Annual Report 2008

ANNUAL REPORT 2008

INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY EDITORS Prof. Jacek Michalik, Ph.D., D.Sc. Wiktor Smułek, Ph.D. Ewa Godlewska-Para, M.Sc.

PRINTING Sylwester Wojtas

GENERAL INFORMATION 9

MANAGEMENT OF THE INSTITUTE 11 MANAGING STAFF OF THE INSTITUTE 11 HEADS OF THE INCT DEPARTMENTS 11 SCIENTIFIC COUNCIL (2007-2008) 11 SCIENTIFIC COUNCIL (2008-2012) 13

SCIENTIFIC STAFF 15 PROFESSORS 15 ASSOCIATE PROFESSORS 15 SENIOR SCIENTISTS (Ph.D.) 15

RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 19

PULSE RADIOLYSIS GENERATION OF THE RADICAL ANIONS AND CATIONS DERIVED FROM OXOISOAPORPHINE IN ORGANIC SOLVENTS K. Bobrowski, G. Kciuk, E. Sobarzo-Sanchez, J.R. De la Fuente 21 PULSE RADIOLYSIS STUDY OF INTERMEDIATES GENERATED IN IONIC LIQUIDS J. Grodkowski, R. Kocia, J. Mirkowski, T. Szreder, J.F. Wishart, A. Skrzypczak, A.R. Cook 23 PROMISING CALCITE-BASED TISSUE ENGINEERED PRODUCT FOR BONE A. Chróścicka, Z. Jaegermann, J. Wójtowicz, A. Ratajska, J. Sadło, P. Wychowański, G. Hoser, S. Michałowski, J. Przybylski, M. Lewandowska-Szumieł 27 EPR STUDY OF DOSIMETRIC MATERIALS G. Strzelczak, J. Sadło, J. Michalik 28 DENSITY FUNCTIONAL THEORY STUDY OF NONFRAMEWORK CATIONS IN ZEOLITE LATTICE M. Sterniczuk, J. Sadło, G. Strzelczak, J. Michalik 29 SOFTWARE AND HARDWARE IN THE ORIGINS OF LIFE CHEMISTRY Z.P. Zagórski 31 RADIATION COMPATIBILIZATION OF DISPERSED PHASE IN COMPOSITES A. Nowicki, G. Przybytniak, W. Starosta 33 THE INFULENCE OF IONIZING RADIATION ON THE THERMAL PROPERTIES OF SEGMENTED POLYURETHANES FOR BIOMEDICAL PURPOSES M. Walo, G. Przybytniak 35 SELECTION OF POLYMER MATRICES FOR RADIATION GRAFTING E.M. Kornacka, G. Przybytniak, K. Mirkowski 38 UNIT PROCESSES AND UNIT OPERATIONS IN RADIATION PROCESSING Z.P. Zagórski, W. Głuszewski 40 APPLICATION OF DRS FOR INVESTIGATIONS OF PROTECTION EFFECTS IN RADIOLYSIS OF POLYPROPYLENE W. Głuszewski, Z.P. Zagórski 42 GAMMA IRRADIATION AND HEAT TREATMENT INFLUENCE ON STRUCTURAL PROPERTIES OF POTATO STARCH-LIPID SYSTEMS STUDIED BY MEANS OF WAXS DIFFRACTION AND FTIR SPECTROSCOPY K. Cieśla, K. Łyczko 43 SCANNING ELECTRON MICROSCOPY STUDIES OF STRUCTURAL PROPERTIES OF FILMS PREPARED USING NON-IRRADIATED AND GAMMA-IRRADIATED POTATO STARCH K. Cieśla, B. Sartowska 46 DEGRADATION OF PERFLUORINATED CARBOXYLIC ACIDS IN AQUEOUS SOLUTIONS WITH THE USE OF IONIZING RADIATION A. Bojanowska-Czajka, P. Drzewicz, L. Wójcik, M. Trojanowicz 51 DOSIMETRIC PROPERTIES OF TWO PVC FILMS PRODUCED FOR PHARMACEUTICAL PURPOSES Z. Peimel-Stuglik, S. Fabisiak 53 ANALYTICAL ACTIVITY OF THE LABORATORY FOR DETECTION OF IRRADIATED FOOD ACCREDITED BY THE POLISH CENTRE FOR ACCREDITATION W. Stachowicz, K. Malec-Czechowska, G.P. Guzik, M. Laubsztejn, K. Lehner 55 LONG-LIVED RADICALS IN IRRADIATED GLUCOSE STUDIED AS A FUNCTION OF STORAGE TIME AND ELEVATED TEMPERATURE G.P. Guzik, W. Stachowicz 57 DETECTION OF RADIATION TREATED DRY PLANT EXTRACTS BY THERMOLUMINESCENCE AND PULSED PHOTOSTIMULATED LUMINESCENCE K. Lehner, K. Malec-Czechowska, W. Stachowicz, G. Guzik 60

RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 63

MACROCYCLIC COMPLEXES OF 44/47Sc AS PRECURSORS OF RADIOPHARMACEUTICALS A. Majkowska, A. Bilewicz 65 THE SUBSTITUTION OF CHLORIDES IN A RHODIUM-BASED DRUG PRECURSOR BY HUMAN PLASMA THIOLS S. Krajewski, A. Bilewicz 66

176 177 SEPARATION OF Yb AS YbSO4 FROM A Yb TARGET FOR PRODUCTION OF Lu VIA THE 176Yb(n,γ)177Yb → 177Lu PROCESS A. Bilewicz, K. Żuchowska, B. Bartoś 68 DESIGN OF NEW PET RADIOPHARMACEUTICALS BASED ON ACYCLIC COMPLEXES OF 89Zr M. Połosak, A. Bilewicz 69 PROCESSING OF GENERATOR-PRODUCED 44Sc FOR MEDICAL APPLICATION M. Pruszyński, N.S. Loktionova, F. Rösch 71 SYNTHESIS AND STRUCTURE OF TETRAKIS(TROPOLONATO)TIN(IV) K. Łyczko, K. Woźniak 73 “2+1” TRICARBONYLTECHNETIUM(I) AND -RHENIUM(I) COMPLEXES WITH N-METHYL-2-PYRIDINECARBOXYAMIDE AND β-ALANINE tert-BUTYL ISOCYANIDE – POTENTIAL PRECURSORS OF RADIOPHARMACEUTICALS E. Gniazdowska, L. Fuks, P. Koźmiński, J. Mieczkowski, J. Narbutt 74 VASOPRESSIN PEPTIDE (AVP) LABELLED WITH A “4+1” MIXED-LIGAND TECHNETIUM COMPLEX E. Gniazdowska, P. Koźmiński, K. Bańkowski, H.-J. Pietzsch 77 PLATINUM(II) COMPLEXES WITH THE THIOUREA DERIVATIVES L. Fuks, N. Sadlej-Sosnowska, E. Anuszewska, S. Siekierski 81 KINETICS OF ION EXCHANGE OF GALLIUM AND INDIUM IONS BETWEEN AQUEOUS HCl SOLUTIONS AND ANION EXCHANGER DOWEX 1-X8 I. Herdzik, J. Narbutt 86 CHEMICAL CHARACTERIZATION OF SEVERAL SAMPLES OF IRON TYPE METEORITES Z. Samczyński, R. Dybczyński, J. Kučera, J. Mizera, E. Chajduk, B. Danko 88 PROFICIENCY TESTING SCHEME PLANTS 8: DETERMINATION OF As, Cd, Cu, Hg, Pb, Se AND Zn IN DRY CAROOT ROOT POWDER H. Polkowska-Motrenko, E. Chajduk, J. Dudek, E. Czerska 90 INTERLABORATORY COMPARISON ON THE DETERMINATION OF 137Cs AND 90Sr IN WATER, SOIL AND LIQUID MILK H. Polkowska-Motrenko, L. Fuks, E. Chajduk, M. Pyszynska 93 RADIOCHEMICAL SCHEME FOR IRON DETERMINATION IN BIOLOGICAL MATERIALS BY NEUTRON ACTIVATION ANALYSIS B. Danko, M. Pyszynska, R. Dybczyński, M. Sadowska-Bratek, E. Czerska 96 FULLERENE AS SORBENT FOR SEPARATION AND DETERMINATION OF TOXIC ELEMENTS BY GF AAS J. Chwastowska, W. Skwara, M. Sadowska-Bratek, J. Dudek, M. Dąbrowska, L. Pszonicki 98

SYNTHESIS OF TiO2 THIN FILMS ON POROUS Ni OR Ni/NiO CATHODES FOR MCFC BY SOL-GEL PROCESS W. Łada, A. Deptuła, D. Wawszczak, T. Olczak, E. Simonetti 100 SYNTHESIS AND TESTING OF GEL METAL-OXIDE COMPOSITES AS FILLING MATERIALS FOR 188W/188RE GENERATOR COLUMNS E. Iller, A. Deptuła, F. Zaza, W. Łada, T. Olczak, D. Wawszczak, M. Brykała 102 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXVIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF PYRIDAZINE-4-CARBOXYLIC ACID HYDROCHLORIDE W. Starosta, J. Leciejewicz 105 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXIX. THE CRYSTAL AND MOLECULAR STRUCTURES OF HYDRAZINUM ADDUCTS OF THREE ISOMERIC PYRAZINE DICARBOXYLIC ACIDS W. Starosta, J. Leciejewicz 106 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXX. THE CRYSTAL AND MOLECULAR STRUCTURE OF A DIOXOURANIUM COMPLEX WITH PYRIDAZINE-3-CARBOXYLATE AND WATER LIGANDS J. Leciejewicz, W. Starosta 107 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXXI. THE CRYSTAL AND MOLECULAR STRUCTURES OF TWO CALCIUM(II) COMPLEXES WITH PYRIDINE-2,3-DICARBOXYLATE AND WATER LIGANDS W. Starosta, J. Leciejewicz 108 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXXII. THE CRYSTAL AND MOLECULAR STRUCTURE OF Pb(II) COMPLEX WITH PYRIDAZINE-4-CARBOXYLATE AND WATER LIGANDS W. Starosta, J. Leciejewicz 110 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXXIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF A LEAD(II) COMPLEX WITH A 2,2’-DIPYRIDINE-5,5’-DICARBOXYLATE LIGAND W. Starosta, J. Leciejewicz 111

RADIOBIOLOGY 113

BIOLOGICAL EFFECTIVENESS OF 12C AND 20Ne IONS WITH VERY HIGH LET J. Czub, I. Buraczewska, A. Wójcik 115 EXCESS PCC FRAGMENTS IN UNIRRADIATED HUMAN LYMPHOCYTES S. Sommer, S. Ritter, E. Nasonova 116 ESTIMATION OF GENOTOXICITY OF A HISTIDINE DINITROSYL IRON COMPLEX WITH AN IN VITRO PLASMID TEST T. Stępkowski, G. Wójciuk, K. Brzóska, M. Kruszewski 117 DINITROSYL IRON COMPLEX FORMATION IN K562 CELLS: EFFECTS OF AMMONIUM CHLORIDE AND OVEREXPRESSION OF THE HEAVY CHAIN OF FERRITIN K. Rumianek, J. Sadło, M. Kruszewski 118 DINITROSYL IRON COMPLEX FORMATION IN K562 CELLS: EFFECT OF N-ACETYL-Leu-Leu-Nle-ALDEHYDE (ALLN) K. Rumianek, J. Sadło, M. Kruszewski 119 DINITROSYL IRON COMPLEX FORMATION IN K562 CELLS: EFFECT OF HEMIN S. Męczyńska-Wielgosz, J. Sadło, H. Lewandowska-Siwkiewicz, M. Kruszewski 119 NO EFFECT OF TEMPERATURE DURING IRRADIATION ON THE LEVEL OF CYTOGENETIC DAMAGE IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES EXPOSED TO NEUTRONS K. Brzozowska, G. Obe, A. Wójcik 120 NO EFFECT OF TEMPERATURE DURING X-IRRADIATION ON THE LEVEL OF THE INITIAL DNA DAMAGE IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES K. Brzozowska, A. Wójcik 121 EFFECTS OF 1,4-DIHYDROPYRIDINE DERIVATIVE TREATMENT ON MUTATION FREQUENCY IN X-IRRADIATED CHO CELLS M. Wojewódzka, I. Grądzka, I. Buraczewska, K. Brzóska, R.I. Goncharova, I. Szumiel 122 EFFECTS OF 1,4-DIHYDROPYRIDINE DERIVATIVE TREATMENT ON BASE DAMAGE IN X-IRRADIATED CHO CELLS M. Wojewódzka, K. Brzóska, I. Szumiel 123 CLA SUPPLEMENTATION – INDUCED CHANGES IN THE PATTERN OF CHOLESTEROL AND EGFR DISTRIBUTION IN THE LIPID RAFTS OF HT29 CELL I. Grądzka, I. Buraczewska, I. Szumiel, Ch. Degen, G. Jahreis 123 NUCLEAR TECHNOLOGIES AND METHODS 125 PROCESS ENGINEERING 127

ELECTRON BEAM DECOMPOSITION OF TOLUENE IN GASEOUS PHASE Y. Sun, A.G. Chmielewski, S. Bułka, Z. Zimek 127 INDUSTRIAL TESTS ON BIOGAS PRODUCTION PROCESSES FROM FERMENTATION OF WASTE MATERIALS FROM THE MILK AND SUGAR INDUSTRIES P. Wojciechowski, A.G. Chmielewski, J. Palige, K. Szewczyk, J. Usidus 127 LABORATORY INVESTIGATIONS OF BIOMASS-GROWTH KINETICS ON BIOGAS PROCESS P. Wojciechowski, A. Dobrowolski, A.G. Chmielewski 128

NOx REMOVAL IN THE PROCESS OF ELECTRON BEAM FLUE GAS TREATMENT – CFD STUDY ON THE CONSTRUCTION OF REACTION CHAMBER A. Pawelec, A. Dobrowolski, A.G. Chmielewski 130 LABORATORY OF STABLE ISOTOPE RATIO MASS SPECTROMETRY – APPLICATION OF THE QUALITY SYSTEM AND ACCREDITATION K. Malec-Czechowska, R. Wierzchnicki, K. Plewka, P. Wojciechowski 131

SAMPLE COLLECTION AND PREPARATION FOR CO2 ISOTOPIC ANALYSIS IN INDUSTRIAL OFF-GASES K. Plewka, R. Wierzchnicki 133 PREPARATION AND CHARACTERIZATION OF PVDF MEMBRANES FOR ENVIRONMENTAL APPLICATIONS M. Harasimowicz, M. Khayet, G. Zakrzewska-Trznadel 134 APPLICATION OF RTD METHOD TO STUDY FLOW STRUCTURE AND HYDRODYNAMIC CONDITIONS IN APPARATUS WITH HELICAL FLOW A. Miśkiewicz, A. Dobrowolski, G. Zakrzewska-Trznadel 136 REMOVAL OF COPPER FROM AQUEOUS SOLUTIONS BY MICELLAR-ENHANCED ULTRAFILTRATION I. Xiarchos, A. Jaworska, G. Zakrzewska-Trznadel 137

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 139

INAA IN THE STUDIES OF LEAD WHITE IN THE MEDIAEVAL POLISH PAINTING OF THE POMERANIAN SCHOOL J. Olszewska-Świetlik, E. Pańczyk, L. Waliś 139 INCORPORATION OF RARE EARTH ELEMENTS Ce AND La INTO 316 STEEL USING HIGH INTENSITY PULSE PLASMA BEAM TECHNIQUE B. Sartowska, J. Piekoszewski, L. Waliś, M. Barlak, Z. Werner 143 ANALYSIS OF THE CHANNEL SHAPES IN TRACK MEMBRANES BY THE ELECTRON MICROSCOPY METHOD O.L. Orelovich, B. Sartowska, A. Presz, P.Yu. Apel 145 INVESTIGATIONS OF A PROTON PASSING THROUGH SOLID STATE NUCLEAR TRACK DETECTORS PM-355 TYPE B. Sartowska, A. Szydłowski, M. Jaskóła, A. Korman, A. Malinowska, T. Kuehn 146 THE ROLE OF Cr IN FORMATION OF NITROGEN EXPANDED AUSTENITE PHASE IN Fe-Cr ALLOY TREATED BY HIGH INTENSITY NITROGEN PLASMA PULSES J. Piekoszewski, L. Dąbrowski, B. Sartowska, C. Pochrybniak, P. Stoch, W. Starosta, L. Waliś, M. Barlak, Z. Werner 148 INFLUENCE OF DISTRIBUTION OF Ti ALLOYED INTO CARBON AND CARBIDE CERAMICS BY INTENSE PLASMA PULSES ON THEIR SURFACE WETTABILITY WITH LIQUID Cu M. Barlak, J. Piekoszewski, B. Sartowska, L. Waliś, Z. Werner,, E. Składnik-Sadowska, J. Kierzek, W. Starosta, A. Kolitsch, R. Grötzschel, K. Bocheńska 149 INFLUENCE OF IONIZING RADIATION ON SILVER CHLORIDE MICRORODS DEPOSITED INTO PARTICLE TRACK-ETCHED MEMBRANES M. Buczkowski, B. Sartowska, W. Starosta, J. Kierzek 150 SILICA BIOCIDAL MATERIALS WITH SILVER D.K. Chmielewska, A. Łukasiewicz 152

CHARACTERIZATION OF Ni POROUS ELECTRODE COVERED BY A THIN FILM OF LiMg0.05CO0.95O2 A. Deptuła, W. Łada, T. Olczak, E. Simonetti, R. Lo Presti 153 DYNAMIC CORRELATIONS IN MAGNETIC COMPOSITE UNDER MAGNETIC FIELD STUDIED BY XPCS H. Grigoriew, L. Wiegart, A. Boczkowska 155 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS 157

