

o o 0 0 III H-Acid - 105 -

RADIOLYTIC DEGRADATION OF PARACETAMOL IN DILUTE AQUEOUS SOLUTION

L. SzabóI,2), T. Tóth2', R. Homlok1', E. Takács1' and L. Wojnárovits1' ^Institute of Isotopes o f the Hungarian Academy of Sciences, Budapest, Hungary 2)Budapest University of Technology and Economics, Budapest, Hungary

Paracetamol or with other name acetaminophen is widely used as analgesic and antipyretic drug. Due to its heavy use it is regularly detected in the surface waters. The degradation of the compound formerly was studied in several advanced oxidation processes (UV/H2 O2 , UV/TÍO2 , electrochemical oxidation, ozonation). Here we report on the radiolytic degradation. V/CH, Ö

Paracetamol

In the experimental work we combined a wide variety of techniques. For the investigation of the intermediates pulse radiolysis, for end-product experiments (decolouration, mineralization) gamma irradiation were used together with UV-Vis spectroscopy, HPLC separation (with diode array and MS-MS detection), chemical oxygen demand, total organic carbon content and toxicity measurements. ’OH radicals are the main oxidative species during irradiation. They add to the aromatic ring producing hydroxycyclohexadienyl type radicals. These radicals either transform to hydroxy-paracetamol stable products in several reaction steps, or after water elimination transform to semi-iminoquinone radical. The reaction o f hydroxycyclohexadienyl radicals with O2 yields peroxi radicals. The latter radicals may eliminate HO2 * or undergo ring opening and transformation, first to different carboxylic acids, and finally (mineralization) to CO2 , H2 O and NH 3 or NO 2 . Paracetamol has a relatively low toxicity. In 10' mol dm'3 DCF solution after irradiation with 0.4 kGy dose there is an increase in toxicity. It means that during irradiation some products (e.g. hydroquinone, acetamide) are more toxic than paracetamol. By increasing the dose the toxicity suddenly decreases. It seems that the toxic products are highly sensitive to irradiation treatment. - 106 -

DECOMPOSITION OF PERSISTENT PHARMACEUTICALS IN WASTEWATER BY IONIZING RADIATION

A. Kimura!), M. Osawa2) and M. Taguchi1* Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma 370-1292 JAPAN 'Gunma Prefectural Sewerage Manegement General Office, 1846-1 Kaminote, Tamamura-machi, Sawa-gun, Gunma 370-1127 Japan

The environmental movement and risk evaluation of some pharmaceuticals are studied recently, and the concentrations of the pharmaceuticals in the water environment increased gradually because of population growth and the diversification of advanced medical worldwide. Some anti-inflammatory medications, anticonvulsant drugs, antiviral drugs, antilipemic agents and so on were detected at the downstream of water treatment plant, and could not be decomposed by the activated sludge system completely. However, it is difficult to manage the environment risk of the pharmaceuticals having great benefits for human life. The development of new treatment method is required to minimize their risk. The purpose of this work is to treat the pharmaceuticals in combination of the activated sludge and the ionizing radiation. Oseltamivir, aspirin and ibuprofen at 5 p.mol dm'3 in wastewater were decomposed by activated sludge at reaction time for 4 h. Carbamazepine, ketoprofen, mefenamic acid, clofibric acid, and diclofenac were not biodegraded completely, but eliminated by y-ray irradiation at 2 kGy. The rate constants of the reactions of these pharmaceuticals with hydroxyl radicals produced by water radiolysis were estimated by the competition reaction method to be 3.4 - 10 x 109 mol'1 dm3 s'1. Decompositions of the pharmaceuticals in wastewater by ionizing radiation were simulated using parameters of the obtained rate constants and the amount of total organic carbon. Simulation curves of concentrations of these pharmaceuticals as function of dose were responsible for the experimental data, and the required dose for the elimination of them in wastewater by ionizing radiation can be estimated by this simulation. - 1 0 7 -

GAMMMA IRRADIATION FOR THE PREVENTION OF BIODETERIORATION OF HISTORIC AND MODERN TEXTILES

K. Kavkler1,2', A. Demsar3), B. Katusin-Razem4), I. Pucic4), B. Mihaljevic4), P. Zalar5) and N. Gunde-Cimerman3' ^Gorenjska predilnica d.d., Skoija Loka, Slovenia; 2)Institute for the Protection of Cultural Heritage, Restoration Centre, Ljubljana, Slovenia; 3)University of Ljubljana, Faculty of Natural Sciences and Engineering, Department of Textiles, Ljubljana, Slovenia; 4,Ruder Boskovic Institute, Zagreb, Croatia; 5)University of Ljubljana, Biotechnical Faculty, Department of Biology, Ljubljana, Slovenia

The susceptibility of natural fibers to biological damage is a serious problem in the protection of textile cultural heritage (CH) objects. The treatment with ionizing radiation has been widely used for disinfestation and decontamination of CH artifacts. Textile items, mostly of ethnological significance, were efficiently disinfected by irradiation with less than 2 kGy dose at the 60Co gamma irradiation facility of the Ruder Boskovic Institute in Zagreb, Croatia [1], However, the application of higher doses for the control of fungi needs to be justified by investigating the effects of irradiation on textile fibers. The model samples of three textile materials: cotton, flax and wool were prepared and inoculated with six different fungal species, which had been previously isolated from textile objects in several Slovenian museums. The inoculated samples were incubated for 20 weeks before y-irradiation to 5 and 10 kGy. Microbiological analyses showed that no fungal species survived the dose of 5 kGy. Structural analyses were performed by Fourier Transform Infrared Spectroscopy Attenuated Total Reflectance (FTIR ATR) and scanning electron microscopy (SEM). The results of inoculated and of inoculated and irradiated samples were compared to the results of the non-inoculated unirradiated materials. The formation of carbonyl band was observed in many inoculated samples of all three materials and disappeared after irradiation. The changes in crystallinity generally indicated some degree of degradation. The dose of 5 kGy, efficient at killing fungi, did not cause physical changes compared to unirradiated samples. However, further investigations are needed to determine changes caused by doses higher than 5 kGy, as well as long term postirradiation effects. Nevertheless, it is safe to say that doses up to 1 kGy, accepted by conservation specialists, can be considered safe for desinsection of textile materials.