SOFTWARE MODIFICATION OF DUST POLLUTION MONITORING NETWORK A. Jakowiuk 157 ALPHA IRRADIATION FACILITY AIF-08 J.P. Pieńkos, E. Świstowski 158 EXAMINATIONS OF TH-2158 KLYSTRON MODULATOR FOR THE LINEAR ELECTRON ACCELERATOR TYPE LAE 10/15 Z. Zimek, Z. Dźwigalski, S. Warchoł, K. Roman, S. Bułka 158

PUBLICATIONS IN 2008 161 ARTICLES 161 BOOKS 167 CHAPTERS IN BOOKS 167 THE INCT PUBLICATIONS 169 CONFERENCE PROCEEDINGS 170 CONFERENCE ABSTRACTS 171 SUPPLEMENT LIST OF THE PUBLICATIONS IN 2007 182

NUKLEONIKA 184

THE INCT PATENTS AND PATENT APPLICATIONS IN 2008 188 PATENTS 188 PATENT APPLICATIONS 188

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 190

Ph.D. THESES IN 2008 217

EDUCATION 218 Ph.D. PROGRAMME IN CHEMISTRY 218 TRAINING OF STUDENTS 218

RESEARCH PROJECTS AND CONTRACTS 220 RESEARCH PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008 220 DEVELOPMENT PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008 220 IMPLEMENTATION PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008 220 RESEARCH PROJECTS ORDERED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008 221 INTERNATIONAL PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008 221 IAEA RESEARCH CONTRACTS IN 2008 221 IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2008 222 PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN 2008 222 INTERNATIONAL RESEARCH PROGRAMMES IN 2008 222 OTHER FOREIGN CONTRACTS IN 2008 223 LIST OF VISITORS TO THE INCT IN 2008 224

THE INCT SEMINARS IN 2008 226

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2008 228 LECTURES 228 SEMINARS 229

AWARDS IN 2008 231

INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 233

INDEX OF THE AUTHORS 246 GENERAL INFORMATION 9

GENERAL INFORMATION

Institute of Nuclear Chemistry and Technology (INCT) was established in 1983. It had been formerly operating since 1955 as the Chemistry Division of the former Institute of Nuclear Research. The Institute has an interdisciplinary character. The activities of the INCT include basic research, R&D as well as various services. The results of the INCT works have been implemented in various branches of national economy, particularly in industry, medicine, environmental protection and agriculture. Since the early sixties the Insti- tute has played a leading role in developing and implementing nuclear technologies, methods and instruments in the country. Nowadays the Institute is one of the most advanced centres in the field of: radiation chemistry and technology; application of nuclear methods in material engineering and process engineering; design and production of instruments based on nuclear techniques; radioanalytical techniques; environmental research. Basic research is focused on: radiochemistry, chemistry of isotopes, physical chemistry and engineering of separation processes, cellular radiobiology and radiation chemistry, particularly that based on pulse radiolysis method. Nowadays with its nine electron accelerators in operation and with the staff experienced in the field of electron beam application, the Institute is one of the most advanced centers of science and technology in this domain. The Institute is listed in the I cathegory scientific institutions group in accordance to the Ministry of Science and Higher Education. Scientific Council has rights to grant D.Sc. and Ph.D. degrees in the field of chemistry, and the Institute carries out third level studies (doctorate) in the field of nuclear and radiation chemistry. In 2008 six Ph.D. diplomas were granted. The Institute has four pilot plants equipped in six electron accelerators: for radiation sterilization of medical devices and tissue graft, for radiation modification of polymers, for removal of SO2 and NOx from flue gases and for food hygenization. The Institute is composed of three centers: Centre of Radiation Research and Tech- nology, Centre of Radiochemistry and Nuclear Chemistry, Centre of Radiobiology and Biological Dosimetry and seven laboratories: Laboratory for Measurements of Technological Doses, Laboratory for Detection of Irradiated Food, Laboratory of Nu- clear Control Systems and Methods, Laboratory of Stable and Environmental Iso- topes, Laboratory of Nuclear Analytical Methods, Laboratory of Material Research, Pollution Control Technologies Laboratory, a library and an information center. It is editor of the scientific journal “Nukleonika” (listed on ISI IF journals), INCT reports and Annual Report. *** In 2008, the INCT scientists published 85 papers in scientific journals registered in the Philadelphia list, among them 43 papers in journals with an impact factor (IF) higher than 1.0. Three scientific books and 17 chapters in the books written by the INCT research workers were published in 2008. In 2008, the INCT was carrying out 26 research projects granted by the Ministry of Science and Higher Education including three ordered projects, one implementation project and two development projects. The INCT scientists participated in 18 international research projects: seven granted by the UE (three in 6 FP and 7 FP, three in COST and one from Transition Facility), six IAEA projects, four bilateral cooperative 10 GENERAL INFORMATION projects and one supported by the Polish-Norwegian Research Fund. The Institute is a main counterpart for IAEA regional projects: RER 8010 (RER 8017 now) Quality control methods and procedures for radiation technology and RER 8011 Standard feasibility study for electron beam flue gas treatment technology. Annual rewards of the INCT Director-General for the best publications in 2008 were granted to the following research teams: • first degree team award to K. Bobrowski, D. Pogocki, G. Strzelczak, J. Mirkowski for a series of six articles concerning mechanisms of radiation-induced free-radical reactions in chemical compounds important from the biological point of view; • second degree team award to R. Dybczyński, H. Polkowska-Motrenko, B. Danko, Z. Samczyński, E. Chajduk for a series of eight publications summing the achievements of the team in the field of application of activation analysis to verify the content of trace elements in reference materials; • third degree team award to B. Sartowska, J. Piekoszewski, L. Waliś for a set of five publications on surface engineering concerning the modification of steel surface structure and enhancement its usable quality by nitrogen pulsed plasma treatment. In 2008, the research teams in the INCT were involved in organization of ten scientific meetings. Two of them won broad recognition and brought researchers from many countries, all over the world: • 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics PULS’2008 (6-12 September 2008, Kraków) The contributed papers were published in “Nukleonika” (editors: P. Urbański and G. Zakrzewska-Trznadel); • International Conference on Recent Developments and Applications of Nuclear Technologies (15-17 September 2008, Białowieża) The contributed papers will be published in the “Research on Chemical Intermedi- ates” (editors: K. Bobrowski and J.L. Gębicki). Patents of the Institute won awards at the 6th International Exhibition (SuZhou) of Inventions (Shanghai, China), the 57th World Exhibition of Innovation, Research and New Technology “Brussels Eureka 2008” (Belgium) and the Seoul International Invention Fair 2008 (Seoul, Korea). The Institute is representing of Polish Government in Euroatom Fuel Supply Agency, Fuel Supply Working Group of Global Nuclear Energy Partnership and Radioactive Waste Management Committee of the Nuclear Energy Agency (Organisation for Eco- nomic Co-operation and Development). MANAGEMENT OF THE INSTITUTE 11

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

Director Assoc. Prof. Lech Waliś, Ph.D./Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

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

Deputy Director for Maintenance and Marketing Roman Janusz, M.Sc.

Accountant General Małgorzata Otmianowska-Filus, M.Sc.

HEADS OF THE INCT DEPARTMENTS

• Department of Nuclear Methods of Materials • Department of Analytical Chemistry Engineering Prof. Rajmund Dybczyński, Ph.D., D.Sc. Wojciech Starosta, Ph.D. • Department of Radiobiology and Health • Department of Radioisotope Instruments Protection and Methods Prof. Marcin Kruszewski, Ph.D., D.Sc. Prof. Piotr Urbański, Ph.D., D.Sc. • Experimental Plant for Food Irradiation • Department of Radiochemistry Assoc. Prof. Wojciech Migdał, Ph.D., D.Sc. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. • Laboratory for Detection of Irradiated Food • Department of Nuclear Methods of Process Wacław Stachowicz, Ph.D. Engineering Prof. Andrzej G. Chmielewski, Ph.D., D.Sc./ • Laboratory for Measurements of Technological Jacek Palige, Ph.D. Doses Zofia Stuglik, Ph.D. • Department of Radiation Chemistry and Technology Zbigniew Zimek, Ph.D.

SCIENTIFIC COUNCIL (2007-2008)

1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology University of Łódź • radiation chemistry, photochemistry, biophys- • biochemistry ics 2. Prof. Aleksander Bilewicz, Ph.D., D.Sc. 4. Prof. Stanisław Chibowski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Maria Curie-Skłodowska University • radiochemistry, inorganic chemistry • radiochemistry, physical chemistry 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. (Vice-chairman) Institute of Nuclear Chemistry and Technology 12 MANAGEMENT OF THE INSTITUTE

• chemical and process engineering, nuclear chem- 20. Prof. Stefan Lis, Ph.D., D.Sc. ical engineering, isotope chemistry Adam Mickiewicz University 6. Prof. Jadwiga Chwastowska, Ph.D., D.Sc. • inorganic chemistry Institute of Nuclear Chemistry and Technology 21. Zygmunt Łuczyński, Ph.D. • analytical chemistry Institute of Electronic Materials Technology 7. Prof. Andrzej Czerwiński, Ph.D., D.Sc. • chemistry University of Warsaw 22. Prof. Andrzej Marcinek, Ph.D., D.Sc. • radiochemistry Technical University of Łódź 8. Prof. Rajmund Dybczyński, Ph.D., D.Sc. • radiation chemistry Institute of Nuclear Chemistry and Technology 23. Prof. Jacek Michalik, Ph.D., D.Sc. • analytical chemistry Institute of Nuclear Chemistry and Technology 9. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. • radiation chemistry, surface chemistry, radical (Chairman) chemistry Warsaw University of Technology 24. Prof. Andrzej Olszyna, Ph.D., D.Sc. • chemical technology Warsaw University of Technology 10. Prof. Zbigniew Galus, Ph.D., D.Sc. • material engineering University of Warsaw 25. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. • radiochemistry Institute of Nuclear Chemistry and Technology 11. Prof. Henryk Górecki, Ph.D., D.Sc. • radiochemistry, coordination chemistry Wrocław University of Technology 26. Prof. Jerzy Pączkowski, Ph.D., D.Sc. • process engineering University of Technology and Life Science in Bydgoszcz 12. Prof. Leon Gradoń, Ph.D., D.Sc. • photochemistry Warsaw University of Technology • chemical and process engineering 27. Jan Paweł Pieńkos, Eng. Institute of Nuclear Chemistry and Technology 13. Assoc. Prof. Jan Grodkowski, Ph.D., D.Sc. • electronics Institute of Nuclear Chemistry and Technology • radiation chemistry 28. Assoc. Prof. Dariusz Pogocki, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 14. Assoc. Prof. Edward Iller, Ph.D., D.Sc. • radiation chemistry Institute of Atomic Energy – Radioisotope Centre POLATOM 29. Assoc. Prof. Grażyna Przybytniak, Ph.D., D.Sc. • chemical and process engineering, physical Institute of Nuclear Chemistry and Technology chemistry • radiation chemistry 15. Assoc. Prof. Marek Janiak, Ph.D., D.Sc. 30. Prof. Leon Pszonicki, Ph.D., D.Sc. Military Institute of Hygiene and Epidemiology Institute of Nuclear Chemistry and Technology • radiobiology • analytical chemistry 16. Iwona Kałuska, M.Sc. 31. Prof. Irena Szumiel, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology • radiation chemistry • cellular radiobiology 17. Prof. Marcin Kruszewski, Ph.D., D.Sc. 32. Prof. Marek Trojanowicz, Ph.D., D.Sc. (Vice-chairman) Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology • analytical chemistry • radiobiology 33. Prof. Piotr Urbański, Ph.D., D.Sc. 18. Prof. Marek Lankosz, Ph.D., D.Sc. (Vice-chairman) AGH University of Science and Technology Institute of Nuclear Chemistry and Technology • physics, radioanalytical methods • radiometric methods, industrial measurement equipment, metrology 19. Prof. Janusz Lipkowski, Ph.D., D.Sc. 34. Assoc. Prof. Lech Waliś, Ph.D. Institute of Physical Chemistry, Polish Academy of Sciences Institute of Nuclear Chemistry and Technology • physicochemical methods of analysis • material science, material engineering MANAGEMENT OF THE INSTITUTE 13

35. Prof. Andrzej Wójcik, Ph.D., D.Sc. 36. Zbigniew Zimek, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology • cytogenetics • electronics, accelerator techniques, radiation processing

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2007-2008)

1. Prof. Antoni Dancewicz, Ph.D., D.Sc. 2. Prof. Sławomir Siekierski, Ph.D. • biochemistry, radiobiology • physical chemistry, inorganic chemistry

SCIENTIFIC COUNCIL (2008-2012)

1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. 17. Zygmunt Łuczyński, Ph.D. University of Łódź Institute of Electronic Materials Technology 2. Prof. Aleksander Bilewicz, Ph.D., D.Sc. 18. Prof. Andrzej Marcinek, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Technical University of Łódź 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 19. Prof. Bronisław Marciniak, Ph.D., D.Sc. (Vice-chairman) Adam Mickiewicz University Institute of Nuclear Chemistry and Technology 20. Assoc. Prof. Wojciech Migdał, Ph.D., D.Sc. 4. Prof. Stanisław Chibowski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Maria Curie-Skłodowska University 21. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. 5. Prof. Rajmund Dybczyński, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 22. Jan Paweł Pieńkos, Eng. 6. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology (Chairman) 23. Assoc. Prof. Dariusz Pogocki, Ph.D., D.Sc. Warsaw University of Technology Institute of Nuclear Chemistry and Technology 7. Prof. Zbigniew Galus, Ph.D., D.Sc. 24. Halina Polkowska-Motrenko, Ph.D. University of Warsaw Institute of Nuclear Chemistry and Technology 8. Prof. Henryk Górecki, Ph.D., D.Sc. 25. Assoc. Prof. Grażyna Przybytniak, Ph.D., D.Sc. Wrocław University of Technology Institute of Nuclear Chemistry and Technology 9. Prof. Leon Gradoń, Ph.D., D.Sc. 26. Prof. Leon Pszonicki, Ph.D., D.Sc. Warsaw University of Technology Institute of Nuclear Chemistry and Technology 10. Assoc. Prof. Jan Grodkowski, Ph.D., D.Sc. 27. Ryszard Siemion, M.Sc. Institute of Nuclear Chemistry and Technology PKN ORLEN 11. Assoc. Prof. Edward Iller, Ph.D., D.Sc. Institute of Atomic Energy 28. Prof. Irena Szumiel, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 12. Tomasz Jackowski, M.Sc. Ministry of Economy 29. Prof. Marek Trojanowicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 13. Iwona Kałuska, M.Sc. Institute of Nuclear Chemistry and Technology 30. Hanna Ewa Trojanowska, M.Sc. Polska Grupa Energetyczna S.A. 14. Prof. Marcin Kruszewski, Ph.D., D.Sc. (Vice-chairman) 31. Andrzej Tyrała, M.Sc. Institute of Nuclear Chemistry and Technology Warszawskie Zakłady Farmaceutyczne POLFA S.A. 15. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc. 32. Prof. Piotr Urbański, Ph.D., D.Sc. AGH University of Science and Technology (Vice-chairman) Institute of Nuclear Chemistry and Technology 16. Prof. Janusz Lipkowski, Ph.D., D.Sc. Institute of Physical Chemistry, Polish Academy 33. Assoc. Prof. Lech Waliś, Ph.D. of Sciences Institute of Nuclear Chemistry and Technology 14 MANAGEMENT OF THE INSTITUTE

34. Prof. Zbigniew Zagórski, Ph.D., D.Sc. 36. Zbigniew Zimek, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 35. Assoc. Prof. Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2008-2012)

1. Prof. Antoni Dancewicz, Ph.D., D.Sc.2. Prof. Sławomir Siekierski, Ph.D. SCIENTIFIC STAFF 15

SCIENTIFIC STAFF

PROFESSORS

1. Bilewicz Aleksander 10. Ostyk-Narbutt Jerzy radiochemistry, inorganic chemistry radiochemistry, coordination chemistry 2. Bobrowski Krzysztof 11. Piekoszewski Jerzy radiation chemistry, photochemistry, biophysics solid state physics 3. Chmielewski Andrzej G. 12. Pszonicki Leon chemical and process engineering, nuclear chem- analytical chemistry ical engineering, isotope chemistry 13. Siekierski Sławomir 4. Chwastowska Jadwiga physical chemistry, inorganic chemistry analytical chemistry 14. Szumiel Irena 5. Dybczyński Rajmund cellular radiobiology analytical chemistry 15. Trojanowicz Marek 6. Kruszewski Marcin analytical chemistry radiobiology 16. Urbański Piotr 7. Leciejewicz Janusz Tadeusz radiometric methods, industrial measurement crystallography, solid state physics, material science equipment, metrology 8. Łukasiewicz Andrzej 17. Wójcik Andrzej material science cytogenetics 9. Michalik Jacek 18. Zagórski Zbigniew radiation chemistry, surface chemistry, radical physical chemistry, radiation chemistry, electro- chemistry chemistry

ASSOCIATE PROFESSORS

1. Grigoriew Helena 5. Przybytniak Grażyna solid state physics, diffraction research of non- radiation chemistry -crystalline matter 6. Waliś Lech 2. Grodkowski Jan material science, material engineering radiation chemistry 3. Migdał Wojciech 7. Zakrzewska-Trznadel Grażyna chemistry, science of commodies process and chemical engineering 4. Pogocki Dariusz radiation chemistry, pulse radiolysis

SENIOR SCIENTISTS (Ph.D.)

1. Barlak Marek 3. Bazaniak Zbigniew chemistry chemistry 2. Bartłomiejczyk Teresa 4. Bojanowska-Czajka Anna biology chemistry 16 SCIENTIFIC STAFF

5. Buczkowski Marek 27. Machaj Bronisław physics radiometry

6. Chajduk Ewelina 28. Mikołajczuk Agnieszka chemistry chemistry

7. Cieśla Krystyna 29. Mirkowski Jacek physical chemistry nuclear and medical electronics 8. Danilczuk Marek 30. Nowicki Andrzej chemistry organic chemistry and technology, high-temperature technology 9. Danko Bożena analytical chemistry 31. Ostapczuk Anna chemistry 10. Deptuła Andrzej chemistry 32. Palige Jacek metallurgy 11. Derda Małgorzata chemistry 33. Pawelec Andrzej chemical engineering 12. Dobrowolski Andrzej chemistry 34. Pawlukojć Andrzej 13. Drzewicz Przemysław physics chemistry 35. Polkowska-Motrenko Halina 14. Dudek Jakub analytical chemistry chemistry 36. Pruszyński Marek 15. Dźwigalski Zygmunt chemistry high voltage electronics, electron injectors, gas 37. Rafalski Andrzej lasers radiation chemistry 16. Frąckiewicz Kinga 38. Sadło Jarosław chemistry chemistry 17. Fuks Leon 39. Samczyński Zbigniew chemistry analytical chemistry 18. Gniazdowska Ewa 40. Sartowska Bożena chemistry material engineering 19. Grądzka Iwona 41. Skwara Witold biology analytical chemistry 20. Harasimowicz Marian 42. Sochanowicz Barbara technical nuclear physics, theory of elementary particles biology 21. Kierzek Joachim 43. Sommer Sylwester physics radiobiology, cytogenetics 22. Kornacka Ewa 44. Stachowicz Wacław chemistry radiation chemistry, EPR spectroscopy 23. Krejzler Jadwiga 45. Starosta Wojciech chemistry chemistry 24. Kunicki-Goldfinger Jerzy 46. Strzelczak Grażyna conservator/restorer of art radiation chemistry 25. Lewandowska-Siwkiewicz Hanna 47. Stuglik Zofia chemistry radiation chemistry 26. Łyczko Krzysztof 48. Sun Yongxia chemistry chemistry SCIENTIFIC STAFF 17

49. Szreder Tomasz 54. Wojewódzka Maria chemistry radiobiology

50. Tymiński Bogdan 55. Zielińska Barbara chemistry chemistry

51. Warchoł Stanisław 56. Zimek Zbigniew solid state physics electronics, accelerator techniques, radiation processing 52. Wierzchnicki Ryszard chemical engineering 53. Wiśniowski Paweł radiation chemistry, photochemistry, biophysics RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 21 PULSE RADIOLYSIS GENERATION OF THE RADICAL ANIONS AND CATIONS DERIVED FROM OXOISOAPORPHINE IN ORGANIC SOLVENTS Krzysztof Bobrowski, Gabriel Kciuk, Eduardo Sobarzo-Sanchez1/, Julio R. De la Fuente2/ 1/ University of Santiago de Compostela, Spain 2/ Universidad de Chile, Santiago de Chile, Chile

Oxoisoaporphines are the family of oxoisoquino- kinetic behavior of oxoisoaporphine radical ions line-derived alkaloids that have been isolated from and triplet excited states will be useful in inter- Menispermaceae and Sciadotenia toxifera as the preting some of the transient phenomena ob- sole known natural source [1,2]. It has been claimed that these compounds could be phytoalexins generated by plants against pathogen infections [3]. The only radiation chemical studies performed so far on these compounds are those for 2,3-dihydrooxoisoaporphine derivatives [4-6]. Application of pulse radiolysis allowed selective generation and identification of radical ions and triplet states derived from 2,3-dihydrooxoisoaporphine and its 5-methoxy derivative. The main difference between previously studied 2,3-dihydrooxoisoaporphines and oxoisoaporphines studied currently (Chart 1) Chart 1. The structures of 2,3-dihydrooxoisoaporphine (left) arises from an aromatic character of the ring con- and oxoisoaporphine (right). taining N-atom in the latter compounds, what causes as a consequence their planarity. We have served in the pulse radiolysis and flash photolysis initiated this study in order to generate isolated of these compounds in the various solvents. oxoisoaporphine radical-ion species, and further It is well known that both acetonitrile and ace- to confront them with the spectra of radical-ions tone can be used for pulse radiolytic generation of generated in 2,3-dihydrooxoisoaporphine and radical cation and/or radical anion precursors. In 5-methoxy-2,3-dihydrooxoisoaporphine [4-6]. In these two solvents, either both radical ions or only addition, knowledge regarding the spectral and radical cations are formed under N2 and O2 satu-

Fig.1. Absorption spectra recorded in Ar-saturated (open symbols) and O2-saturated (filled symbols) acetonitrile solutions containing 0.1 mM oxoisoaporphine. Spectra taken after the following time delays: (□) 300 ns, (○) 6 μs, (Δ) 25 μs and (●) 6 μs. Inset: time profiles representing growth and/or decays at λ=410, 460 and 490 nm. 22 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES ration, respectively [7,8]. A transient absorption acetonitrile solutions of oxoisoaporphine (0.1 mM) spectrum obtained 300 ns after the electron pulse exhibit an absorption band with λmax=405 nm. in Ar-saturated acetonitrile solution containing This absorption is assigned unequivocally to the 0.1 mM of oxoisoaporphine, exhibits a distinctive radical cation (A●+) (Fig.1, curve D). absorption band with λmax=490 nm, and a second Acetone, in comparison to acetonitrile, is a much broader, and rather flat absorption band in much better solvent for generation of excited states. the 500-600 nm range with no distinct absorption The optical absorption spectra, obtained in the maxima (Fig.1, curve A). Both absorption bands pulse irradiation of Ar-purged acetone solutions build-up and reach plateau within 300 ns time do- of oxoisoaporphine (0.1 mM), are shown in Fig.2. main. They decay by a relatively rapid first-order The transient spectrum recorded 1.2 μs after elec- process with k=(2.8±0.2)×105 s–1 (Fig.1, insets). tron pulse exhibits two absorption bands with Upon O2 saturation (Fig.1, curve D) absorption λmax=465 and 490 nm, and a long shoulder be- band with λmax=490 nm is suppressed suggesting tween λ=500 and 600 nm (Fig.2, curve A). This that it might be associated with the oxoisoapor- two bands build-ups with the first-order rate con- phine radical anion (A●–). After 6 μs, the absorp- stant k=(2.2±0.1)×106 s–1 and k=(3.5±0.2)×106 –1 tion band with λmax=490 nm decay more than by s for λ=465 and 490 nm, respectively (Fig.2, left half and the transient spectrum is dominated by inset). This observation implies that two different

Fig.2. Absorption spectra recorded in Ar-saturated (open symbols) and O2-saturated (filled symbols) acetone solutions containing 0.1 mM oxoisoaporphine. Spectra taken after the following time delays: (□) 1.2 μs, (Δ) 12 μs, (○) 48 μs and (▲) 6 μs. Inset: time profiles representing growth and/or decays at λ=435, 465 and 490 nm. the 410 nm band (Fig.1, curve B). This absorp- species might be responsible for these absorption tion band is formed in the first-order process bands. Upon O2 saturation (Fig.2, curve D) all ab- k=(4.0±0.1)×105 s–1 (Fig.1 left inset), however, sorption bands were suppressed suggesting that the decay of the 410 nm transient is slower and they might be associated with the radical anion more complex in comparison to the decay of the (A●–) and triplet state (3A) of oxoisoaporphine. 490 nm transient (Fig.1, right inset). With the time Based on the assignment in acetonitrile, the λ=490 elapsed when the 490 nm disappeared, the spec- nm band is assigned to oxoisoaporphine radical trum recorded after 25 μs time after the pulse, ex- anion (A●–). It decays with the first-order rate con- hibited two absorption bands with λ=410 and 460 stant k=(1.5±0.02)×105 s–1. The λ=465 nm band nm (Fig.1, curve C). The nature of a transient as- is assigned to oxoisoaporphine triplet state (3A) sociated with a new band with λ=460 nm is not decaying with the first-order rate constant clear, but one can consider either the dimer of k=(1.3±0.02)×105 s–1 (Fig.2, right inset). On the ●+ radical cation (A2 ) or the triplet state of oxoiso- longer time-scale, the transient spectrum is domi- aporphine (3A). The transient spectrum recorded nated by the 465 nm band (Fig.1, curve B). The 6 μs after electron pulse irradiation of O2-purged spectrum recorded 48 μs after electron pulse ex- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 23 hibited rather flat absorption band in the 420-500 [3]. Flors C., Nonell S.: Acc. Chem. Res., 39, 293-300 nm range with two absorption maxima located at (2006). λ=435 and 465 nm. [4]. Bobrowski K., Kciuk G., Sobarzo-Sanchez E., De la The transient spectrum recorded 6 μs after elec- Fuente J.R.: J. Phys. Chem. A, 112, 10168-10177 (2008). [5]. Bobrowski K., Kciuk G., Sobarzo-Sanchez E., De la tron pulse irradiation of O2-purged acetone solu- Fuente J.R.: Pulse radiolysis generation of the radical tions exhibits two absorption bands with λmax=390 anion derived from 2,3-dihydro-oxoisoaporphine in and 410 nm – unequivocally assigned to the oxo- organic solvents. In: INCT Annual Report 2006. In- ●+ isoaporphine radical cation (A ) (Fig.2, curve situte of Nuclear Chemistry and Technology, Warsza- D). The contribution of the absorption band of wa 2007, pp.22-23. (A●+) is not seen on spectra A-C because of a sub- [6]. Bobrowski K., Kciuk G., Sobarzo-Sanchez E., De la stantial bleaching in the region between λ=380 Fuente J.R.: Pulse radiolysis generation of the radical and 410 nm associated with a consumption of the anions and cations derived from 5-metoxy-2,3-dihydro- native oxoisoaporphine. oxoisoaporphine in organic solvents. In: INCT Annual Report 2007. Insitute of Nuclear Chemistry and Tech- References nology, Warszawa 2008, pp.21-23. [7]. Bobrowski K., Das P.K.: J. Phys. Chem., 90, 927-931 [1]. Sugimoto Y., Babiker H.A.A., Inanaga S., Kato M., (1986). Isogay A.: Phytochemistry, 52, 1431-1435 (1999). [8]. Bobrowski K., Das P.K.: J. Phys. Chem., 89, 5733-5738 [2]. Killmer L., Vogt F.G., Freyer A.J., Menachery M.D., (1985). Adelman C.M.: J. Nat. Prod., 66, 115-118 (2003).

PULSE RADIOLYSIS STUDY OF INTERMEDIATES GENERATED IN IONIC LIQUIDS Jan Grodkowski1/, Rafał Kocia1/, Jacek Mirkowski1/, Tomasz Szreder1,2/, James F. Wishart3/, Andrzej Skrzypczak4/, Andrew R. Cook3/ 1/ Institute of Nuclear Chemistry and Technology; Warszawa, Poland 2/ Faculty of Biotechnology and Food Sciences, Technical University of Łódź, Poland 3/ Brookhaven National Laboratory, Upton, USA 4/ Institute of Technology and Chemical Engineering, Poznań University of Technology, Poland

Room temperature ionic liquids (IL) are consider- Photochemical activity of TP was particularly ed as non-volatile and non-flammable solvents. investigated in connection with CO2 reduction [18]. They serve as good media for various reactions Yield of intersystem singlet-triplet crossing in the and have been proposed as green solvents in many case of TP is not very effective (φ ~0.05-0.11) [19] applications [1-4]. Their specific properties and and to get the 3TP* triplet state the energy trans- promising experiments concerning application of fer between 3BP* and TP was used instead. This IL in the nuclear industry [1,5] brought the ques- process was applied in the present experiments. tion of radiation chemistry of IL. Fast kinetic measurements have been carried To cope with problems of radiation chemistry out using 10 ns, 10 MeV, electron pulses from a in IL several elementary processes as solvated and LAE 10 linear electron accelerator delivering the “dry” electrons reactions, charge and H transfer dose up to 20 Gy per pulse. The data were nor- have been studied by the pulse radiolysis tech- malized to a dose of 15 Gy per pulse measured by nique [6-14]. Radiation stability of IL under ion- a KSCN dosimeter, this value corresponds to the izing irradiation has been also studied in few cases dose of 17.4 Gy absorbed by MB3NNTf2 [6,9]. [15-17]. To our best knowledge there is no direct observation of excited states formation in irradiated IL. However, there is a strong indication that excited state formation cannot be neglected in the radiolysis of IL [15]. In the present study the formation of excited states in methyltributylammonium bis[(tri- fluoromethyl)sulfonyl]imide (MB3NNTf2) has been examined by the pulse radiolysis method. As sensors of excited state formation benzophenone (BP) and p-terphenyl (TP) have been selected. Both molecules form singlet and triplet excited states with absorption spectra in a convenient for pulse radiolysis wavelength range. Radiolysis of BP was already studied in IL solutions with emphasis on radical anions and radical formation [6,8]. Reac- Fig.1. Absorption spectra in the pulse irradiated Ar-satu- 3 tivity of BP* in IL has been also observed in photo- rated, 80 mM BP solution in MB3NNTf2, measured in 30 lytic experiments. ns, 200 ns, 500 ns, 2 μs and 10 μs after the electron pulse. 24 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

1 Radiolysis of MB3NNTf2 leads to production Absorption of singlet TP* is too short-lived to of electrons, dry and eventually solvated, protons, be observed in actual experimental conditions. radical cations, neutral radicals and excited states Solubility of TP in MB3NNTf2 is limited to ~14 formed by geminate ions recombination [7-9,15]. mM. For the maximum concentration of TP and The 80 mM concentration of BP in MB3NNTf2 the BP concentration of 80 mM, the electrons was used to ensure effective scavenging electrons should react predominantly with BP, thus diminish- and possibly excited states of pulse irradiated so- ing formation of TP●– radical anions. Direct radio- lution. lytical creation of oxidizing products in MB3NNTf2 BP reacts with solvated electrons with a rate is not very effective, and formation of radical cat- constant k=(1.6±0.1)x108 dm3mol–1s–1 [9]. At 80 ions with yield comparable to reducing species is mM concentration of BP only ~28% of electrons not expected. can survive to be solvated [9]. The spectra observed in Ar-saturated pulse ir- Pulse radiolysis of benzophenone solution pro- radiated 80 mM BP solutions with addition of 3 to duces transients characterized by initial broad ab- 14 mM TP for wavelength with λ>500 nm repre- sorption spectra with a maximum at ~700 nm. The sent all the features ascribed earlier to BP derived results presented in Fig.1, are similar to those re- intermediates. Figure 2 shows the intermediate ported earlier and can be explained by the reac- absorption spectra in 14 mM TP solution in the tion of BP with electrons (dry and solvated) and presence of 80 mM BP. H● radicals [8]. – ● – (C6H5)2CO + e [(C6H5)2CO] (1) ● ● (C6H5)2CO + H C6H5COC6H6 (2) ● – The absorption of [(C6H5)2CO] radical anion (BP●–) is the main component contributing to the absorption spectra observed during first 200 ns after the pulse. The band with a small maximum ● at ~460 nm probably corresponds to C6H5COC6H6 radical formed in reaction (2). Triplet excited state of benzophenone 3BP* has the absorption with a maximum in the visible range at 525 nm (in acetonitrile) and molar absorption coefficient ε=6700 dm3mol–1cm–1 [20]. In the present experimental conditions its yield and ε are too small to have an effect on the absorption spectra of irradiated samples. Overall decrease of the intensity of the spectra Fig.2. Absorption spectra in the pulse irradiated Ar-satu- in the first 200 ns after the pulse corresponds rated, 14 mM TP and 80 mM BP solution in MB3N NTf2, probably to solvated electrons decaying in reac- measured in 30 ns, 200 ns, 500 ns, 2 μs and 10 μs after the tion (1). On the longer time scale there is a simul- electron pulse. Insert: absorbance vs. time dependence at taneous decay of absorption with a maximum at 450 nm. ~700 nm and formation of more stable absorption characterized by a maximum at ~540 nm. The Absorption connected with TP intermediates new, more stable, absorption band is ascribed to are characterized by bands with maxima at ~430, ● ● (C6H5)2C OH radical (BP H) as it was already ob- 450 and 480 nm. Bands with absorption maximum served in MB3NNTf2 [12]. The decay and forma- at λ=480 nm and partly at 430 nm indicate formation can be fitted by pseudo first order kinetics tion of TP●− radical anion. Even at 3 mM concen- with the same rate constants k=2.8x105 s–1. The tration of TP some of the electrons react with TP process, observed also before in similar conditions to form the corresponding radical anions. [6,8], could be explained by protonation of BP●– The most pronounced band with a maximum radical anion and formation of benzophenone at 450 nm behaves differently than those indicated ketyl radical BP●H in reaction (3): above. It is formed in two steps, the first already ● – + ● [(C6H5)2CO] + H (C6H5)2C OH (3) during the pulse followed by partial decay in ~200 Assuming the molar absorption coefficient at ns, which was the consequence of the background 540 nm of BP●H from acetonitrile solution ε=3500 absorption decay of the other components of the dm3mol–1cm–1 [20], the radiation yield of ketyl rad- spectra, including some left-over solvated elec- ical will be G=2.1x10–7 mol J–1. This also corre- trons. The second phase of the formation lasts 2-5 sponds to the total yield of electrons reacting with μs, depending on the TP concentration. The plot BP, if all of the BP●– radical anions decay in reac- of the rate constants of pseudo-first order formation (3). The present G value is higher than that tion as the function of TP concentration gives the reported earlier, however it was calculated with second order reaction rate constant of k=~2x108 different value of ε of the BP●H radical [6]. dm3mol–1s–1. However, the second step corresponds Depending on the experimental conditions, the only to ~10% of total absorption at 450 nm. intermediates: radical anions, radical cations and From the experiments with TP as a sole com- excited states, can be derived from TP irradiated ponent present in MB3NNTf2 solvent and litera- systems. All of them have absorption spectra in a ture data concerning 3TP* absorption, there are a similar region [21]. strong indication that the triplet state of p-terphe- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 25 nyl 3TP* is responsible for the intermediate ab- In addition to investigations presented above, sorption with a maximum at 450 nm. we made an effort to examine the influence of a The fast formation could be energy transfer cation and anion structure on generated, post-irra- from excited state of ionic liquid formed due to diated species and their reactivity in ILs. These ex- geminate recombination or direct photoexcitation periments were carried out with a picosecond-time and slower step most probably is the effect of TP resolution using a laser electron accelerator facility reaction with 3BP* (formed in small yield). (LEAF) at Brookhaven National Laboratory (BNL). 3BP* + TP BP + 3TP* (4) The details of equipment are described elsewhere The experiment with solution saturated with [22]. Samples for investigations were synthesized by N2O, a known scavenger of solvated electrons, our collaborator Andrzej Skrzypczak from Poznań gives additional evidence of the nature of “450 University of Technology. nm” absorption. The results presented in Fig.3 indicate that saturation of the system with N2O completely removes solvated electrons from irra-

Fig.4. Cation structures.