Reference

[ 1] B. Katusin-Razem, D. Razem, M. Braun, Radiat. Phys. Chem., 78, 729 (2009) - 108 -

PRACTICAL ASPECTS DURING STERILIZATION VALIDATION FOR MEDICAL DEVICES AT IRASM MICROBIOLOGICAL LABORATORY

L. Trandafir, M. Ene, M. Alexandru, M. Constantin, A. lonitá, F. Zorilá and I.V. Moise "Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH), IRASM Radiation Processing Centre, Romania

The state of being free of living microorganisms is called sterility. The sterility state can be achieved by different means of sterilization. In practice the results of the process cannot be fully verified by tests, so the efficacy of the sterilization process must be validated. ISO 11137 established regulations for setting or substantiating the dose for achieving the desired sterility assurance level. The validation studies can be designed in particular for different types of product. Each product needs distinct protocol for bioburden determination and sterility testing. During time, the Microbiological Laboratories from Multipurpose Irradiation Center deals with different types of products, mainly for VDmax 25 method. When it comes to microbiological evaluation the most challenging was cotton gauze. Special situation for establishing the sterilization validation method appears in cases of cotton, packed in large quantities. VDmax 25 method can not be applied for items with average bioburden more than 1000 CFU / pack, no matter which is the weight of the package. This is a method limitation and implies increased costs for manufacturer, when choosing other method. For microbiological tests, culture condition should be selected in both cases the bioburden and sterility testing. These are time and money consuming. The costs can be reduced if taking into account some aspects. Reason for performing the bacteriostasis- fungistasis just for sterility testing will be given. The present study puts forward aspects during the validation studies for medical devices (cotton wool, cotton gauze, surgical sutures, dental screws), at IRASM Microbiological Laboratory. - 109 -

MICROBIOLOGICAL ASPECTS OF THE IRRADIATION TREATMENTS FOR PRESERVATION OF ARCHIVES

F. Zorila1*, L. Trandafir1*, M. Alexandru1*, S. Nisipeanu2’, M. Haiducu2*, I.V. Moise1* and R. Georgescu1* r,"Horia Hulubei" National Institute of Physics and Nuclear Engineering (IFIN-HH) 2)” Alexandra Darabont’’ National Institute for Work Safety, Romania

Cultural heritage conservation is very important for a community, not only for protecting economically valuable physical assets, but also for preserving its practices, history, and a sense of continuity and identity. One of the reasons of decaying of cultural heritage and particularly of archives is the harmful activity of microorganisms. Their activity affects not only the material of books and documents, but also the working personnel, by inducing occupational diseases. One of the methods used to prevent these negative effects is the use of ionizing radiation, in order to decrease the microbial contamination. This work presents microbiological results obtained during the development of irradiation treatments for archive materials: initial contamination of paper items, environment control and radiation resistance of microorganisms isolated from the paper items. The irradiation dose should be effective but as low as possible because it is known that a high dose of radiation could induce damage by modification of the cellulose and its degree of polymerization, making it more fragile and brown-colored. The use of a statistical method derived from VDmax Method (ISO 11137-2) is proposed for the substantiation of the decontamination dose for archives. - 1 10 -

SWELLING KINETICS AND ANTIMICROBIAL ACTIVITY OF RADIOLYTICALLY SYNTHESIZED NANO-Ag/PVA HYDROGELS

J. Krstic, J. Spasojevic, A. Krkljes and Z. Kacarevic-Popovic Vinca Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, Belgrade, Serbia

Synthesis of nanocomposite materials for biomedical applications, is being systematically developed. The materials having metal nanoparticles incorporated into polymer network have been widely investigated due to their unique properties induced by the synergy of two different materials. Silver nanoparticles (nano-Ag) have been proved to be effective antimicrobial agent and their enhanced antibacterial properties have been demonstrated both in vitro and in vivo. Recent research efforts are directed towards exploiting the in situ synthesis of nano-Ag within polymeric network architectures and products of these approaches are new hybrid nanocomposite systems. Due to characteristic properties such as swellability in water, hydrophilicity, biocompatibility and lack of toxicity, hydrogels have been utilized in a wide range of biological, medical, pharmaceutical and environmental applications. Among different synthetic methods, y-irradiation induced synthesis has been recognized as highly suitable tool for production of hydrogel nanocomposites due to formation and sterilization of material in one technological step. In this work, the swelling kinetics of PVA and nano-Ag/PVA hydrogels in distilled water and Kokubo's Simulated Body Fluid (SBF), at 25 and 37 °C, was investigated. The obtained hydrogel nanocomposites had greater swelling capacity and diffusion coefficient compared to PVA hydrogel. Both hydrogel systems show non-Fickian diffusion and Schott second order kinetics, at early and extensive stage of swelling, respectively. Investigated nano-Ag/PVA hydrogel nanocomposites show continuous release of silver over a long period of time and, as consequence, the test of antimicrobial activity was performed. Antimicrobial efficiency was determined by agar-diffusion test and the obtained results clearly show the formation of inhibition zone towards Escherichia coli and Staphylococcus aureus in the case of higher nano-Ag concentration. RADIATION-INDUCED SYNTHESIS AND SWELLING PROPERTIES OF P(2-HYDROXYETHYL METHACRYLATE-CO- ITACONIC ACID-CO-OLIGO(ETHYLENE GLYCOL) ACRYLATE) COPOLYMERIC HYDROGELS

M. Micic and E. Suljovrujic Vinca Institute of Nuclear Sciences, University of Belgrade, Belgrade, Serbia

Since it is presumed that by incorporation of pH-responsive (IA) and temperature- responsive (OEGA) co-monomers it is possible to prepare P(HEMA-co-IA-co-OEGA) hydrogels with dual (pH and thermo) responsiveness, the main purpose of this paper is to investigate the influence of different mole fractions of IA and especially OEGA on the diversity of the swelling properties of obtained hydrogels. For that reason, a series of copolymeric hydrogels with different mole ratios of 2-hydroxyethyl methacrylate (HEMA), itaconic acid (IA) and oligo(ethylene glycol) acrylates (OEGA) was synthesized by gamma radiation. The obtained hydrogels were characterized by swelling studies in the wide pH (2.2-9.0) and temperature range (25-70 °C), confirming dual (pH and thermo) responsiveness and a large variation in swelling capability. It was observed that the equilibrium swelling of P(HEMA-co-IA-co-OEGA) hydrogels, for a constant amount of IA, increases progressively with increasing in OEGA share. On the other hand, the dissociation of carboxyl (-COOH) groups from IA occurs at pH>4; therefore, small mole fractions of IA render good pH sensitivity and a large increase in the swelling capacity of these hydrogels at higher pH values. Additional characterization of structure and properties was conducted by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and mechanical measurements, confirming that the inherent properties of the P(HEMA-co-IA-co- OEGA) hydrogels can be significantly tuned by variation in their composition. According to all presented, it seems that the obtained copolymeric hydrogels can be a beneficial synergetic combination for controlled delivery of bioactive molecules such as drugs, nucleic acids, peptides, and proteins. - 112 -

E-BEAM CROSSLINKED, BIOCOMPATIBLE FUNCTIONAL HYDROGELS INCORPORATING POLYANILINE NANOPARTICLES

C. Dispenza, M.-A. Sabatino, A. Niconov, D. Chmieliewska and G. Spadaro Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Universitá degli Studi di Palermo, Viale delle Seienze 90128 Palermo, Italy

Objective of this research is to develop a functional soft nanocomposites platform that combines the electro-optic properties of conjugated polymer nanoparticles with process flexibility, highly hydrophilic character, 3D structure and biocompatibility of hydrogels, to yield novel soft materials with multi-application potential in diagnostic, therapeutic and regenerative medicine. PANI aqueous nanocolloids in their acid doped, inherently conductive form, are synthesised by means of suitable polymeric stabilisers, i.e. water soluble polymers, that may prevent irreversible PANI particles coalescence and precipitation during synthesis and upon storage. Depending on the nature and concentration of the polymeric stabiliser, e.g. polyvinyl pyrrolidone (PVP), polyvinylalcohol (PVA) or chitosan (CT), PANI has been synthesised in form of nanoscalar rods, spherical particles or rice grains, respectively. In the present work, e-beam irradiation with a 12 MeV Linac accelerator has been tested, in alternative to gamma-rays, as a viable industrial methodology to generate hydrogel nanocomposites via in-situ crosslinking of the polymers already used to stabilise polyanline nanocolloids, at low temperature, with no recourse to further addition of molecular weight chemicals and in a few minutes. In these conditions nanoparticles morphology of PANI should be preserved and interesting electro-optical properties can be imparted. The swelling properties of the different hydrogel nanocomposites have been investigated at the variance of the chemical structure of the matrix material and of the pH of the swelling medium. UV- visible absorption and fluorescence spectroscopies demonstrate the retained optical activity of the dispersed PANI nanoparticles when incorporated in the hydrogels. Selected formulations have been also subjected to MTT assays and absence of cytotoxicity has been ascertained as the first necessary step to assess their biocompatibility. - 113 -

POLYPROPYLENE NANOGEL “MYTH OR REALITY”

W.L. Oliani1*, D.F. Parra1*, H.G. Riella2), L.F.C.P. Lima” and A.B. Lugao1* '^Nuclear and Energy Research Institute, IPEN-CNEN/SP, Av. Prof. Lineu Prestes, 2242 - Cidade Universitária - CEP 05508-000 Sao Paulo - SP - Brasil 2)Federal University of Santa Catarina, UFSC - University Campus - CEP 88040-900 -Florianópolis - SC - Brasil

The objective of this work is to study the formation of nanogel and microgel in modified PP. The modified PP in pellets was synthesized by gamma irradiation of pristine PP under a crosslinking atmosphere of acetylene in dose of 12.5 kGy, followed by thermal treatment for radical recombination and annihilation of the remaining radicals. The thin film gel of the polypropylenes was obtained by extraction in boiling xylene for period of 12 h at 138 °C, followed by decantation in becker at room temperature of 25°C with the total volatilization of the xylene and deposition of dried material film on fine glass blades under agitation by Settling process. The thin film gel formed of pristine PP and modified (i.e., irradiated) was characterized using scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM) and differential scanning calorimetry (DSC). The PP morphology indicated the nanogels and microgel formation with increase of spherulitic concentration and crystallinity at dose 12.5 kGy.

Acknowledgement - The authors thank FAPESP, CAPES for grants, CCTM/IPEN, for microscopy analysis SEM, Eleosmar Gasparin for DSC analysis and Embrarad/CBE for irradiating the samples.