Preliminary pulse radiolysis experiments focused on ILs based on substituted ammonium cations – (Fig.4) combined with NTf2 are shown in Fig.5.

Fig.3. Absorption spectra in the pulse irradiated N2O-satu- Spectra of irradiated IL containing tetra-alkylam- rated, 14 mM TP and 80 mM BP solution in MB3NNTf2, monium cations reveal a broad band in the NIR measured in 30 ns, 200 ns, 500 ns, 2 μs and 10 μs after the region. This band was assigned to solvated elec- electron pulse. Inset: absorbance vs. time dependence at – trons (es) based on experiments involving N2O, 450 nm. CO2, Pyr (well known electron scavengers). Ob- served within a few nanosecond after the pulse diated solution. As a consequence, also the yield electron solvation process is relatively slow (com- of BP●H is lower, absorption at 540 nm decreases paring with molecular solvents) due to the high – from 0.01 to 0.007 in N2O-saturated samples. Fast viscosity of ILs. The decay of es was described by a formation of 450 nm absorption is then followed single exponential function. The pseudo-fist order – by an increase in the next 2 μs, without intermedi- kinetic of es decay was apparently connected with ate decay. The second step in that case represents impurities remaining in investigated systems. ~20% of total absorbance at 450 nm. Taking the molar absorption coefficient of 3TP* measured in benzene, ε=90000 dm3mol–1cm–1, and absorbance at 450 nm 2 μs after the electron pulse OD=0.029 in 14 mM TP and 80 mM BP solution, the radiation yield of 3TP* will be G=1.8x10–8 mol J–1. This value is ten times smaller than the yield of BP●H ketyl radicals, under conditions that both molar absorption coefficients, taken from different media, could be applied in IL solvent. It seems that the energy transfer from excited solvent to solute is the marginal process in the radiolysis of MB3NNTf2. The energy of solvent excited states Fig.5. Transient absorption spectra of irradiated ILs based – could be involved in fragmentation of particular on NTf2 anion taken 20 ns after the pulse: (×) MB3NNTf2, ions instead [15]. (○) HB3NNTf2, (+) Et3NHNTf2, (□) S1NNTf2, (Δ) S2NNTf2. The 10 MeV electron irradiation is accompanied by Čerenkov light generated in the solution In the case of salts based on tri-alkylammonium + and in the cell. In both compounds, BP and TP cation (R3NH ), the band in NIR region was com- excited states are easily formed in photolytical ex- pletely eliminated on nanosecond time scale due – periments. The fast formation of benzophenone to the reaction of thermal electrons (eth) with + and p-terphenyl excited states could be then caused R3NH . However, it is likely that traces of signal by direct photolysis. To prove such assumption more observed within a few picoseconds at 800 nm us- experiments will be needed. ing pulse-probe technique were connected with 26 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

– – + es. Rate constants of es with R3NH was investi- References 7 gated in R4NNTf2 and varied from 2.6(2)x10 to [1]. Ionic liquids: industrial applications to green chem- 7 3 –1 –1 + + 3.93(8)x10 dm mol s for Bu3NH and Me3NH istry. Eds. R.D. Rogers, K.R. Seddon. ACS Symp. Ser., 818 (2002). [2]. Chiappe C., Pierracini D.: J. Phys. Org. Chem., 18, 275-297 (2005). [3]. Endres F., El Abedin S.Z.: Phys. Chem. Chem. Phys., 8, 2101-2116 (2006). [4]. Plechkova N.V., Seddon K.R.: Chem. Soc. Rev., 37, 123-150 (2008). [5]. Harmon C.D., Smith W.H., Costa D.A.: Radiat. Phys. Chem., 60, 157-159 (2001). [6]. Behar D., Neta P., Schultheisz C.: J. Phys. Chem. A, 106, 3139-3147 (2002). [7]. Grodkowski J., Neta P.: J. Phys. Chem. A, 106, 5468-5473 (2002). [8]. Grodkowski J., Neta P., Wishart J.F.: J. Phys. Chem. Fig.6. Transient absorption spectra of irradiated ILs based A, 107, 9794-9799 (2003). + on MB3N cation taken 20 ns after the pulse (295 K): (×) [9]. Wishart J.F., Neta P.: J. Phys. Chem. B, 107, 7261-7267 MB3NNTf2, (○) MB3NDCA, (#) MB3NCH3COO, (*) (2003). MB3NC2H5COO, (◊) MB3NCCl2HCOO, (+) MB3NCF3COO. [10]. Grodkowski J., Nyga M., Mirkowski J.: Nukleonika, 50, Suppl. 2, s35-s38 (2005). – cation, respectively. The efficiency of reaction eth [11]. Yang J., Kondoh T., Norizawa K., Nagaishi R., Tagu- + with R3NH was evaluated based on Q37 factor. chi M., Takahashi K., Katoh R., Anishchik S.V., Yoshi- + + For Me3NH and Bu3NH cations values of Q37 da Y., Tagawa S.: Radiat. Phys. Chem., 77, 1233-1238 were calculated to be equal to 4.2(4) and 1.2(2) (2008). l/mol, respectively. [12]. Takahashi K., Sato T., Katsumura Y., Yang J., Kon- Spectra of aryl substituted ammonium cations doh T., Yoshida Y., Katoh R.: Radiat. Phys. Chem., revealed a new broad band with a maximum 77, 1239-1243 (2008). [13]. Asano A., Yang J., Kondoh T., Norizawa K., Nagaishi around 900 nm. This band was not affected by R., Takahashi K., Yoshida Y.: Radiat. Phys. Chem., common electron scavengers, so it is likely that it 77, 1244-1247 (2008). originates from initially generated holes (localized [14]. Kimura A., Taguchi M., Kondoh T., Yang J., Yoshida on the aryl group of cations) or its successors. Y., Hirota K.: Radiat. Phys. Chem., 77, 1253-1257 Pulse radiolysis spectra of series ILs based on (2008). + MB3N cation combined with different types of [15]. Wishart F., Funston A.M., Szreder T.: Radiation carboxylic anions are presented in Fig.6. In all chemistry of ionic liquids. In: Molten salts XIV. Eds. R.A. Mantz et al. The Electrochemical Society, Pen- cases except for MB3NCCl2HCOO characteristic – nington 2006, pp.802-813. es bands were recorded. This will make it possible – [16]. Shkrob I.A., Chemerisov S.D., Wishart J.F.: J. Phys. to investigate, in the future, es and solvation process – Chem. B, 111, 11786-11793 (2007) and references in ILs in which expensive NTf2 or dicyanamid therein. – (DCA ) anion will be replaced by an inexpensive [17]. Qi M., Wu G., Li Q., Lu Y.: Radiat. Phys. Chem., 77, carboxylic anion. In addition, it is worth to note that 877-883 (2008). – salts based on CCl2HCOO anion are very effective, [18]. Grodkowski J., Neta P., Fujita E., Mahammed A., – – es and eth, scavengers. Both, rate constant of the Simkhovich L., Gross Z.: J. Phys. Chem. A, 106, – 7 3 –1 –1 4772-4778 (2002) and references therein. reaction with es equal to 3.93(8)x10 dm mol s – [19]. Cai X., Sakamoto M., Hara M., Tojo S., Kawai K., as well as Q37=9.5(7) l/mol for reaction with eth are higher than the corresponding values for Endo M., Fujitsuka M., Majima T.: J. Phys. Chem. A, + 108, 9361-9364 (2004). R3NH cation despite of unfavorable repulsion of [20]. Demeter A., Bérces T.: J. Photochem. Photobiol. A: anions. Chem., 46, 27-40 (1989). The authors wish to thank Krzysztof Bobrowski [21]. Svetlichnyi V.A., Kopylova T.N., Mayer G.V., Lapin and Marie Thomas. I.N.: Russian Phys. J., 48, 901-906 (2005). Supported in part by the U.S. Department of [22]. Wishart J.F., Cook A.R., Miller J.R.: Rev. Sci. Inst., Energy under contract DE-AC02-98-CH10886. 75, 4359 (2004). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 27 PROMISING CALCITE-BASED TISSUE ENGINEERED PRODUCT FOR BONE Anna Chróścicka1/, Zbigniew Jaegermann2/, Joanna Wójtowicz1/, Anna Ratajska3/, Jarosław Sadło, Piotr Wychowański4/, Grażyna Hoser5/, Sławomir Michałowski2/, Jacek Przybylski1/, Małgorzata Lewandowska-Szumieł1/ 1/ Department of Biophysics and Human Physiology, Medical University of Warsaw, Poland 2/ Institute of Glass, Ceramics, Refractory and Construction Materials, Warszawa, Poland 3/ Department of Pathological Anatomy, Center of Biostructure, Medical University of Warsaw, Poland 4/ Department of Dental Surgery, Medical University of Warsaw, Poland 5/ Department of Clinical Cytology, Medical Center of Postgraduate Education, Warszawa, Poland

Tissue engineering applies biological, medical and nance spectroscopy (EPR; samples were reirradi- technical science for the sake of regeneration, ated with a dose of 35 kGy). maintenance and improvement of tissue functions. Basing on the measurements of activity of en- Studies concerning new materials for cell culture zymes of succinate dehydrogenase (XTT test) it was scaffolds are a quickly developing domain of bio- shown that the synthetic calcite was well tolerated medical engineering. Scaffold design for bone by HBDCs in a dynamic culture before implanta- tissue engineering applications involves many pa- tion. The precultured samples were mechanically rameters that directly influence the rate of bone stronger than the control. A well organized con- tissue regeneration onto its microstructural sur- nective tissue (Fig.1), rich in blood vessels, with face. To improve scaffold functionality, increasing slight inflammation, was seen in histological ob- interest is being focused on in vitro and in vivo re- servations of both precultured and control explants. search in order to obtain an optimal scaffold de- After 12 weeks, the bone tissue was found within sign for specific application. the implants – only in scaffolds with HBDCs. The In our research synthetic calcite (CaCO3) was EPR analysis supported the histological results – tested as a candidate scaffold for tissue engineered hydroxyapatite-characteristic spectra were found product (TEP). The aim was to confirm the bio- in HBDC-seeded explants after longer observa- compatibility of synthetic calcite (until now only tion (Fig.2). natural CaCO3 materials have been used) and its competence for osteoinduction when seeded with human bone derived cells (HBDCs) – verified in vivo in SCID mice. The 3-dimensional calcite samples (5/5/5 mm) were precultured with HBDCs for 2 weeks in a special bioreactor (Spinner Basket®) or pre-wet in a culture medium (control) before implantation. Simultaneously, using samples with a diameter of 15 and 5 mm high, the mechanical properties of the precultured scaffolds (after 5-week long dynamic culture) and the control ones were measured. The precultured and control samples were subcutaneously implanted in SCID mice contralaterally (one TEP and one control per mouse). The viability of the cells was assessed prior to their implantation by XTT test. Four or twelve weeks after implantation the explants were investigated histologically (HE staining) and by electron paramagnetic reso-

Fig.2. EPR spectra of calcite scaffolds. Scaffolds were steri- lized by electron beam before implantation and reirradiated with a dose of 35 kGy before EPR measurement. Arrows indicate perpendicular and parallel components of signal

Fig.1. Calcite samples after 12 weeks of implantation. in bone (g⊥=2.003, gll=1.997). 28 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES In conclusions, 3D synthetic calcite may serve in blood vessels can be organized inside the 3D as a scaffold for HBDCs – cell proliferation is pro- porous synthetic calcite implants, as shown in SCID ceeding, the mechanical properties of the scaffold subcutaneously. HBDCs implanted into SCID mice with cells were enhanced as compared to the scaf- on the calcite scaffolds are able to produce bone fold alone. Well-organized connective tissue, rich tissue in vivo.

EPR STUDY OF DOSIMETRIC MATERIALS Grażyna Strzelczak, Jarosław Sadło, Jacek Michalik

Electron paramagnetic resonance (EPR) spectroscopy is a very good method for radiation dosimetry, because of its accuracy, sensitivity and fast results. Materials in which stable paramagnetic species are induced by irradiation can be used as EPR dosimeters in radiation research and technologies. When the relationship between EPR signal intensity of stable paramagnetic center and the dose has linear character, the material can be used as a dosimeter of absorbed radiation. Depending on sensitivity and range of linearity of intensity-dose dependence, the dosimeters can be used for different purposes as geological and archeological dating, standard and accidental dosimetry, detection of irradiated food. Fig.1. The EPR spectrum at X-band of CaCO3 precipitat- Among the materials, which were irradiated ed with vitamin C, gamma-irradiated at room temperature. and detected by this method we have selected synthetic materials and natural materials based on ples at room temperature. EPR spectra recorded amino acids, sugars, natural bones. in X-band, mainly in natural samples, are complex

Fig.2. The EPR spectra of l-alanine, gamma-irradiated at room temperature: X-band – left spectrum, Q-band – right spectrum. Usually, after the action of ionizing radiation and difficult to interpret because signals of differ- several paramagnetic species are stabilized in sam- ent centeres are overlapped.

Fig.3. The EPR spectra of glucose, gamma-irradiated at room temperature: X-band – left spectrum, Q-band – right spectrum. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 29 In our study we made the analysis of X- and materials one should be aware that the complexity Q-bands spectra of irradiated materials in order of the EPR signal, when used for dose estimation, to overcome that problem. In both bands the EPR may influence the dose response, because deter- measurements were performed at room tempera- mination of signal intensity is based on the mea- ture. surement of the signal amplitude.

Fig.4. The EPR spectra of fresh bone, gamma-irradiated at room temperature: X-band – left spectrum, Q-band – right spectrum. The best material for radiation dosimetry is the Because of that, we recommend as a routine one in which only one type of radical signal with a EPR dosimeter the deproteinized human bone [1] linear signal-to-dose dependence is recordable or at least one of the signal distincly dominates. How- ever, usually the EPR spectra in dosimetric materials are complex. The aim of our analysis is to differentiate between paramagnetic centres contributing to the complex EPR spectra of these materials. As synthetic material – calcium carbonate, CaCO3, precipitated in the presence of vitamin C has been investigated as an potential EPR dosimeter. Depending on the reaction conditions, we were able to record after irradiation a single line of very stable single radicals. The EPR signal of that radical, with g⊥=2.0053 and gII=2.0022 can be recorded only in special conditions using very low microwave power (0.02 mW) and modulation Fig.5. The EPR spectrum at X-band of deproteinized bone, amplitude (0.02 mT) (Fig.1). In this case this ma- gamma-irradiated at room temperature. terial is useful only for high doses of irradiation. As natural material, we have chosen amino which we have studied earlier (Fig.5). After irra- acid (alanine) (Fig.2), sugar (glucose) (Fig.3), and diation, only one radical is recorded in that system a natural fresh bone (Fig.4). The EPR spectra of at room temperature. those materials detected in X-band are complex. The Q-band measurements did not resolve the References spectra enough to help us with spectral analysis. [1]. Strzelczak G., Sadlo J., Danilczuk M., Stachowicz W., Thus, we can only claim that EPR spectra consist Callens F., Vanhaelewyn G., Goovaerts E., Michalik of two or more different species. So, using those J.: Spectrochim. Acta A, 67, 1206 (2007).