AUTHOR INDEX

Abas, M.R. 14 Cardoso, E.L.C. 70 Abbasova, D. 86, 93 Casimiro, M.H. 22, 30 Adu-Gyamfi, A. 94 Celik, G. 62 Agyei-Amposah, J. 94 Chamam, M. 99 Akbulut, M. 59 Charpentier, T. 42 Alba-Simionesco, C. 42 Chatelain, C. 42 Alberti, A. 51,52, 98 Chaychian, M. 11 Albu, M.G. 58 Cherubini, R. 9 Alessi, S. 64 Chiaravalle, A.E. 51,52,98 Alexandru, M. 108, 109 Chiesa, L.M. 52, 98 Alkan, H. 95 Chmielewski, A.G. 15,39 Al-Sheikhly, M. 11 Chmieliewska, D. 112 Alves, L.C. 24 Constantin, M. 108 Amato, V.S. 46 Cook, A.R. 49 Anan’ev, V. 91 Copuroglu, M. 26 Antonio, A.L. 95 Coqueret, X. 16, 17 Apea-Bah, F.B. 94 Corvo.M.C. 30 Baidak, A. 1 Crowell, R.A. 49 Ballay, L. 36 Cuba, V. 45 Baranova, I.A. 6, 50 Cutrubinis, M. 13,54, 97 Bárány, T. 66 Czvikovszky, T. 66, 73 Barbu, O.H. 97 Csay, T. 100, 104 Bárdi, M.A.G. 27 Dauvois, V. 42 Barreira, J.C.M. 95 De Nadal, V. 9 Barsbay, M. 62 Demsar, A. 107 Bárta, J. 45 Deng, B. 65 Bartoszek, N. 21 Dispenza, C. 38, 64, 112 Baumberger, S. 16 Docekalova, Z. 45 Beiler, B. 60 Dole, P. 16 Bento, A. 95 Dombi, A. 4,12 Bliard, C. 16 Dondi, D. 9, 88 Boniglia, C. 96 Du, Y. 47 Borsa, J. 74 Dumas, L. 19 Bortolin, E. 96 Dumitra§cu, M. 58 Botelho, M.L. 95 Durand, D. 42 Bracco, S. 88 Durchschlag, H. 8 Brodie-Linder, N. 42 Dzeba, I. 55 Brunet, F. 42 Emmi, S.S. 48 Bubueanu, Gh. 56, 63, 87 Ene, M. 108 Buchmüller, Y. 61 Ershov, B.G. 92 Bugheanu, P. 13 Esposito, B. 48 Bulone, D. 64 Fainchtein, O.L. 103 Buttafava, A. 9, 88 Falcao, A.N. 24 Cai, R. 65 Farah, K. 33 Caminati, S. 48 Faucitano, A. 9,88 Cao, W. 77 Fazoli, M. 79 Fekete, T. 74 Homlok, R. 102,104, 105 Feldman, V.I. 6, 50, 90 Hosni, F. 33 Fernandes, Á. 95 Hosseini, A.M. 99 Fernandes, N. 30 Ignatovich, M. 35, 79, 80 Fernandes, W. 20 Illés, E. 12 Ferreira, H.P. 31 Indrei, J. 45 Ferreira, I.C.F.R. 95 loan, A. 57 Ferreira, L.M. 22, 24, 30 Ionitá, A. 108 Fleury, E. 19, 28 Isik, S.D. 43 Floridi, F. 52 Iwamatsu, K. 2 Fontana, G. 68 Janata, E. 44 Forster, P.L. 68 Jelcic, Z. 69 Fortin, N. 28 Jiang, H. 65 Földváry, Cs.M. 99 Jurkin, T. 18, 84 Fugaru, V. 63 Kacarevic-Popovié, Z. 110 Fuochi, P.G. 51,52, 98 Kadlubowski, S. 21 Gajda-Schrantz, K. 12 Kan, K. 3,89 Galovic, S. 71 Kang, W. 10 Gargiulo, R. 96 Katsumura, Y. 2 Gbur, T. 45 Katusin-Razem, B. 107 Georgescu, R. 109 Kavkler, K. 107 Georgescu, R. 54, 56 Kelemen, A. 34, 35, 79, 80 Geraldo, A.B.C. 20 Khandal, D. 16 Gerardi, S. 9 Kim, S-M. 10 Giacomazza, D. 64 Kimura, A. 106 Goldstein, S. 7, 47 Ko, K.R. 81 Gonter, K. 12, 101 Kobzarenko, A.V. 50 Gopalan, A. 81,83 Komathi, S. 81 Grasselli, M. 82 Komathi, S. 83 Grimaldi, N. 64 Kondoh, T. 3, 89 Gubler, L. 61 Koós, M. 60 Gunde-Cimerman, N. 107 Kovács, A. 33,34 Guo, J. 77 Kovalev, G.V. 50 Günaydi, T. 95 Kozawa, T. 3, 89 Gürsel, S.A. 23 Krkljes, A. 110 Güven, 0 . 40, 43, 59, 62 Krstié, J. 110 Haiducu, M. 109 Kurashima, S. 2 Haji-Saeid, M. 37 Laikov, D.N. 6 Han, B. 10 Lancastre, J.J.H. 30 Hashim, S.A. 14 LaVeme, J.A. 1,25 Hayrabolulu, H. 72 Le Caér, S. 42 Helt-Hansen, J. 32 Leal, J.P. 24 Himics, L. 60 Lee, K.-P. 81,83 Hj Dahlan, K.Z. 14 Lee, S.-H. 81,83 Holodkova, E.M. 92 Li, J. 65, 75, 76 Flolovey, V. 80 Licli, J. 15 Lima, L.F.C.P. 113 Oliani, W.L. 113 Liu, W. 29 Oliveira, M.J.A. 46 Lugao, A.B. 31,46, Oliveira, M.R.R. 53 68, 70, 113 Orlov, A.Y. 50 Ma, H. 75 Osawa, M. 106 Macciantelli, D. 51 Osvay, M. 34, 36 Machado, L.D.B. 27 Owulah, C. 94 Mahami, T. 94 Paes, H.A. 20 Mandarino, J.M.G. 53 Pák, V. 91 Manea, M.M. 13,54,58,97 Pálfi, T. 104 Mangiacotti, M. 51,52, 98 Parra, D.F. 31,46, 68, 113 Manzoli, J.E. 20 Pavelková, T. 45 Marchesani, G. 51,52, 98 Pavlova-Schmitz, P.I. 25 Marchini, L.G. 68 Pawelec, A. 15 Margaca, F.M.A. 30 Pawlak, E. 82 del Mastro, N.L. 53 Peng, J. 76 Medvedovici, A.V. 13 Pimblott, S.M. 25 Mejri, A. 33 Pinto, J.V. 22 Meltzer, V. 58 Ponomarev, A.V. 92 Mesterházy, D. 34, 80 Ponta, C.C. 13,97 Mészáros, L. 66 Portinha, D. 19, 28 Michaela, M. 57 Pospisil, M. 45 Micic, M. 8 5 ,111 Postolache, C. 56, 63, 87 Mihai, C. 57 Przybytniak, G. 64, 78 Mihaljevic, B. 55, 107 Pucic, I. 18, 84, 107 Mikus, P-Y. 16 Rabani, J. 47 Milicevic, D. 67,71 Rácz, G. 100 Milivojevic, D. 67 Ramamoorthy, N. 37 Miller, A. 32 Ramos, A.M. 22 Minea, R. 58 Ranogajec, F. 69 Miranda Salvado, I.M. 30 Ranoux, G. 17 Mirzadeh, H. 41 Renault, J.-P. 42, 49 Moise, I.V. 13,54,58,97, Riella, H.G. 113 108, 109 Risso,V. 82 Monaca, S.D. 96 Rodrigues, P.A. 24 Morgunov, V.V. 103 Romhány, G. 73 Moura, E. 20 Rosiak, J.M. 21 Múcka, V. 45 Rouif, S. 19, 28 Musat, R.M. 49 Sabatino, M.A. 64,112 Negut, C.D. 13,54, 97, Saenko, E.V. 6 Nesterov, S.V. 90 Sáfrány, A. 37, 60 Niconov, A. 112 Sampa, M.H.de O. 37 Nisipeanu, S. 109 Sanli, L.l. 23 Norizawa, K. 3,89 Saracino, M. 48 Nowicki, A. 78 Sasson, U. 10 Ogata, A. 3,89 Scagliusi, S.R. 70 Scherer, G.G. 61 Vajna, B. 73 Schiller, R. 5 Vancea, C. 58 Secerov, B. 71 Veres, M. 60 Seidl, C. 8 Veres, M. 81 Seifalian, A.M. 41 Virgolici, M. 13,54,58, 97 §en, M. 26, 72 Vital, J. 22 Shahdo-Alam, M. 42 Vlk, M. 45 Shkilko, A.M. 103 Vukasinovic Milic, T. 85 Silva, A.G. 22 Wang, M. 29, 75 Silveira, C.G. 20 Witman, S. 15 Silverman, J. 11 Wojnárovits, L. 12, 74, 99, 100, Sima, E. 58 101,102, 104, 105 Siragusa, G. 52 Wokaun, A. 61 Smietanko-Chmielewska, 39 Wong, C.S. 14 Smolko, E.E. 82 Wu, G. 29 Solouk, M. 41 Xing, Z. 29 Somessari, S.M. 20 Xu, L. 76 Soto Espinoza, S.L. 82 Yamaguchi, M. 2 Souza, C.A. 20 Yang, J. 3,89 Sozzani, P. 88 Yao, S. 75 Spadaro, G. 64, 112 Yarar, B. 40 Spasojevic, J. 110 Yoshida, Y. 3,89 Stanculescu, l.R. 13,97 Yu, Y. 65 Sugo, Y. 2 Zakurdaeva, O.A. 90 Sukhov, F.F. 50 Zalar, P. 107 Suljovrujic, E. 67,71,85, Zavadilová, A. 45 111 Zeffiro, A. 88 Sun, Y. 15 Zeng, X. 77 Suvaila, R. 54 Zhai, T. 77 Szabó, L. 105 Zhai, M. 76 Szebényi, G. 73 Zhang, Y. 76 Tagawa, S. 3, 89 Zhao, L. 76 Taguchi, M. 2, 106 Zhou, C. 77 Takács, E. 12, 74, 99, 100, Zimek, Z. 15 101,102, 104, 105 Zimek, Z. 78 Tiefenbach, K-J. 8 Zommer, N. 10 Todaro, S. 64 Zorilá, F. 108 Toigawa, T. 3 Zorila, F. 109 Tóth, T. 105 Trandafir, L. 108 Trandafir, L. 109 Trifunovic, S. 71 Tungler, A. 99 Túrák, 0 . 36 Tuta, C. 56, 63, 87 Ulanski, P. 21 LIST OF PARTICIPANTS