DENSITY FUNCTIONAL THEORY STUDY OF NONFRAMEWORK CATIONS IN ZEOLITE LATTICE Marcin Sterniczuk, Jarosław Sadło, Grażyna Strzelczak, Jacek Michalik

In this paper we present examples of theoretical Zeolites are crystalline microporous solids often calculations of silver cations in zeolite LTA. The used in the chemical industry. They have well-de- aim of this work is to prove the applicability of fined structures containing tetrahedral TO4 build- DFT (density functional theory) methods in order ing blocks that are connected to each other by to identify the preferential location of exchange- sharing O atoms. T represents Si, Al or other tetra- able Ag+ cations and a small silver cluster in zeo- hedrally coordinated atoms. Their features like lite lattice. shapeselective properties, well-defined micropo- 30 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES rous network and good thermal and mechanical Starting geometry was based on the crystallo- stability make them attractive for catalysis. The graphic data [4]. Terminal hydrogen and silicon metal cluster stabilized in zeolites are very interest- atoms in “low” layer were frozen [5] in order to ing for fundamental and applicable research. How- simulate more distant parts of zeolite lattice and ever, little is known about their location in zeolite prevent against the unrealistic collapse of struc- network and stabilization mechanizm. ture during optimalization process. This happens quite often for that type of computations. Because the size of computed lattice used for optimalization was large, we used the convengance criterium at a level of 10–5 (conver=5) simultaneously increasing the number of cycles and not talking into account the symmetry of orbitals (nosymm). All calculations have been performed by using the Gaussian03W program. The visualization of the computation results were done using a ChemCraft freeware program. Three different locations of Ag+ in zeolite lattice were calculated: the first one – close to the plane of hexagonal window, the second one – in the plane of octagonal window and the third one – in the plane of square window. In the vicinity of hexagonal window Ag+ cation interacts with the three nearest oxygen and Ag+-O distances 2.32, 2.42 and 2.67 Å were found from computations (Fig.1). From crystallographic data [5] all three Ag+-O distances are the same and equal to 2.33 Å. Fig.1. Sodalite cage with Ag+ cation stabilized near hexago- The observed differences might be due to the pres- – nal window of LTA zeolite. ence of only one AlO4 centre in computed system. Nevertheless, the differences are small and essen- The computations strategy counted on the em- tialy the interaction pattern of Ag+ is close to the ployment of the 3-layer ONIOM [1] model. First crystallographic one. “low” layer (24T+24H – Figs.1 and 2, 16T+16H For Ag+ in octagonal window (Fig.3), the com- – Fig.3) was computed at MO level with UFF puted Ag+-O distances are 2.29 and 2.72 Å are force field. The next two layers – ”medium” (24T nearly similiar to 2.30 and 2.69 Å of the literature – Figs.1 and 2, 8T – Fig.3) and “high” (Ag+) were data [5]. The computed results of Ag+ in square calculated at DFT level with the use of LANL2DZ window (Fig.2) show that at this site Ag+ interacts [2] basis set with effective core potential for Ag with two oxygens at a distance of 2.25 and 2.49 Å. atoms and B3LYP [3] hybrid functional. 24T rep- There are no literature data on Ag+-O distances resents a part of zeolite structure with 24 tetrahe- for Ag+ in square window of LTA zeolites. – drons (23SiO4 i AlO4 “medium” layer and 24 tetra- hedrons SiO4 in “low” layer).

Fig.3. Sodalite cage with Ag+ cation stabilized near square Fig.2. The Ag+ cation stabilized near octogonal window of window of LTA zeolite. LTA zeolite. The single point computations showed that the The conformational space scan was made for β system energy for Ag+ at hexagonal window of cage and part of cage α of LTA zeolite. 0.26 eV is lower than for Ag+ in square window. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 31 This confirms the preferential tendency of Ag+ ONIOM method we can get more define geome- cations to locate close to the hexagonal windows. tries from which it will be possible to calculate The presented results show that the used compu- more reliable EPR parameters which allows us to tation method can be applied for the calculation verify our conclusions based on EPR experiments. of geometry of the structures as large as zeolite lattices. References To conclude it should be mentioned that the [1]. Morokuma K.: Bull. Korean Chem. Soc., 24, 797 ONIOM method makes it possible to compute (2003). complex geometries with a relatievly low compu- [2]. Hay P.J., Wadt W.R.: J. Chem. Phys., 82, 270 (1985). tational cost. In the future we plan to use that [3]. Becke A.D.: J. Chem. Phys., 98, 5648 (1993). method to define the structure and location of [4]. Kim Y., Seff K.: J. Phys. Chem., 82, 921 (1978). small cationic silver cluster in zeolites. It is based [5]. Pantu P., Pabchanda S., Limtrakul J.: Chem. Phys. on the preliminary results that by appling the Chem., 12, 1901 (2004).

SOFTWARE AND HARDWARE IN THE ORIGINS OF LIFE CHEMISTRY Zbigniew P. Zagórski

By analogy to informatics, one can discuss the tainer serving for collection of primary products prebiotic chemistry on primitive Earth as divided to be used later after ages of hibernation. The solu- into chemical reactions (e.g. those leading to the bility of racemic amino acids, products of Miller’s RNA world, that is “software” now developed in reactions, is lower than the homochiral compo- contemporary laboratories) and into physicochem- nents, therefore they form precipitate after reach- ical transformations which proceed in real geo- ing well defined concentration, and due to higher physical conditions (e.g. fractional crystallizations, density than the mother liquor, they are falling to natural “chromatographic” separations on sand the bottom of the crater, waiting there, perhaps dunes watered by oceanic waves, etc.). One can for other chemical changes and transformations. also invoke the analogy with chemical technology Another feature of real chemical reactions on dealing with unit processes (a sequence of chemi- prebiotic Earth are periodically repeated cycles of cal reactions) and unit operations (e.g. a small crater temperature change due to day/night, more fre- filled with water, collecting reactive fallout from quent than now, and longer temperature cycles due the nearby volcano). to seasonal summer/winter variations. These vari- Only the terrestrial “hardware” acting as a ations can be helpful to explain some physicochem- natural laboratory, plus proper chemical “soft- ical separations. For instance, periodical partial ware” could have been functioning as a cradle of freezing of aqueous solution can be accompanied life. Most ideas on possible chemical mechanisms by the formation of higher concentration of salts leading to prebiotic compositions are developed and new formed organic compounds. Natural sep- in laboratory glassware, without reference to real aration of crystals of ice from the solution and conditions. However, already the classic case of repetition of the phenomenon could pay a tribute Stanley Miller’s experiment has translated easily to the lowering of entropy of the system, desired into the landscape of primitive Earth, with atmos- for explanation, from the point of view of the ori- pheric electric discharges supporting energetically gin of life. the formation of organics, via free radicals and On the other hand, the periodicity of the endother reactive intermediates. less repetition of “software” in a specific “hard- There is a sizeable library of “software”, sup- ware”, may not contribute to the effective develop- posed to proceed on primitive Earth. However, ment of prebiotic chemistry as the introduction to not all of them had equal chances to happen. For life. In that case, nature offers places on Earth, instance, all catalytic, homogeneous reactions in- screened from day/night fluctuations and flatten- cluding autocatalytic ones, demand rather high ing the seasonal summer/winter effects. These concentrations, in closed containers, all that ac- places are caves with underground lakes, rather cording to chemical kinetics. Reactions involving seldom in prebiotic Earth, because of volcanic heterogeneous catalysis had higher chances, e.g. if origin, formed sometimes in basalt rocks. Present the walls of the containment were at the same day, plentiful caves are product of life: calcium time catalytically active. carbonate rocks penetrated with streams of water. Important difference between chemical reac- More popular sites, isolated from day/night and tions realized in the laboratory and the same reac- from seasonal changes of weather, are bottoms of tions supposed to run on the primitive Earth is a aqueous world. Photochemistry does not exists allow, relatively production to large volume of the ready on reasonable depths and no temperature medium in the second case. For instance, in the effects exist in almost thermostating conditions. case of the classic Miller reaction, the portions of No storms are reaching the depths, and the move- amino acids are formed rapidly, as sequences of ments of water are very slow, or non-existent in free radical reactions, but almost disappear in a closed lakes. large mass of water containment. That reservoir, The full presentation quotes publications sug- as the kind of hardware, could act as a storage con- gesting possible “hardware”, like crystalline, spe- 32 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES cifically layered minerals at the bottom of aqueous ganics. Some minerals can have catalytic effects; pond, monochiral crystal faces, reactive solids sup- sulphides can, hopefully act both as a cradle and plied by volcanic eruptions, concentrated sources at the same time as catalyst. of ionizing radiations, even aerosols suggested as One can discuss other possibilities of the “hard- sites of prebiotic chemical reactions. One can ware” in the origin of life. For instance, one can speculate in what way they can be combined with imagine formation of a shallow meteorite crater, laboratory “software” to create new proposals for filled with rain water initially and later supplied by origins of life. In author’s Laboratory a construc- small stream, keeping from drying off. If placed tion is started of a complicated box, with a con- near a volcano, the crater would be supplied by trolled atmosphere, according to supposed com- ejecta. In the case of calcium carbide present in it, position of one of accepted version of early Earth. the reaction would yield highly reactive acetylene, The chamber, carefully isolated from the rest of starting an efficient chemical “software”. The in- the laboratory, is kept sterile, therefore avoiding teresting organic -C-C- bond occurring unexpect- difficulties met by Miller who had to add strong edly from inorganic volcanic magma, can play an bacteria killing compounds to prevent energy important role in further reactions, involving, e.g. which provided the change of internal energy of seconadary organic products of electric discharges the system on early Earth, including photochemi- in the atmosphere above the crater, as well prod- cal energy, rather neglected in considerations of ucts of photochemical reactions in the case of creation of prebiotic chemical systems. List of shallow water basins. “hardware”, even simple ones and obvious in the All sites hosting prebiotic chemistry are impor- laboratory, but imagined to work on early Earth, tant not only because of the possible site of origin is limited. of life. If they involve the place in which organic Chosen sites on primitive, lifeless Earth, ready products formed can be deposited during thou- to harbor chemical “software” sequences of pre- sand of years, they can be considered as the pro- biotic chemistry, most promising in turning into ducers of the feedstock for microorganisms appear- cradles of life: ing later. Dried “Miller’s soup” containing amino • the surface of Earth covered in substantial degree acids, even as racemates, usually can be consumed, with oceans of still changing mineral content; leaving D-aminoacids as waste. Therefore, specu- • movement of substantial parts of land, creating lations on the prebiotic chemistry running in the favorable niches; natural “hardware” should be considered not only • intensive volcanic activity, both on land and at as the raw material for the origin of life, but also the bottom of oceans, producing variety of com- as the food for living creatures formed in other pounds, including important carbon compounds; parts of Earth. In the “astronomical” scale of time • occasional bombardment of Earth by meteor- involved, deposits of such food can be of substan- ites and asteroids, changing the surface of Earth tial size. and supplying some exotic compounds; Special “hardware” conditions have to be con- • the presence of sources of energy, feeding the sidered in the case of photochemical “software”. high energy chemistry, like radioactive isotopes The range of light quanta in the UV/Vis range in of variety of energy of quanta and/or particles the medium with chromophoric groups is very and general activity by two orders of magnitude short. Depending on the value of the ε (molar ex- higher than now; tinction coefficient) and concentration, the range • electric discharges in the atmosphere, of various is seldom deeper than 1 mm. The proper example, energy and intensity of single acts, sufficient to but in the developed life world, is a plant leave, produce reactive intermediates; always thin, absorbing the sun light with produc- • UV/Vis light, of the rich spectrum, emitted by tion of oxygen from water and of carbohydrates the young Sun, generating excited chemical en- from CO2. Returning to prebiotic chemistry, pure tities in media containing proper chromophoric water exhibits transparency to UV/Vis and, there- groups; fore, light absorbing object, e.g. a micelle can be • large differences of temperature from freezing several centimeters below the surface and will be (probably) to the heat close to the boiling point reached by quanta, if matched the absorption of water, also climatic changes, in the day/night spectrum. rhythm more rapid than know, seasonal varia- After consideration of all that: if I were nomi- tions summer/winter; nated as the intelligent designer (tous proportions • more intensive tides than now, due to the closer guardee) of prebiotic chemistry, I would quit distance of the Moon to Earth, causing changes quickly, because it is a mission impossible! of the coastline and penetration of sea water Unfortunately, the problem of hosting chemical into the land. reactions on the early Earth is continuously spoiled All these sides contribute to heterogeneity of by occurring time and now the idea of panspermia, chemical changes which might be serving positive- supposed to solve all problems of origin of life on ly to the origin of life. Earth. It has been shown, that radiation chemistry Some sites supposed to harbor developing shows impossibility of panspemia, even of trans- prebiotic chemistry are described in the literature portation of blocks of chemical structures, precur- precisely. For instance, vents of hot water at the sors of life [1]. Acceptance of panspermia makes bottom of oceans. They contain rich spectrum of the need of the “hardware” second priority. Obvi- inorganic reactive material which can turn into or- ously, rejecting of panspermia, places problems of RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 33 sites and conditions on the key position in projects is acknowledged, as well as membership in the Ma- leading to recognition of origins of life. nagement Committee (2008-2012). The project is This is a combined report of international pre- supported by the grant from the Ministry of Science sentations: “Software and hardware in the origins and Higher Education no 365/N-COST/2008/0 of life chemistry”, invited for High Level European (2008-2012). Science Foundation Conference “Systems Chem- istry”, Maratea, Italy, 3-7.10.2008 and as a lecture References at the Workshop of the COST action CM0703, Mara- [1]. Zagórski Z.P.: Origins Life Evol. Biosph., 37, 351 tea, Italy, 8-10.10.2008. Support by the CSF/COST (2007).

RADIATION COMPATIBILIZATION OF DISPERSED PHASE IN COMPOSITES Andrzej Nowicki, Grażyna Przybytniak, Wojciech Starosta

Introduction tylamine) with neat p-vinylbenzyl chloride or oleoyl Aim of the presented studies was to obtain fillers chloride [3]. of specific properties that might be used for the MMT containing above 90% pure montmo- polymer reinforcement. In order to prepare poly- rillonite in the form of Na-salt was purchased from mer-montmorillonite (MMT) nanocomposites of Riedel deHaen (RdH). For comparison, standard of improved stability, variety of methods and modifi- modified MMT, Cloisite 10, was tested. Modification cations were tested in the past [1,2]. Application of MMT with the synthesized salts was carried out of ionizing radiation for the modification of MMT in water-acetone solution, following mechanical

Fig.1. Formulas of salts. reinforced polypropylene led to changes in the na- mixing for 24 h at RT or for 5 h in aqueous solu- nocomposite structure, flammability and better tion at 95oC. thermal stability of the product, depending on the Modified MMT samples were irradiated in an absorbed dose. On the basis of the above informa- Elektronika 10/10 electron accelerator with a dose tion, for MMT modification we have proposed of 56 kGy. using quaternary ammonium salts containing in WAXS (wide angle X-ray scattering) diffracto- the molecule unsaturated bond, and subsequently, grams were obtained on a D8-Advance X-ray diffrac- irradiation of the fillers in order to generate ac- tometer in the range of 2Θ from 4 to 70 deg. Layer tive species able to initiate covalent bonds between spacing was calculated using formula 2d sinΘ=λ. polymer chains and MMT during process of mix- IR spectra of the samples were measured on a ing. Bruker Fourier-Transform apparatus for KBr pel- Experimental lets in the range of 400-4000 cm–1. Unsaturated ammonium salts of the formulae la- EPR (electron paramagnetic resonance) spec- belled A, B and C (Fig.1) were obtained by mixing tra of irradiated samples were detected on an particular tertiary amines (triethylamine or trioc- X-band Bruker ESP-300 spectrometer at RT.

Fig.2. Diffractograms of samples in the range of 2Q=4-70 deg (left) and 2Q=4-10 deg (right). Symbols as in the Table. 34 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES Thermogravimetric analysis (TGA) was con- EPR spectroscopy ducted using Q500 TA Instruments apparatus in EPR signals of salt A modified MMT are more air at a heating rate of 10oC/min. intensive and more stable than for MMT modified Results and discussion with salt C, however both of them decay for sev- X-ray diffraction eral days. Poorly resolved traces of hyperfine split- MMT intercalation was estimated by the dif- ting reveal interaction between unpaired spins fraction measurements presented in Fig.2 and sum- and hydrogen atoms typical of alkyl-type radicals marized in Table. The most considerable change (Fig.3). Is seems that the observed signal might be

Fig.3. EPR spectra of irradiated samples: (left) MMT modified with salt A, (right) MMT modified with salt C; both prepared in aqueous solution at 95oC. in MMT basal spacing is observed for samples assigned to the product formed upon addition of modified with salt A, and the results do not de- hydrogen atom, abstracted, e.g. from MMT, to un- pend on the applied method. The modification saturated bonds (Fig.4). with salt C is less effective and salt B intercalation IR spectroscopy is insignificant. Unfortunately, in comparison with The IR spectra might confirm absorption and the commercial material all results are less satisfy- intercalation of both salts into montmorillonite ing. Thus, synthesized salts show less utility as structure (Fig.5). Spectra of modified MMT re- modifying agents than Cloisite 10 that induces ex- veal bands belonging to the salts that are interca- foliation of MMT. The problem of limited effi- lated between MMT layers. The bands in the range ciency of salt B might be related to the structure of 2950-2990 cm–1 (aliphatic C-H bonds stretch- of the compound. ing) are observed for salts A and B and in modi- Table. Basal spacing for modified MMT.

Name of sample Diffraction, 2Θ [deg] Basal spacing [nm] a unmodified montmorillonite RdH 7.05 1.25 b montmorillonite modified with salt A* 5.7 1.55 c montmorillonite modified with salt C* 5.8 1.52 d montmorillonite modified with salt A** 5.7 1.55 e montmorillonite modified with salt B** 6.6 1.34 f commercially modified montmorillonite 4 2.21

* Intercalation in water-acetone solution at RT. ** Intercalation in aqueous solution at 95oC. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 35 fied MMTs, however their intensity for samples containing B salt is very low. For the modified

Fig.4. Possible mechanism of hydrogen abstraction.

MMT, the band at 2850 cm–1 is growing, probably due to interaction of the salts with MMT. Addition- ally, characteristic bands in the range of 1100-1400 cm–1 (probably C-C and aromatic C=C stretch- Fig.6. TGA measurements: a – MMT, b – MMT modified with salt A, c – MMT modified with salt B, d – commercially modified MMT, e – salt A. other hand, commercially modified MMT remains stable up to 230oC. No effect of sample irradiation on the thermal decomposition processes is observed. TGA results also confirm the intercalation of the salts. Conclucions We synthesized quaternary ammonium salts containing unsaturated bonds designed for the modification of MMT and forming relatively stable radicals that in mixing process initiate chemical bonds between the filler and polymer matrix. The prepared ammonium salts probably inter- calate into MMT layers, as was found by the WAXS IR methods and TGA. Fig.5. IR spectra of: a – unmodified MMT, b – commercially modified MMT, c – MMT modified with salt A, d – Mechanism of the radiation-induced processes MMT modified with salt B, e – salt B, f – salt A. All sam- in the modified MMT, consisting in the transfer of ples in the form of KBr pellets. hydrogen atoms from MMT to unsaturated bond and formation of alkyl-type, radical was proposed. ing) also appear. In these ranges pure MMT does The obtained products can be used as fillers in not absorb, thus identification of the signals is un- in situ polymerization, polycondensation or hard- ambiguous. The correlation between IR and dif- ening of some monomers or resins, but the method fraction measurements is apparent – low intensity of mixing must be improved. of salt B absorption in the modified MMT results from insignificant intercalation reflected by a small References shift in basal spacing measured by the WAXS [1]. Leszczynska A., Njuguna J., Pielichowski K., Banerjee method. J.R.: Thermochim. Acta, 453, 75-96 (2007). Thermogravimetric analysis [2]. Leszczynska A., Njuguna J., Pielichowski K., Banerjee Although salt A is stable up to 200oC, decom- J.R.: Thermochim. Acta, 454, 1-22 (2007). position of MMT modified with this compound [3]. Nowicki A., Przybytniak G., Kornacka E., Mirkowski starts at about 170oC (Fig.6). Similar process was K., Zimek Z.: Radiat. Phys. Chem., 76, 893-900 (2007). confirmed for MMT modified with salt B. On the

THE INFULENCE OF IONIZING RADIATION ON THE THERMAL PROPERTIES OF SEGMENTED POLYURETHANES FOR BIOMEDICAL PURPOSES Marta Walo, Grażyna Przybytniak

Segmented polyurethanes (PUs) have found ap- between soft and hard segments. Therefore, they plication in medicine as biomaterials due to good are commonly used for production of scaffolds in biocompatibility, hydrolytic and oxidative biosta- tissue engineering and for manufacturing medical bility, excellent mechanical properties and good devices, such as vascular grafts, artificial hearts, processibility [1]. Polyurethanes represent a class catheters, mammary implants [2]. of synthetic elastomers whose physicochemical The aim of this study was to characterize the properties may be modified by changing the ratio influence of ionizing radiation on the thermal 36 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES properties of segmented polyurethane, which can ture rises with increasing heating rate. Obtained be potentially used as a biomaterial for medical polyurethane remains thermally stable up to 270oC, applications. and above this temperature the first stage of de- The thermal degradation behavior of neat and composition is observed. The character of thermo- electron beam irradiated PU were investigated us- grams points out to a multi-stage mechanism of ing two methods, which do not demand a precise the decomposition. The temperature of maximum knowledge of the reaction mechanism. The activa- mass loss was observed in the range of 383-417oC tion energy E can be determined by using Kissinger’s and 381-415oC, for neat and irradiated polyure- method (1) and Flynn-Wall-Ozawa’s (2) method thane, respectively. The thermogravimetric analysis according to the following equations [3,4]: showed that the polymer is slightly more stable before than after irradiation with a dose of 112 qE kGy. It is necessary to stress that an applied dose ln(2 )=− + const (1) TRTmax max of 112 kGy is substantially higher than a standard dose used usually for sterilization of medical de- 1.05E vices. Therefore, upon exposition to a sterilization ln(q)=α− ln((f( )) (2) RT dose of about 25 kGy polyurethane undoubtedly i preserves thermal stability. where: Tmax – the temperature of the maximal rate The activation energies obtained using Flynn- of decomposition, q – heating rate, Ti – the tem- -Wall-Ozawa’s method are shown in Table (Fig.2 perature at which the degree of conversion α is (I)). From these data it seems that in the case of attained. irradiated polymer, E decreases with growing de- Segmented polyurethane based on poly(1,4-bu- gree of conversion, α. The E values decrease from tylene adipate)diol end-capped by –OH group 153 to 117 kJ/mol for 5 and 20% degree of conver-

Fig.1. DTG thermograms of PU: (A) before irradiation and (B) after irradiation with a dose of 112 kGy.

(PBA) of molecular weight MW=1000, isophorone sion. For non-irradiated polyurethane, the changes diisocyanate (IPDI) and 1,4-butanediol (BDO) are noticeable smaller and vary in the range of were synthesized in bulk by a two-step reaction. 141-132 kJ/mol. The activation energy was also de- The molar ratio of PBA:IPDI:BDO was 1:1.66:0.66. termined using Kissinger’s method, according to The polycondensation process was carried out with- equation (1) – Fig.2 (II). The activation energies out catalyst. The samples used for measurements of 162 and 155 kJ/mol were found for neat and ir- were irradiated in air with an electron beam in an radiated sample, respectively. accelerator Elektronika 10/10 to a dose of 112 The DSC thermogram of PU for the second kGy. Thermogravimetric analysis (TGA) was per- cycle of heating is shown in Fig.3. Glass transition formed on TA Instruments (Q500) thermal analyzer under nitrogen atmosphere from 30 to 600oC Table. Activation energies of PU obtained from Flynn-Wall- -Ozawa’s method. at various heating rates: 5, 10, 15, 20, 25oC/min. DSC (differential scanning calorimetry) experi- Activation energy [kJ/mol] ments were carried out on a TA Instruments dif- Degree of conversion dose ferential scanning calorimeter (MDSC 2920) under [%] nitrogen atmosphere. The samples were scanned 0 kGy 112 kGy at a heating rate of 10oC/min for a temperature range from -100 to 250oC. 5 141 153 Thermal degradation derivatives obtained at 10 132 132 various heating rates: 5, 10, 15, 20 and 25oC/min are shown in Fig.1. DTG (derivative thermogravi- 15 141 124 metry) curves for non-irradiated and irradiated 20 137 117 polyurethanes show that the degradation tempera- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 37 I

Fig.2. Flynn-Wall-Ozawa’s (I) and Kissinger’s (II) analysis of the thermal degradation of PU: (A) before irradiation and (B) after irradiation with a dose of 112 kGy. of the soft segment chains were observed at -31.3 terials. Reduction of activation energy in PU upon and -32.4oC for neat and irradiated polyurethane, exposure to ionizing radiation with degree of con- respectively. The endothermic peaks that corre- version might result from oxidative degradation spond to the melting phase transition of the hard since carbon centered radicals generated by irra- segment domain were observed at 100.1oC for diation are usually converted to peroxyl radical non-irradiated PU. For PU irradiated with a dose that is a precursor of many oxygen containing of 112 kGy this temperature is shifted to 111oC. groups. Decay of easily decomposed carbonyl, The significant enhancement of the temperature carboxyl or hydroperoxyl groups gives rise to the results from crosslinking of polyurethane initiated decrease in onset temperature as well as activa- by ionizing radiation. tion energy. Rate of emission of the volatile sub- Investigation of thermal properties enables to stances is in such a case faster, especially during estimate the changes in irradiated polymeric ma- the first stage of decomposition. On the other hand, simultaneously crosslinking of hard segments proceeds as seen from the increase of melting transition temperature for irradiated polyurethane. Thus, two parallel, competitive processes were confirmed, however, their efficiency for a dose of 112 kGy is limited. References [1]. Lan P.N., Corneillie S., Schacht E., Davies M., Shard A.: Biomaterials, 17, 2273-2280 (1996). [2]. Gorna K., Gogolewski S.: Polym. Degrad. Stab., 79, 465-474 (2003). [3]. Barral L., Cano J., Lopez J., Lopez-Bueno I., Nogueira P., Abad M.J., Ramirez C.: Eur. Polym. J., 36, 1231-1240 (2000). [4]. Pielichowski K., Flejtuch K.: J. Anal. Appl. Pyrolysis, 73, 131-138 (2005). Fig.3. DSC thermogram of PU. 38 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES SELECTION OF POLYMER MATRICES FOR RADIATION GRAFTING Ewa Maria Kornacka, Grażyna Przybytniak, Krzysztof Mirkowski

Development of the chemical industry, purifica- vestigations, the influence of ionizing radiation on tion and concentration of valuable materials in the trunk polymers was studied, i.e. level of radi- dilute solution, or difficult separation system have cals stable at room temperature and radiation become important research topic. On the other yield of evolved hydrogen were estimated for each hand, the effective treatment of heavy metals in polymer. Grafting yield might depend on the level the environment has become one of the major of radicals initiated in polymeric matrix. The ana- issues of public interest due to their toxicity. One lysis of paramagnetic species performed by EPR of many techniques used for this purpose is an ion (electron paramagnetic resonance) spectroscopy exchange method based on cation exchange ad- enables to estimate the ability of particular poly- sorbents. Radiation-induced grafting of vinyl monomers to radiation-induced formation of radicals mers onto polymer substrates has attracted consi- and reveals indirectly the ability to construct cova- derable interest because it imparts some desirable lent bonds with monomer molecules. properties, such as chelation and ion exchange. PS is considered as the most radiation resistant In our studies three types of polymers, i.e. poly- polymer due to the efficient conversion of absorbed propylene (PP), polyethylene (PE) and polystyrene radiation energy into heat by aromatic rings. Thus, (PS), were applied as matrices. It is well known radiation processes are very limited and radiation that these polymers are inert, hydrophobic, mechanically strong and following irradiation produce long-lived paramagnetic species. Therefore, it seems that all of them are appropriate matrices for radiation-induced grafting. At first stage of in-

Fig.1. EPR spectra of radicals formed in PS by ionizing ra- Fig.2. EPR spectra of radicals formed in PP by ionizing radiation with a dose of 25 kGy (electron beam, air atmo- diation with a dose of 25 kGy (electron beam, air atmosphere) and expected radical structures. sphere) and expected radical structures. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 39 yield of the radicals in PS is much lower than in trum of PE is a composite signal arising from the other polymers. According to Clough et al. [1] various contribution of several radical individuals three radicals can be produced – two formed upon (Fig.3). Deconvolution of the experimental spec- abstraction of hydrogen and one created via addi- tra leads to the conclusion that eventually alkyl, tion of hydrogen atom to the aromatic ring. allyl and polyenyl radicals are produced under The EPR spectrum measured upon irradiation vacuum. The dominant intermediate is a second- with a dose of 25 kGy (Fig.1) is uncharacteristic ary alkyl radical; less populated are allyl type radi- and of low intensity. The shape of signals points cal and polyenyl radical that might be selected out that oxidative degradation must be limited as upon partial decay of the main product. Significant the contribution of peroxyl radical signal is insig- level of paramagnetic species should facilitate the nificant. This is another reason for unusual radia- formation of covalent bonds during grafting. The

Fig.3. EPR spectra of radicals formed in PE by ionizing radiation with a dose of 25 kGy (electron beam, vacuum) and expected radical structures. tion resistance of PS. On the other hand, low effi- concentration of radicals in PE estimated directly ciency of the radical production might inhibit upon irradiation overcome that found in PP. We radiation-induced grafting. must emphasize that the used polymers are com- Figure 2 shows the EPR spectra of the radicals mercial products, thus the observed variations formed in PP upon exposure to an electron beam. among radical populations concern only these par- Tertiary alkyl radical is a dominant product that ticular materials. fast undergoes oxidation. Formed peroxyl radical The melting points of crystalline phases of PP is very stable and can be detected even many months and PE before and after grafting processes do not upon irradiation thus PP seems to be a proper ma- change considerably values (Fig.4). Analysis of trix for applying pre-oxidation method of grafting. the melting endothermic peaks (as well as crystal- However, such a procedure requires exposure of lization exotherms, not shown results) reveals that the polymer to much higher doses than in the di- enthalpies of transitions decrease. These data pro- rect method, thus the risk of polymer degradation vide information on the changes in structural order increases. The level of radicals, as was roughly de- of polymer chains promoted by the grafting. Taking termined by double integration of obtained EPR into account enhancement of the total weights by signal is more than 4 times higher in PP than in PS. 25% due to AAc grafting, the enthalpy of phase PE also is considered as a radiation resistant transitions ought to be reduced by 20%. Observed polymer, but the background of the phenomenon decline of the enthalpies is ca. 33 and 20%, respec- is different than in the case of PS. A dominant fac- tively for PE and PP. It seems that radiation graft- tor determining final effect of irradiation is the ing induces in PE reduction of the degree of crys- formation of bonds between the main chains that tallinity while proportion between the ordered occur in amorphous phase. Except effective cross- and disordered phases in PP remains unchanged. linking, ionizing radiation induces residual radi- Disintegration of crystalline regions in grafted PE cals in crystalline phase. The experimental spec- was also confirmed by Gupta et al. [2]. 40 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

Fig.4. Endotherms of PE (A) and PP (B) before grafting (2) and after grafting (1). Degree of grafting – 25%. Finally, we found by EPR spectroscopy that search project No. POL14431) and by the Min- concentration of radicals generated in PE back- istry of Sciences and Higher Education (Poland) bone is higher than in PP, and much higher than in (165/W-IAEA/2008/0 project). irradiated PS. Additionally, lifetime of the intermediates in PS is shorter than in the irradiated PE References and PP thus conversion to diamagnetic product [1]. Clough R.L., Malone G.M., Gillen T.K., Wallace J.S., might concur with initiation of the grafting pro- Sinclair M.B.: Polym. Degrad. Stab., 49, 305-313 cesses. (1995). On the basis of the above data, polyethylene [2]. Gupta B., Muzyyan N., Saxena S., Grover N., Alam S.: was chosen as the most promising matrix for radia- Radiat. Phys. Chem., 77, 42-48 (2008). tion grafting. This work was partly supported by the Inter- national Atomic Energy Agency (co-ordinated re-

UNIT PROCESSES AND UNIT OPERATIONS IN RADIATION PROCESSING Zbigniew P. Zagórski, Wojciech Głuszewski

The concept of unit processes and operations has tion of the A-bomb. Authors of the success were been introduced early in the history of chemical chemists from DuPont, experienced with critical technology, already at the beginning of the XX stages of polymer production, in that case of the century. Elements of the technological procedures specific polyamid, later called nylon. were divided into unit processes and unit opera- There is no need to list the usefulness of appli- tions. The intention was a rationale and economic cation of the idea of unit operations and processes combination of, e.g. operation of liquid-liquid sep- in more cases in chemistry. One of the present au- aration in the process of extraction, with the reduc- thors, Zagórski [1], has indicated the usefulness of tion of time of contact of two liquid phases. Such the idea in analytical chemistry, where proper contact has to be reduced as much as possible dur- combination of processes (chemical reactions run- ing the process of separation of radioactive con- ning with high rate constant and without second- stituents in the processing of spent nuclear fuel. ary reactions) combined with proper operations Unexpectedly, a unique operation involving cen- (mainly separations) yielded best results, especial- trifuge in the extraction, developed in the Institute ly in automation of industrial control [2] and in of Nuclear Research (now the Institute of Nuclear distant operations, like present day robotic devices Chemistry and Technology – INCT) in the early performing chemical research in far places, like seventies by Professor Przemysław Hoffmann, has the planet of Mars. shown advantage in the production of antibiotics, It is not difficult to see unit processes and unit where the contact of the extractant with the basic operations in the technology of radiation process- solution has to be reduced to avoid the decay of ing. Unit processes are chemical, ionizing radia- the antibiotic. tion-induced reactions and secondary phenomena, More examples of advantages, which are reached e.g. applied in radiation sterilization. They are de- by matching proper unit operation to most strange fined by the dose/effect value, which has to be unit process can be find in the history of rapid and achieved by matching proper unit operation. The successful separation of constituents, plutonium latter is the source of radiation and mode of its mainly, of spent reactor fuel in Hartford, USA in operative delivery. A unit process in radiation pro- the years 1943-1945, with the purpose of construc- cessing, as above, has to be developed with the RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 41 orientation toward particular unit operation, in supplies in boxes on the conveyor and the third for our case on the kind of source which will be used. irradiation of large objects for the purpose of radi- In some cases it is advisable to develop the chemi- ation crosslinking of polymers with extremely high cal side of the task to be possible to apply with doses. That is the development of hardware in the both basic kinds of a source – isotopic and/or elec- Department of Radiation Chemistry and Tech- tric. Geometric shape of processed material has to nology, INCT, in agreement with the unit processes be defined, allowing sometime the use of quite and operation principles. It will find the final solu- specific unit operation. tion of the Center for Radiation Processing in the Unit operation in radiation processing is either near future. connected with the irradiation chamber surround- For obvious reasons, it was not the case at the ed with a radioisotopic source, usually loaded with beginnings, because one radioisotopic and and one cobalt-60, or with electric one, i.e. with the con- electron source had to be versatile. Our specific veyer running under the electron beam window of needs in the sixties of an multifunctional electron the accelerator. accelerator were realized like at the Risø National The main practical advantage of unit processes Laboratory (called Risø Nuclear Institute at that and unit operations classification is versatility of time) before. The Accelerator Department in that combinations of both, as it was the case in the men- laboratory pioneered with a construction yielding tioned examples. The number of sources produced either high power, scanned electron beam irradi- since the introduction of cobalt-60 in the fifties ating the conveyor with boxes of product under and electron accelerators since the first construc- processing, or yielding straight electron beam for tions in General Electric laboratories at the same pulse radiolysis. Our installation of the accelera- time [3], is comparatively low. Therefore, manu- tor LAE 13/9, securing all needs of irradiation at facturers of irradiation facilities were selling their that time [4], put into operation in the year 1971 product adjusted to the needs of the client. He was the last of that type of unit operations. Our was treating the installation as the unit operation, next accelerators represented single purpose units, matching new unit processes to the existing possi- dedicated to one unit process only. bility. It has not been the best solution, usually de- What happed to our first, double function (ra- manding the help of the producer of the source. diation processing plus pulse radiolysis) accelera- The present development of radiation processing tor? Construction of that accelerator demanded a indicates the need of specialization of unit processes large volume room and an accordingly large vol- and operations. Therefore, the latter become more ume, thick (3 m) heavy concrete walls. After resig- needed and dedicated to specific unit processes. nation of pulse radiolysis, performed now in dedi- The increased availability of different accelerators cated LAE 10 accelerator, the construction became makes it possible that in one plant three different accelerators are operating: one for small samples irradiated with extreme short pulses (pulse radiolysis), one for radiation sterilization of medical