ABBASOVA, Dinara Institute of Radiation Problems of AzNAS Azerbaijan [email protected]

ADU-GYAMFI, Abraham Dep. of Food Science and Rad. Processing,Biotechn.and Nuc. Agr. Res. Inst.,GAEC P.O.Box LG 80, Legon, Accra Ghana adugyamfi2 1 @yahoo.com

AKBULUT, Meshude Department of Chemistry, Hacettepe University 06800 Bytepe, Ankara Turkey [email protected]

AKOVALI, Guneri Dept. Chemistry and Polymer Sci., Middle East Technical University Inönü Bui., 06531 Ankara Turkey

ALKAN GÜRSEL, Selmiye Sabanci University, Faculty of Engineering and Natural Sciences Istambul, 34956 Turkey [email protected]

AL-SHEIKHLY, Mohamad University of Maryland, Department of Materials Science and Engineering BLDG 090, College Park, MD 20742-2115 USA [email protected]

BAHNAREL, Ion National Scientific-Applied Centre of Preventive Medicine NSACPM Gheorghe Asachi street 67a, 2028 Chisinau Republic of Moldova [email protected], [email protected] BARANYAI, Mária Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

BARDI, Marcelo Augusto Gonsalves Universidade de Sao Paulo, Institute de Pasquisas Energeticas e Nucleares, IPEN/USP Av. Professor Lineu Prestes 2242,Cidade Universitária, Sao Paulo , 05505-000 Brazil [email protected]

BEILER, Barbara Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

BEKMURATOV, Timur Institute of Nuclear Physics, National Nuclear Centre of the Republic Kazakhstan NNC Ulitsa Ibragimova 1, 050032 Almaty Kazahstan bekmuratov@inp .kz

BORTOLIN, Emanuela Istituto Superiore di Sanita Viale Regina Elena 299, Rome 00161 Italy [email protected]

BOSHNAKOVA, Nelly Sopharma Ltd. Iliensko Shosse 16,1220, Sofia Bulgaria [email protected]

BROCARDO MACHADO, Luci Diva IPEN-CNEN/SP Avenida Professor Lineu Prestes, 2242, 05508-000, Sao Paulo Brazil [email protected] BUBUEANU, George Horia Hulubei National Institute for Physics and Nuclear Engineering, IFIN HH Atomistilor street 407, Magurele, Ilfov, 077125 Romania [email protected]

BUCHMÜLLER, Yves Paul Scherrer Institut PSI Viliigen, CH 5232 Switzerland [email protected]

BUZDUGAN, Artur National Agency for Regulation of Nuclear and Radiological Activities, NARNRA A. Russo St. 1, MD2068 Chisinau Republic of Moldova [email protected]

CASIMIRO, Maria Helena Departamento de Quimica, Faculdade de Ciéncias e Tecnologia, REQUIMTE/CQFB Universidade Nova de Lisboa, 2829-516 Caparica Portugal [email protected], [email protected]

CHAMAM, Mounir Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

CHMIELEWSKI, Andrzej G. Institute of Nuclear Chemistry and Technology, Warsaw University of Technology Dorodna 16, Pl-03-195, Warsaw Poland [email protected]

CONSTANTIN, Mihai Horia Hulubei National Institute for Physics and Nuclear Engineering, IRASM Str. Reactorului no 30, Magurele, Bucharest 077125 Romania [email protected] COPUROGLU, Mehmet Department of Chemistry, Polymer Chemistry Division, Hacettepe University 06800 Bytepe, Ankara Turkey [email protected]

COQUERET, Xavier ICMR, UMR,CNRS 6229, Université de Reims Champagne Ardenne 51687 Reims France [email protected]

CSAY, Tamás Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

CUBA, Václav Czech Technical University in Prague Brehová Street 7, 115 19 Prague 1, Prague Czech Republic [email protected]

CZVIKOVSZKY, Tibor Budapest University of Technology and Economics H-1111, Budapest, Műegyetem rkp.3. Hungary [email protected]

DISPENZA, Clelia Dipertimento di Igegneria Chimica, Gestionale, Informatica, Meccanica, Universitá degli Studi di Palermo Via delle Scienze 90128, Palermo Italy [email protected]

DOMBI, András Institute of Materials Sciences and Engineering, University of Szeged H-7620, Szeged, Tisza L. Krt.103 Hungary [email protected] DONDI, Daniele Dipartimento di Chimica-Universita' di Pavia V.le Taramelli 12 27100 Pavia Italy [email protected]

DUMAS, Ludovic Université de Lyon, INSA-Lyon, CNRS UMR 5223, Bat. Jules Veme, 17 avenue Jean Capelle, F-69621, Villeurbanne France [email protected]

DUMITRA§CU, Maria National Institute for Lasers Plasma and Radiation Physics 409 Atomistilor Street, 077125, Magurele Romania maria_dumitrascu@yahoo. com

DURCHSCHLAG, Helmut University of Regensburg, Institute of Biophysics Physical Biochemistry Universitaets Strasse 31., Regensburg, D-93040 Germany [email protected]

DZEBA, Iva Radiation Chemistry and Dosimetry Laboratory, Ruder Boskovic Institute Bijenicka 54,10000 Zagreb Croatia [email protected]

EMMI, Salvatore Silvano ISOF-CNR Via P. Gobetti 101,1-40129, Bologna Italy [email protected]

ESPOSITO, Biagio Ruggero CNR Via P. Gobetti 101,1-40129, Bologna Italy [email protected] FARAH, Khaled Unité de recherche: Maitrise et développement des techniques nucléaires á caractére pacifique, CNSTN 20201 Sidi-Thabet Tunisia [email protected], [email protected]

FAUCITANO, Antonio Department of Chemistry, University of Pavia V.le Taramelli 12 27100 Pavia Italy . [email protected], [email protected]

FELDMAN, Vladimir Department of Chemistry, Moscow State University Moscow, 119991 Russia [email protected]

FERREIRA, Henrique Perez Nuclear and Energy Research Institute, IPEN-CNEN Av. Professor Lineu Prestes, 2242, 05508-000, Sao Paulo Brazil [email protected]

FERREIRA, Luis M. Unidade de Fisica e Aceleradores, Institute Tecnológico e Nuclear, UFA-ITN 2656-953, Sacavém Portugal [email protected], [email protected]

FUGARU, Viorel Horia Hulubei National Institute for Physics and Nuclear Engineering, IFIN HH Atomistilor street 407, Magurele, Ilfov Romania [email protected]

FULOP, Marko Slovak Medical University Limbova 12, 831 31 Bratislava Slovakia [email protected] FUOCHI, Piergiorgio ISOF-CNR Via P. Gobetti 101,1-40129, Bologna Italy [email protected]

GERALDO, Aurea Institute de Pesquisas Energéticas e Nucleares IPEN/CNEN-SP Av. Professor Lineu Prestes, 2242, 05508-000, Sao Paulo Brazil [email protected] . -

GOLDSTEIN, Sara Institute of Chemistry, the Hebrew University of Jerusalem Jerusalem 91904 Israel [email protected]

GONTER, Katalin Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary gonter @iki .kfki .hu

GOP ALAN, Anantha Iyengar Kyungpook National University 1370, Sankyuk-dong, Buk-gu, Daegu South Korea [email protected]

GRASSELLI, Mariano Universidad Nációnál de Quilmes Roque Saenz pena 352, Bernal, Buenos Aires, B1876BXD Argentina [email protected], [email protected]

GRIMALDI, Natascia Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Universitá degli Studi di Palermo Viale delle Scienze Ed. 6, 90128, Palermo Italy [email protected] GÜVEN, Olgun Hacettepe University, Department of Chemistry Ankara Turkey [email protected]

HAJI-SAEID, Mohammad International Atomic Energy Agency Vienna International Centre, Wagramerstrasse, A -1400, Vienna Austria [email protected]

HAN, Bumsoo EB TECH Co., Ltd 550 Yongsam-dorig, Yuseong-gu, Daejeon 305-500 Korea [email protected]

HARGITTAI, Péter Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

HASHIM, Siti Aisah Malaysian Nuclear Agency Bangi, Kajang, Selangor, 43000 Malaysia [email protected]

HOMLOK, Renáta Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

IGNATOVYCH, Magdalyna Chuoki Institute of Surface Chemistry, NASU 17 Gen, Naumov Str., Kyiv 03164 Ukraina [email protected] ILLÉS, Erzsébet Institute of Materials ciences and Engineering, University of Szeged H-6720, Szeged, Tisza L.krt 103 Hungary [email protected]

ISIK, Semiha Duygu Department of Chemistry, Hacettepe University 06800, Ankara Turkey [email protected]

JANATA, Eberhard Helmholtz Zentrum Berlin fur Materialien und GmbH Hanh- -meitner-Platz 1, Berlin, D-14109 Germany [email protected]

JURKIN, Tanja Ruder Boskovié Institute Bijenicka 54, Zagreb, 10 000 Croatia [email protected]

KALUSKA, Iwona Monika Institute of Nuclear Chemistry and Technology ul. Dorodna 16, 03-195 Warsaw Poland i.kaluska@ichtj .waw.pl

KATU SIN -RAZEM, Branka Ruder Boskovic Institute Bijenicka 54, Zagreb, 10 000 Croatia [email protected]

KELEMEN, András Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected] KHAILOV, Zahur Institute of Radiation Problems of AzNAS B. Vakhabzade Avenue 9,1143 Baku Azerbaijan [email protected]

KLIMENKO, Sergey Institute of Nuclear Physics, National Nuclear Centre of the Republic Kazakhstan NNC Ulitsa Ibragimova 1, 050032 Almaty Kazahstan [email protected]

KOBZARENKO, Alexey Department of Chemistry, Moscow State University Leninskie Gory1/3, 119991 Moscow Russia [email protected]