Fig.2. Door in the biological shield is 3 m thick.

obsolete. In the mean time, next accelerators real- Fig.1. Show the layout, with indication of the zone previ- ized as units for irradiation of boxes only, became ously used for pulse radiolysis (crossed area). insufficient to work for irradiation of large objects, 42 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES volved the rails, on which the pulse radiolysis stand, prepared just outside the irradiation room, was wheeled through the revolving door in the biological shield, 3 m thick (Fig.3). The stand was large, because it involved all infrastructure of pulse radiolysis. The adaptation to irradiation of large objects involves reconstruction of the straight beam port of electrons to irradiation of large objects. Conclusion: The number of irradiation facilities in the world is comparatively low, but nevertheless they have to be constructed according to the unit processes/unit operations principle, with the possibility of final tuning of the construction to the needs of the user. The case of the oldest electron accelerator in the INCT (put into full operation in 1971), constructed as bifunctional, is changed in a non-expensive way to serve a new unit process, to realize a need which arose only in the 2000s. The part of this work has been presented at the “Recent Development and Applications of Nuclear Technologies” Białowieża Meeting in 2008 [5]. References [1]. Zagórski Z.P.: Chem. Anal., 2, 412 (1957). [2]. Zagórski Z.P.: Automatyzacja w chemii analitycznej. II wyd. Wydawnictwa Naukowo-Techniczne, Warszawa 1966, 252 p. (in Polish). Fig.3. Construction of that accelerator demanded large [3]. Lawton E.J., Buechera M., Balwit J.S.: Nature, 172, volume room and accordingly large volume, thick (3 m) 76-77 (1953). heavy concrete walls. [4]. Zagórski Z.P.: Postępy Techniki Jądrowej, 12, 601-608 (1983), in Polish. like bobbin with polyethylene tubes for hot water. [5]. Zagórski Z.P., Głuszewski W.: Unit processes and unit Our next project is the reconstruction of the first operations in radiation processing. In: International accelerator into the unit for irradiation of large Conference on Recent Developments and Applica- objects. Figures 1 and 2 show the layout, with indi- tions of Nuclear Technologies”. Conference Abstracts. cation of the zone previously used for pulse radio- Białowieża, Poland, 15-17.09.2008. Institute of Nuclear lysis. That zone is quite large, because it has in- Chemistry and Technology, Warszawa 2008, p.67.

APPLICATION OF DRS FOR INVESTIGATIONS OF PROTECTION EFFECTS IN RADIOLYSIS OF POLYPROPYLENE Wojciech Głuszewski, Zbigniew P. Zagórski

This study has been undertaken in order to estab- dose rate from 1.5 to 3 kGy. All added styrene has lish the reaction mechanisms of protection effects polymerized totally, and its percentage was checked in radiolysis of aliphatic/aromatic blends of poly- gravimetrically. All irradiations, except gamma mers. Further stages of oxidative degradation of exposure mentioned above, were done with an polypropylene (PP) were studied by diffuse reflec- electron linacs, Elektronika 10/10 (10 MeV, 9 kW) tion spectrophotometry (DRS) [1]. That is the only or LAE 13/9 (up to 13 MeV, 9 kW straight beam, possible technique, due to the opacity of the polymer samples. Introduction of small molecule additives into a polymer composition is simple, but preparation of aliphatic/aromatic polymer blends is more complicated and demands the development of new procedures. The case of polypropylene/polystyrene (PS), i.e. of a semicrystalline, non-polar thermoplastic polymer and a polar, amorphous polymer is known to be immiscible. Mechanical mixing proved formation of unsatisfactory blend from the point of view of energy transfer, but other approaches described here resulted in a proper mixture. The sample was prepared by soaking polypropylene powder with sta- bilizer-free styrene and polymerization/grafting Fig.1. DRS spectra of blend PP/PS irradiated in oxygen to processed in the gamma field from cobalt-60 at a the dose of 60 kGy, after irradiation. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 43 or 6 kW bent beam of improved monoenergetic spectrum). Spectra were recorded on a Perkin Elmer Lambda 7 spectrophotometer with an integrating sphere. That technique has been applied earlier in the investigation of radiation chemistry of neat polypropylene. The DRS method is by two orders of magnitude more sensitive than IR spectroscopy because of much higher molar extinction values of UV/Vis absorbing groups. Results by DRS are connected with oxidation phenomena, described in [2,3]. As preliminary information, Fig.1 shows the oxidation phenomena in the PP/PS mixture. The bands at 210, 245 and 295 nm were assigned to peroxy and ketone groups. Absorbtion bands are within the range of 295 nm (Fig.2). They are due to the scission of PP chains and can be considered Fig.3. Formation of oxidation products on PP chain (λ=295 as the indication of degradation of polymer in the nm) in the function of composition of the PP/PS blend. Dose – 25 kGy.

A rough estimate shows that the protection extends to a distance of 14-18 mers of polypropylene. That is connected with the energy transfer of single ionization spurs, which have some freedom of movement along the chains. Chains of both polymers, aliphatic and aromatic must have sufficient area of contacting, or exhibit short distance sites for energy transfer to the aromatic structure, which is the sink of energy. In conclusion one can state that DRS is simple, convenient and promising. In the future, it would be interesting approach to apply DRS in investi- Fig.2. DRS spectra of blend PP/PS irradiated in oxygen to gations of protection effects by the pulse radiolysis the dose of 25 kGy, after 3 month. method adapted to polymers. Following the procedure adopted previously, this research is con- region of single ionization spurs. In the process of tinued. aging the intensity of bands assigned to primary of peroxy radicals is diminishing, as well as the pres- References ence of intermediate carbonyl groups formed in [1]. Zagórski Z.P.: J. Polym. Mater., 52, 323-333 (2003). the middle of the chains. The band characteristic of [2]. Zagórski Z.P., Głuszewski W.: Radiacyjna modyfikacja carbonyl group formed after the scission of chain polipropylenu. Oficyna Wydawnicza Politechniki Czę- is appearing. stochowskiej, Częstochowa 2008, pp.247-254 (in Polish). [3]. Głuszewski W., Zagórski Z.P.: Nukleonika, 53, 21-24 Samples were of really tightly packed polymers, (2008). and the protection effect could appear, as it is visible from the concave shape of the curve (Fig.3).

GAMMA IRRADIATION AND HEAT TREATMENT INFLUENCE ON STRUCTURAL PROPERTIES OF POTATO STARCH-LIPID SYSTEMS STUDIED BY MEANS OF WAXS DIFFRACTION AND FTIR SPECTROSCOPY Krystyna Cieśla, Krzysztof Łyczko

Our previous studies, carried out by means of dif- the complexions formed in the non-irradiated and ferential scanning calorimetry (DSC) have shown irradiated systems, containing potato starch and the differences between interaction of the irradi- cetyl-trimethylammonium bromide (CTAB), lauric ated and non-irradiated potato starch with natu- acid, palmitic acid, sodium laurate and sodium rally occurring or admixed lipids and surfactants palmitate, applying WAXS (wide angle X-ray scat- [1-5]. The results suggest that the species formed tering) diffraction and FTIR (Fourier transform in the systems containing the irradiated and non- infrared) spectroscopy. -irradiated starches differs in structural properties. Potato starch, lauric acid and palmitic acid That conclusion covers the structure of starch-lipid were products of Sigma. Beside, CTAB by Aldrich inclusion complexes. Therefore, at present, the and sodium laurate and sodium palmitate (both studies were initiated dealing with the structure of Fluka products) were used. Potato starch was irra- 44 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES diated with Co-60 gamma radiation applying a of B-type structure occurs probably according to dose of 30 kGy. Irradiations were carried out in a the partially reversible transformations (endother- gamma cell Issledovatel placed in the Department of Radiation Chemistry and Technology, Institute of Nuclear Chemistry and Technology (INCT). WAXS diffraction was carried out using an HZG4-C diffractometer (Carl-Zeiss Jena) applying a CuKα radiation with a tube voltage of 34 kW and a tube current of 18 mA. FTIR spectroscopy measurements were recorded in the range 400-4000 cm–1 by means of a Bruker Equinox 55 spectrometer using KBr pellets (2.5 mg/250 mg). Presentation of the data was done after normalization of the intensities of the bands with a maximum at 1021 cm–1. Starch-lipid preparations were obtained by heating of mixed systems, containing 3% starch gels and an addition of fatty acid derivatives, mixed at ligand:starch ratios varying in the range 0.016÷0.100 Fig.2. Diffractograms of the products containing non-irradiated or irradiated starch and sodium palmitate (palmi- g/g (corresponding to 0.082÷0.0339 mmol of lipid tate to starch ratio equal to 0.061), obtained after heating per 1 g of starch) The procedure appropriate for at 140oC. lipid complexation was applied. Starch was thus pregelatinized at 90oC during 2 h, the ligand solu- mal accompanied by exothermal), taking place dur- tion was added at 70oC and the gel was continued ing heating in the temperature range 120-150oC [3]. to be heated at 90oC during 4 h. However, in the Diffractograms of the products formed by the cases of sodium laurate and sodium palmitate, heat- irradiated starch with lauric or palmitic acids indi- ing was carried out also at a temperature of 140oC cated the presence of two phase system, probably (2 h). Negligible amounts or none of lipids were B and V or A and V, with a high content of V then observed in the products. The products dried phase (Fig.3). The starch-lipid complexes char- at ambient temperature were used for WAXS ex- acterized by A structure, as well as those revealing aminations, while in the purpose of FTIR studies similar to our diffraction patterns were already the lyophilized samples were obtained. Simultane- described [4-7]. Creation of the semi-crystalline ously, pregelatinized starch samples were prepared. structure in the present samples, basing starch de- Diffractograms of the V-type typical for starch graded by irradiation, reminds the effect of acid gels were recorded in the case of gelatinized hydrolysis [8]. The evidence of the crystalline frac- starch, non-irradiated and irradiated as well as in tion was detected easier when a larger lipid amount the cases of standard products prepared with the was introduced to the sample (at starch:lipid ra- addition of CTAB, sodium laurate and sodium tion of ca. 0.016 and 0.056), in contrary to the palmitate (an example is shown in Fig.1). In the known data [8]. That result can be related to de- case of the products obtained using the irradiated creased ability of the irradiated starch for joining starch and those lipids, the broad reflections and surfactants [4]. Structural modification associated the hightened background level were observed. with an increase of the lipid content in the sample However, 2 h of treatment in a heating chamber at can be related to the modified melting and crystal- a temperature of 140oC led to formation of the lization processes, observed by differential scan- semi-crystalline B structure on the base of the ir- ning calorimetry [1-4]. radiated starch-palmitate system, while in the case The appearance of characteristic bands corre- of the initial starch-palmitate the standard product sponding to C=O stretching vibrations in the with V structure was still obtained (Fig.2). Formation

Fig.1. Diffractograms of the products containing non-irra- Fig.3. Diffractograms of the products containing non-irradiated or irradiated starch and sodium laurate (laurate to diated or irradiated starch and lauric acid (lauric acid to starch ratio equal to 0.075), prepared in standard condi- starch ratio equal to 0.016), prepared in standard conditions. tions, confronted with diffractograms of lauric acid. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 45 range of 1500-1800 cm–1, and their relative inten- al bands occurred after starch irradiation and in- sity in respect to the broad, overlapping bands be- dicated the formation of more homogeneous sys- longing to C–H and C–C vibrations observed in tems. the region 900-1200 cm–1 seemed to be the most interesting in the FTIR spectroscopy studies of the starch-lipid systems. Examples of FTIR absorption spectra are presented in Figs.4 and 5. In the case of the systems containing CTAB or lauric acid, the bands with a maximum at ca. 1643 cm–1 originating from the stretching vibrations of the C=O groups were observed. In addition, for the starch-palmitic acid system the shoulder at

Fig.5. FTIR absorption spectra obtained for the products containing non-irradiated or irradiated starch and sodium laurate (sodium laurate to starch ratio equal to 0,049), heated at 140oC, confronted with the spectra of pure starch and of sodium laurate. The results show the differences between the Fig.4. FTIR absorption spectra obtained for the products structural properties of the products formed by containing non-irradiated or irradiated starch and lauric heating of the system: starch-fatty acid derivative- acid (lauric acid to starch ratio equal to 0.016), prepared in -water, at temperatures of 90 and 140oC basing on standard conditions, confronted with the spectra of pure starch and of lauric acid. The relative intensities of the selected lipids/surfactants and the non-irradiated bands at 1640 cm–1 were equal to 0.39 and 0.19, respectively and the irradiated starch. in the cases of the non-irradiated and the irradiated starch- -lipid systems and to 0.44 in the case of pure starch. References about 1670 cm–1 associated with the ν(C=O) band [1]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 68, 933-940 (2003). occurred. The intensity of that additional shoulder [2]. Cieśla K., Eliasson A.-C.: Acta Aliment., 36 (1), decreased after irradiation. No separate bands 111-126 (2007). were observed connected with the presence of [3]. Cieśla K., Rahier H.: DSC studies of gamma irradia- free lipids in the products although intensities of tion effect on interaction of potato starch with the se- the bands, corresponding to C=O vibrations were lected fatty acids and their sodium salts. In: INCT An- very high in the case of both pure fatty acids nual Report 2006. Institute of Nuclear Chemistry and (Fig.4). It was also discovered that intensity of the Technology, Warszawa 2007, pp.44-47. bands at 1643 cm–1 was lower in relation to the [5] Cieśla K. et al.: Wpływ promieniowania gamma na intensity of the bands in the range of 900-1200 właściwości skrobi: oddziaływania z wodą i z lipidami, cm–1, in the case of the systems containing the ir- folie skrobiowo-lipidowe. Projekt badawczy 2 P6T 026 27. Sprawozdanie merytoryczne 2007 (in Polish). radiated starch and CTAB, lauric acid or palmitic [4]. Cieśla K., Lundqvist H., Eliasson A.-C.: Surface ten- acid, as compared with the systems containing the sion studies of binding cetyltrimethyl-ammonium bro- non-irradiated starch. No differences were noticed mide to gamma irradiated and non-irradiated potato between intensity of these bands in the case of amylopectin. In: INCT Annual Report 2006. Institute pure starch, irradiated and non-irradiated, al- of Nuclear Chemistry and Technology, Warszawa though it is known that irradiation induces the 2007, pp.47-48. formation of carbonyl and carboxyl products [9]. [5]. Eerlingen R.C., Cillen G., Delcour J.A.: Cereal Chem., Two bands with a maximum at approximately 71, 170-177 (1994). 1644 and 1556 cm–1 assigned to C=O vibrations [6]. Tang M.C., Copeland L.: Carbohydr. Polym., 67, 80-85 (2007). were observed in the systems containing sodium [8]. Czuchajowska Z., Sievert D., Pomeranz Y.: Cereal laurate or sodium palmitate. The additional band, Chem., 68 (5), 537-542 (1991). –1 recorded at lower frequency (1556 cm ) were ob- [9]. Raffi J.J., Agnel J.-P.L., Thiery C.J., Fréjaville C.M., served at the same position for the pure fatty acid Saint-Lèbe L.: J. Agric. Food Chem., 29, 1227-1232 salts. A decrease in the intensity of these addition- (1981). 46 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES SCANNING ELECTRON MICROSCOPY STUDIES OF STRUCTURAL PROPERTIES OF FILMS PREPARED USING NON-IRRADIATED AND GAMMA-IRRADIATED POTATO STARCH Krystyna Cieśla, Bożena Sartowska

In recent years a growing interest has evolved in degradation and oxidation, induced by ionizing ra- the enlargement of application of biodegradable diation [4], and can, furthermore, be related to the and edible packaging, in relation to the problems modified interaction of non-irradiated and irradi- of environmental protection and in the purpose to ated starches with fatty acids derivatives [3]. In improve quality of food and commercial products. particular, improvement was stated of hydropho- The trials were run, therefore, on improvement of bic properties of the films prepared basing on po- the properties of such packaging by using a modi- tato starch, potato starch-sodium laurate, or po- fied composition or applying various chemical and tato starch–cetyl-trmethyammonium bromide physical treatment. (CTAB) composition [2]. The improvement of Starch is an abundant and cheap biopolymer strength and elasticity was detected in the case of and the potato starch is an appropriate material potato starch films, while in the case of films con- for the preparation of films and coatings. The ap- taining an addition of CTAB or sodium laurate, a propriate addition of hydrophobic compounds considerable increase in elasticity was noticed. might, moreover, improve barrier properties of bio- Moreover, it was found that storage of the starch- polymer films. -sodium laurate films induces increase in their hy- Our preliminary results [1-3] show radiation-in- drophobicity accompanied by an increase in the duced improvement of the functional properties mechanical strength and decrease in elasticity. of the films prepared basing on potato starch Accordingly, at present the studies of structur- alone as well as the films containing potato starch al properties of the films prepared using potato and admixed lipids/surfactants, as well as the films starch alone or in its composition with admixed prepared basing on wheat starch (containing natu- sodium monolaurate or CTAB were carried out rally occurring lipids). This occur regarding starch applying scanning electron microscopy (SEM). 0 kGy surfaces, 1000x 30 kGy