KOCZOG, Éva Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary koczog@iki .kfki .hu

KONDOH, Takafumi Osaka University 8-1 Mihogaoka, Ibaraki, Osaka, 567-0047 Japan [email protected]

KORZENIO W SKA-SOBCZUK, Anna Malgorzata Institute of Nuclear Chemistry and Technology ul. Dorodna 16, 03-195 Warsaw Poland [email protected] .waw.pl

KOVÁCS, András Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected] KRKLJES, Aleksandra Vinca Institute of Nuclear Sciences P.O.Box 522, Belgrade, 11001 Serbia [email protected]

LANCASTRE, Joana J. H. ITN Nuclear and Technological Institute, Unit of Physics and Accelerators E:N 10,2656-953, Sacavém Portugal [email protected]

LANUZA, Luvimina Philippine Nuclear Research Institute PNRI Commonwealth Avenue, Diliman, P.O.Box 213, Quenzon City 1101 Philippines [email protected]

La VERNE, Jay A. Universiti of Notre Dame 314 Radiation Laboratory, Notre Dame, 46556 USA laveme. 1 @nd.edu

LE CAÉR, Sophie CNRS, CEA/Saclay DMS/IRAMIS SIS2M UMR 3299 Equipe Radiolyse Bat.546, Gif-sur-Yvette, F-91191 France [email protected]

LEE, Kwang-Pill Kyungpook National University 1370, Sankyuk-dong, Buk-gu, Daegu, 702-701 South Korea [email protected]

LI, Jingye Shanghai Institute of Applied Physics, Chinese Academy of Sciences No.2019, _Jialuo Rd., Jiading Dist., Shanghai, 201800 China [email protected] LI, Shufeng Beijing Research Center for Radiation Application A10 Dayangfang, Andingmen Wai, Chaoyang district, Beijing, 100012 China [email protected]

LOPES-ANTONIO, Amilcar Institute Politécnico de Braganca Braganca, 5301-855, Portugal [email protected]

LUGAO, Ademar Benevolo Nuclear and Energy Research Institute, IPEN-CNEN Av. Professor Lineu Prestes, 2242, 05508-000, Sao Paulo Brazil [email protected]

MANGIACOTTI, Michele Istituto Zooprofilattico Sperimentale della Puglia e della Basilicate, Universitá degli Studi di Milano Via Manfredonia 20,1-71121 Foggia Italy [email protected]

MARCHESANI, Giuliana Istituto Zooprofilattico Sperimentale della Puglia e della Basilicate, Via Manfredonia 20,1-71121 Foggia Italy giulianamarchesani@libero it del MASTRO, Nélida Lucia IPEN-CNEN/SP Av. Prof. Lineau Prestes 2240, Sao Paulo 05508-900 Brazil [email protected]

MESTERHÁZY, Dávid Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected] MÉSZÁROS, László Budapest University of Technology and Economics H-1111, Budapest, Műegyetem rkp.3. Hungary [email protected]

MICIC, Maja Vinca Institute of Nuclear Sciences P.OiBox 522, Belgrade, 11001 Serbia [email protected]

MILICEVIC, Dejan Vinca Institute of Nuclear Sciences P:0: Box 522, Belgrade, 11001 Serbia [email protected]

MILLER, Arne Riso High Doe Reference Laboratory, Technical University Riso, TDU, Frederiksborgvej 399, Roskilde, DK-4000 Denmark [email protected]

MIRZADEH, Hamid Polymer Engineering Department, Amirkabir University of Technology 15916-3411, Teheran Iran [email protected]

MOISE, loan Valentin Horia Hulubei National Institute for Physics and Nuclear Engineering 30 Reactorului St., 077125, Magurele, Ilfov Romania [email protected]

MORGUNOV, Volodymyr Ukrainian Engineering Pedagogical Academy Universitetskaya str. 16, 61003, Kharkov Ukraina [email protected] NESTEROV, Sergei V. Enikolopov Institute of Synthetic Polymer Materials of RAS ul. Profsoyuznaya 70, Moscow, 117393 Russia [email protected]

OSVAY, Margit Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

PAK, Valeriy Kemerovo State University Krasnaya st. 6.,Kemerovo, 650043 Russia [email protected]

PARKS, Lew Sterigenics International 7695 Formula Place, San Diego, CA, 92121 USA [email protected]

PARRA, Duclerc Fernandes Nuclear and Energy Research Institute, IPEN-CNEN Av. Professor Lineu Prestes, 2242, 05508-000, Sao Paulo Brazil [email protected]

PÁLFI, Tamás Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected], [email protected]

PIMBLOTT, Simon M. The University of Manchester, The School of Chemistry Oxford Road, Manchester, M l3 9PL United Kingdom [email protected] PONOMAREV, Alexander V. A. N. Frumkin Institute of Physical Chemistry and Electrochemistry Leninsky Prosp., 31, Moscow, 119991 Russia [email protected] .ru

PORTINHA, Daniel Université de Lyon, INSA-Lyon, CNRS UMR 5223,F-69621, Villeurbanne France [email protected]

POSTOLACHE, Cristian Horia Hulubei National Insitute for Physics and Nuclear Engineering Atomistilor street 407, Magurele, Ilfov, 077125 Romania [email protected]

PUCIC, Irina Laboratory for Radiation chemistry and Dosimetry, Ruder Boskovic Institute Zagreb, Bijenicka 54, 10000 Croatia [email protected]

QIN, Peizhong Beijing Research Center for Radiation Application A10 Dayangfang, Andingmen Wai, Chaoyang district, Beijing, 100012 China [email protected]

RABANI, Joseph The Accelerator Laboratory and Institute of Chemistry, The Hebrew University of Jerusalem Jerusalem 91904 Israel [email protected]

RANOGAJEC, Fran jo Ruder Boskovic Institute Bijenicka 54,10000 Zagreb Croatia [email protected] RANOUX, Guillaume Université de Reims Champagne-Ardenne UMR 6229, BP 1039,51687 Reims Cedex 2 France [email protected]

RÁCZ, Gergely Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary rgero@freemail .hu

SABATINO, Mara Antonietta Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Universitá degli Studi di Palermo Viale delle Scienze Ed. 6, 90128, Palermo Italy [email protected]

SARACINO, Micheia IS OF-CNR Via P. Gobetti 101,1-40129, Bologna Italy [email protected]

SÁFRÁNY, Ágnes International Atomic Energy Agency Vienna International Centre, Wagramerstrasse, A-1400, Vienna Austria [email protected]

SCAGLIAUSI, Sandra Nuclear and Energy Research Institute, Center of Chemistry and Environment (CQMA), Av. Professor Lineu Prestes, 2242, - Cidade Universitária 05508-900, Sao Paulo Brazil

SCHILLER, Róbert Central Research Institute for Physics, Atomic Energy Research Institute P.O.B. 49, Budapest H-1525 Hungary [email protected], [email protected] SECEROV, Bojana Vinca Institute of Nuclear Sciences P.O.Box 522, Belgrade, 11001 Serbia [email protected]

§EN, Murat Hacettepe University, Department of Chemistry Beytepe, Ankara, 06800 Turkey [email protected]

STANCULESCU, Ioana Horia Hulubei National Institute of Physics and Nuclear Engineering Str. Reactorului nö 30, Magurele, Bucharest 077125 Romania [email protected]

SULJOVRUJIC, Edin Vinca Institute of Nuclear Sciences P.O.Box 522, Belgrade, 11001 Serbia [email protected]

SZABÓ, László Budapest University of Technology and Economics H-1111, Budapest, Műegyetem rkp. Hungary [email protected]

SZEBÉNYI, Gábor Budapest University of Technology and Economics H-1111, Budapest, Műegyetem rkp.3. Hungary [email protected]

SZÉLES, Éva Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected] TAGUCHI, Mitsumasa Japan Atomic Energy Agency 1233 Watanuki, Takasaki, 370-1292 Japan [email protected]

TAKÁCS, Erzsébet Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected]

TRANDAFIR, Laura Horai Hulubei Institute of Physics and Nuclear Engineering 30, St. Reactorului, Magurele, Ilfov, 077125 Romania [email protected]

TURÁK, Oliver Frederic Joliot-Curie National Research Institute for Radiobiology and Radiohygiene Budapest, Anna U. 5., H-1221 Hungary [email protected]

ULANSK3, Piotr Institute of Applied Radiation Chemistry, Technical University of Lodz Wroblewskiego 15, Lodz, 93-590 Poland [email protected] .lodz.pl

UTKIN, Konstantin State Atomic Energy Corporation,ROSATOM ul. Bolshaya Ordinka24, 119017, Moscow Russia [email protected]

VIRGOLICI, Marian Horia Hulubei National Institute of Physics and Nuclear Engineering 30 Reactorului St., 077125, Magurele, Ilfov Romania m_virg°[email protected] WANG, Min Shanghai Institute of Applied Physics, Chinese Academy of Sciences 2019 Jialuo Road, Jiading, Shanghai, 201800 China [email protected]

WOJNÁROVITS, László Institute of Isotopes, Hungarian Academy of Sciences H-1525 Budapest, P.O.B. 77 Hungary [email protected] t,.

WU, Guozhong Shanghai Institute of Applied Physics, Chinese Academy of Sciences Jialuo Road 2019, Jiading, Shanghai, 201800 China [email protected]

YARAR, Begüm Hacettepe University, Department of Chemistry Beytepe, Ankara, 06800 Turkey [email protected]

YOSHIDA, Yoichi Osaka University 8-lOMihogaoka, Ibaraki, 0saka,567-0047 Japan [email protected]

ZHAI, Maolin Beijing National Laboratory for Molecular Sciences, Dep. of App. Chem., Peking University Yiheyuanlu No. 5,Beijing 100871 China [email protected]

ZHOU, Chengfei Quin Peizhomg, Beijing Research Center for Radiation Application A10 Dayangfang, Andingmen Wai, Chaoyang district, Beijing, 100012 China zhou_chengfei@ 163.com ZIMEK, Zibigniew Institute of Nuclear Chemistry and Technology, Department of Radiation Chemistry ul. Dorodna 16, 03-195 Warsaw Poland z.zimek@ichtj .waw.pl

ZORILA, Fiorina Horia Hulubei National Institute of Physics and Nuclear Engineering Str. Reactorului no 30, Magurele, Bucharest 077125 Romania [email protected]

The Symposium at a Glance

Saturday Sunday Monday Tuesday Wednesday Thursday August 27 August 28 August 29 August 30 August 31 September 1 Breakfast Breakfast Breakfast Breakfast B reakfast 08:20 Invited lecture Invited lecture Invited lecture 08:30 08:40 Coqueret Miller Haji-Saeid &Sáfrány 08:50 09:00 Opening Invited lecture Ranoux Farah Fuochi 09:10 Schiller 09:20 Invited lecture Dispenza Jurkin Mesterházy Mangiacotti 09:30 09:40 LaVcme Dumas Ignatovych Chmielewski Del Mastro 09:50 10:00 T aguchi Geraldo Túrák Giiven Moise 10:10 10:20 Coffee Yoshida Coffee Coffee Coffee 10:30 Poster 10:40 Special lecture intruduction Invited lecture Closing C offee 10:50 Rabani & Isik 11:00 Invited lecture Ulanski Mirzadch 11:10 11:20 Dombi Casimiro Le Caer 11:30 11:40 Schiller Gürsel Isik 11:50 Lunch 12:00 Feldman Ferreira Janata 12:10 Farewell Lunch 12:20 Cuba 12:30 12:40 Parra 12:50 Lunch 13:00 13:20 13:40 Lunch 14:00 Registration Invited lecture 14:10 14:20 Goldstein 14:30 Invited lecture 14:40 Durchschlag 14:50 Pimblott Esposito 15:00 Dondi 15:10 Copuroglu Musat 15:20 Coffee 15:30 Bardi Kobzarenko 15:40 Invited lecture Excursion 15:50 Portinha Coffee 16:00 Han 16:10 16:20 Invited lecture 16:30 Wu 16:40 Al-Sheikhly 16:50 Lancastre 17:00 Illés 17:10 Ferreira 17:20 Posters Stanculescu 17:30 17:40 Hash ini 17:50 18:00 Zimek 18:20 18:30 19:00 O pening 20:00 N ovák & Dinner Dinner C'onferenc Dinner 21:00 Wojnárovits & Dinner 22:00 Dinner