0 kGy fractures, 1000x 30 kGy

Fig.1. Examples of SEM images recorded in the case of chemically stained potato starch films (procedure I). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 47 0 kGy surfaces, 1000x 30 kGy

0 kGy fractures, 1000x 30 kGy(a)

Fig.2. Examples of SEM images recorded in the case of chemically stained potato starch-CTAB films (procedure I). (a) The structural elements are oriented parallel to the film surface (photo made at the non-typical film orientation). Potato starch of Sigma production (S-4251), starch:CTAB (10:0.75) and potato starch-sodium CTAB by Aldrich and sodium laurate by Fluka laurate (10:0.49). Moreover, the potato starch-so- were used for the preparation of films. Irradiations dium laurate (10:0.49) films prepared according with Co-60 gamma radiation were carried out in a to procedure II, were examined. In regard to the gamma cell Issledovatel placed in the Department fact that the films prepared with the addition of of Radiation Chemistry and Technology, Institute sodium laurate were sensitive to mechanical treat- of Nuclear Chemistry and Technology (INCT), ap- ment with solutions, SEM observations were also plying a dose of 30 kGy. Films were prepared by carried out for the films dried during 6 months in casting from gelatinized starch solutions with an air at ambient temperature. Observations were addition of glycerol as a plasticizer (30 wt% of performed for both surfaces of the films (external glycerol in terms of starch mass) and dried at am- and internal), for their fracture and for the section bient temperature. Films containing sodium laurate executed before drying (“old” sections). Conven- and CTAB were prepared after performing the tionally, the images of fractures and sections were procedure, leading to obtaining starch-surfactant taken for the films placed in the holder in such a complexes (at laurate:starch ratio equal to 0.049 way that the surface of the film was parallel to the and CTAB:starch ratio equal to 0.075) [3]. Glycerol top of the picture. was introduced to the composition of films at the Surfaces of all the films formed basing on the end of the preparation, prior to casting (proce- systems, containing non-irradiated and irradiated dure I), or at the beginning, before starch gelatini- starch, as well as fractures obtained after chemical zation (procedure II). Dried films were peeled staining, projected partially a honey-comb struc- from the substrate and kept in atmosphere of rela- ture (Figs.1-5), typical of the gels obtained using tive humidity (56%) before performing the proce- non-irradiated starch [5] and formed in the inter- dure of chemical staining with glutaraldehyde. mediate step of the films preparation. Similarly, SEM studies were carried out at ambient tem- the honey-comb structure was still evident in the perature for 4 types of the films, submitted to case of the “old” sections of the films containing chemical staining with glutaraldehyde [3]. These CTAB and non-irradiated starch (example in were the films prepared according to procedure I Fig.5). For example, the rectangular blocks, ac- on the basis of potato starch alone, potato companied with the cracks parallel to the films 48 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 0 kGy Procedure I: surfaces, 1000x 30 kGy

0 kGy Procedure I: fractures, 1000x 30 kGy

0 kGy Procedure II: fractures, 1000x 30 kGy(a)

Fig.3. Examples of SEM images recorded in the case of chemically stained potato starch-sodium laurate films, prepared according to procedure I and procedure II. (a) Slices of the fixing glue are visible in the images. surface were observed in the fracture of the chem- of these films (Fig.3). The fractures of the prepa- ically stained films prepared basing on non-irradi- rations obtained according to procedure I reveal a ated starch alone (Fig.1). Presence of the honey- fibrinous structure with numerous narrow pores comb structure was particularly evident in the case parallel to the surface and surrounded by thin of the films containing non-irradiated starch and walls (Fig.3). In the case of the films prepared CTAB (Fig.2), regarding its activity as a surfactant. basing on the same system, but according to the Pleated surfaces were observed in the case of procedure II, much more pleated surface was no- both types of non-irradiated films containing so- ticed than in the case of the films obtained using dium laurate (obtained using procedure I and procedure I. Similarly, the structural elements ob- procedure II), probably due to the strong swelling served in their fractures and parallel to the films RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 49 0 kGy starch: external surfaces, 1000x 30 kGy

0 kGy starch: internal surfaces, 1000x 30 kGy

0 kGy starch-sodium laurate (procedure II): fractures, 5000x 30 kGy

Fig.4. Examples of SEM images recorded in the dried potato starch and potato starch-sodium laurate films. The images of sections obtained for a starch film was similar to that observed in the starch-CTAB films. surfaces have appear more swollen and flatten, as These films were characterized by the more par- compared to these detected in the case of the films ticular structure, better ordered packing of mate- obtained according to procedure I (Fig.3). rial and lack in orientation of the structural ele- The films obtained using the irradiated starch ments. Only in the case of the films prepared appear to be more smooth and homogeneous, as basing on starch-sodium laurate system (proce- compared to those obtained using the irradiated dure I) the coarse-grained structure was observed, starch (Figs.1-3). Excluding orientation, the fine- with dimensions reminding dimensions of the -grained structural elements, observed in the case structural elements present in the non-irradiated of the irradiated starches remind the smaller films. structural elements, observed in the cases of the In the cases of the fracture performed after gels prepared basing on the irradiated starch [5]. drying the films containing non-irradiated starch 50 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 0 kGy external surfaces, 1000x 30 kGy

0 kGy internal fractures, 1000x 30 kGy

0 kGy fractures, 1000x 30 kGy

0 kGy “old” sections, 1000x 30 kGy

Fig.5. Examples of SEM images recorded in the dried potato starch-CTAB films (procedure I). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 51 or non-irradiated starch-sodium laurate (example diation correspond to the formation of smoother in Fig.4), the numerous thin trails occured, prob- and more homogeneous films. On the other hand, ably corresponding to the flattening of the cracks a decrease of elasticity in the irradiated films after or of the fibrinous structure, noticed in the cases storage can be related to the facilitated evacua- of the preparations obtained by chemical staining. tion of the plastificator from the smaller internal Just the opposite, the fractures of the irradiated spaces of those films. films is indicative of non-oriented particular structure (Fig.4). On the other hand, the fractures of the References films containing CTAB, irradiated and non-irradi- [1]. Cieśla K., Nowicki A., Buczkowski M.: Radiation modi- ated, show after drying smooth particulate struc- fication of the functional properties of the edible films ture with small precipitates (Fig.5). prepared using starch and starch-lipid system. In: INCT Small precipitates, present in the surfaces of the Annual Report 2007. Institute of Nuclear Chemistry dried films, prepared basing on starch or starch-lau- and Technology, Warszawa 2008, pp.42-45. [2]. Cieśla K.A., Nowicki A., Buczkowski M.J.: Radiation rate systems (Fig.4), appear to be connected with modification of the functional properties of the edible a plastificator leaving the films after drying. The films prepared using starch and starch-lipid system. larger amount of these precipitates, present in the Nukleonika, submitted. cases of the irradiated films as compared to the [3]. Cieśla K. et al.: Wpływ promieniowania gamma na non-irradiated ones suggest facilitation of leach- właściwości skrobi: oddziaływania z wodą i z lipidami, ing the plastificator, connected with irradiation. folie skrobiowo-lipidowe. Projekt badawczy 2 P6T 026 In fact, our studies performed using DMA (dy- 27. Sprawozdanie merytoryczne, 2007 (in Polish). namic mechanical analysis) and DSC (differential [4]. Raffi J.J., Agnel J.-P.L., Thiery C.J., Fréjaville C.M., scanning calorimetry) methods proved the forma- Saint-Lèbe L.: J. Agric. Food Chem., 29, 1227-1232 (1981). tion of two phase system in the films plasticized by [5]. Cieśla K., Sartowska B., Królak E., Głuszewski W.: glycerol and by water [3]. Gamma irradiation influence on structure of potato The results show that the improvement of the starch gels studied by SEM. In: INCT Annual Report hydrophobic and mechanical properties of the starch 2006. Institute of Nuclear Chemistry and Technology, and starch-surfactant films resulting due to irra- Warszawa 2007, pp.49-52.

DEGRADATION OF PERFLUORINATED CARBOXYLIC ACIDS IN AQUEOUS SOLUTIONS WITH THE USE OF IONIZING RADIATION Anna Bojanowska-Czajka, Przemysław Drzewicz, Lena Wójcik1/, Marek Trojanowicz 1/ Department of Chemistry, University of Warsaw, Poland

The continuous development in all areas of con- Earth and in organisms of wild animals in all contemporary human activity, connected among other tinents, in the tissue of fishes and birds. factors to use increasing number of chemical com- They are commonly detected in human organ- pounds in industry, agriculture, health care, or isms, being a serious health threat because, e.g. of households, is associated with unavoidable process destruction of lipid balance and possibility of their of emission of various compounds into the natural incorporation into a bilayer lipid cell membranes environment. This brings, however, a potential [1]. The most commonly detected compounds in danger for all forms of life, including obviously the environment are perfluorinated octanoic acid threat to human health. One of numerous groups (PFOA) and perfluorinated octanesulfonic acid of compounds, which are common pollutants of (PFOC). natural waters are surface active compounds such To widely recently investigated methods of re- as detergents, which are widely used in different moval of organic compounds which are anthropo- branches of industry and households. genic environmental pollutants, belong methods The important group of detergents from the of advanced oxidation processes (AOP), based point of view of environmental protection are per- on the use of radical reactions [2]. One of these fluorinated anionic surfactants, in which in long processes is application of ionizing radiation, which alkyl chains all hydrogen atoms are replaced by in the case of irradiation of aqueous solutions is fluorine atoms. These compounds are widely used an efficient source of radicals both of oxidizing on an industrial scale in fire-extinguishers and for and reducing properties, which can react with or- impregnation of numerous materials, in cosmetics ganic pollutants [3]. and household products. Their environmental threat There is already broad literature on the appli- results first of all from a very large chemical stabil- cation of AOPs with ionizing radiation for decom- ity in the environment, comparable to common position of numerous groups of organic pollutants persistent organic pollutants such as chloroorganic in waters and wastes, including also surfactants, pesticides, polycyclic aromatic hydrocarbons or both of industrial and municipal origin. For in- polychlorinated biphenyls. Since the beginning of stance, gamma irradiation with a 1.8 kGy dose of the 1990-ties, it is known that they occur practi- 75 mg L–1 dialkylbenzene sulfonate in aerated so- cally all over the globe, as they are detected in sur- lution allows to lower the value of COD (chemical face waters in the most remote regions on the oxygen demand) form 151 down to 56 mg L–1 [4]. 52 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES Gamma irradiation was also used for the decom- For initial concentration of PFCA 1.47 mM, a 43% position of calcium lignosulfonate, where an addi- yield of decomposition was obtained after 24 h ir- tional 5-fold increase of the efficiency of oxidation radiation, while in irradiation of solutions in the with hydroxyl radical was observed in the presence concentration range 7.4-74 μM 24 h irradiation re- of hydrogen peroxide [5]. Common environmental sulted in complete decomposition of PFOA [14]. In pollutants are also neutral detergents such as no- such processes as products a perfluorinated car- nylphenol polyethoxycarboxylate [6], and their de- boxylic acids are formed with shorter alkyl chains composition by irradiation with electron beam and fluoride ions are released. Another AOP in- with simultaneous ozonation was applied [7]. The vestigated for decomposition of PFOS is sonolysis decomposition of 420 mg L–1 nonyl ethoxylate with [15]. 99% efficiency required an irradiation dose of 10 Chemical literature contains also some pre- Gy only, and of their main product of radiolysis – liminary works on application of ionizing radia- nonylphenoxy acetic acid – 500 Gy. tion for decomposition of perfluorinated organic The decomposition of fluoroorganic compounds compounds. Gaseous products of direct radiolysis with release of total fluorine can be carried out were investigated for electron beam decomposition with various combustion methods or by the use of of some poly(perfluoro ethers) [16]. The mecha- a very strong reducers such as metallic magnesium nism of electron beam decomposition in aqueous in supercritical carbon dioxide, sodium in dry am- solution was examined for ammonium salt of monia or sodium biphenyl [8]. These methods, PFOA [17]. It was found that perfluorinated car- because of high cost of instrumentation of rea- boxylic acid remains practically non-reactive to- gents are employed mainly in a micro-scale for wards OH● radicals, while the rate constant for the – analytical purposes. For technological purposes, reaction of ammonium salt of PFOA with eaq is including environmental protection, the studies only in the range of 106-107 M–1 s–1. on biodegradation and use of advanced oxidation In this work aqueous solutions of PFOA were processes with the application of radical reactions irradiated with gamma irradiation and electron are carried on. Recently also reductive defluori- beam in different chemical conditions and with dif- nation of perfluorooctane sulfonate (PFOS) with ferent radiation doses. For examination of effec- Ti(III)-citrate and vitamin B12 as catalyst was re- tiveness of decomposition of PFCA, a developed ported [9]. The obtained results suggest the mi- earlier capillary electrophoretic method with direct crobial transformation of some PFOS isomers UV detection has been applied [18]. Determina- might be possible in anaerobic environments. tions were carried out using a Beckman P/ACE Studies of biodegradation were carried out on MDQ CE (capillary electrophoresis) system (Beck- fluorotelomer alcohols, where it was shown that man Instruments, Fullerton, CA, USA) with a products of their aerobic oxidation are unsaturat- diode array detector using as background buffer ed polyfluorinated acids and highly stale PFOA 50 mM sodium phosphate solution of pH 9.3 with [10]. In investigations of aqueous photolysis of addition of 40% isopropanol at 25 kV separation fluorotelomer alcohol in aqueous hydrogen per- voltage. Detection was carried out at 190 nm. oxide solutions it was found that the nitrate pro- The irradiation experiments in this work were moted photolysis whose a major product of pho- carried out for aqueous solutions of PFOA for tolysis pathway was PFOA [11]. Much attention is initial concentration of 5 mM, which allows to use devoted also to studies of photocatalytic decom- CE method for monitoring of decomposition yield. position of perfluorinated carboxylic acids (PFCA) This allows also determination of formation of with heteropolyacid photocatalysts [12-14]. In pho- PFCAs of shorter alkyl chains as products of ra- tocatalytic process with UV irradiation of penta- diolytic decomposition. In examination of effect fluoropropionic acid in the presence of oxygen of irradiation dose up to about 200 kGy it was about 43% of decomposition was observed after found that in aerated solutions the first decompo- 120 h irradiation for 67 mM initial concentration sition product C7-PFCA appears at a dose of [12]. A similar yield of decomposition process was about 100 kGy. Using large irradiation doses, ra- reported for nonaperfluoro-pentanoic acid [13]. diolytic decomposition was also examined in dif- Table. Results of electron beam irradiation of 5 mM aqueous solutions of PFOA in different conditions obtained by capillary electrophoresis. Recorded signal magnitude as peak area Applied dose Conditions [normalized units] [kGy] C8-PFCA C7-PFCA C6-PFCA 100 Ar saturated 3620 450 -

100 N2O saturated, pH 8 3000 - -

192 aerated + 0.2 ml H2O2 4500 770 -

192 aerated + 0.4 ml H2O2 4510 940 - 2– 192 aerated + 27 mM S2O8 pH 8 3050 50 - 2– 192 aerated + 27 mM S2O8 pH 2 2140 1020 550 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 53 ferent chemical conditions, which can favor differ- Because of that, as well as due to the potential ent radical reactions. Experiments were carried technological importance of this processes, more out in solutions saturated with argon and N2O, detailed studies on this subject are planned with and also in the presence of H2O2, which may be a thorough examination of effects of different ex- source of additional amount of hydroxyl radicals, perimental conditions on the effectiveness of ra- besides those formed in water radiolysis. In an- diolytic decomposition of selected perfluorinated other experiment irradiation was carried out in compounds which in recent years are reported as the presence of sodium persulfate, which may be a common persistent organic pollutants in the envi- ●– source of sulfate radicals SO4 formed as a result ronment. of reaction of persulfate ions with solvated electrons. They are strong oxidant, similarly to hydroxyl References radicals [19]. As it is shown in Table, among exam- [1]. Kissa E.: Fluorinated surfactants and repellents, ined conditions, the most pronounced decomposi- Marcel Dekker, New York 2001. tion of PFOA, with the formation of C7-PFCA [2]. Oppenlander T.: Advanced oxidation processes and C6-PFCA, was observed in the most oxidative (AOPs): principles, reaction mechanisms, reactor concepts. Wiley – VCH, Weinheim 2003. conditions. Figure shows the electropherograms [3]. Getoff N.: Radiat. Phys. Chem., 65, 437-446 (2002). recorded for these conditions prior to and after [4]. Bagyo A.N.M., Andayani W., Suhani C.T.: Radiat. irradiation. Phys. Chem., 69, 317-319 (2004). [5]. Zhang S.J., Yu H.Q., Wu L.X.: Chemosphere, 57, 1181-1187 (2004). [6]. Field J.A., Reed R.L.: Environ. Sci. Technol., 30, 35-44 (1996). [7]. Petrovic M., Gehringer P., Eschweiler H., Barcelo D.: Water. Sci. Technol., 50, 227-234 (2004). [8]. Venkateswarlu P.: J. Dent. Res., 69, 514-521 (1990). [9]. Ochoa-Herrera V., Sierra-Alvarez R., Samogyi A., Jacobsen N.E., Wysocki V.H., Field J.A.: Environ. Sci. Technol., 42, 3260-3264 (2008). [10]. Dinglasan M.J.A., Ye Y., Edwards E.A., Mabury S.A.: Environ. Sci. Technol., 38, 2857-3264 (2004). [11]. Gauthier S.A., Marbury S.A.: Environ. Toxicol. Chem., 24, 1837-1846 (2005). [12]. Hori H., Takano Y., Koine K., Kutsuna S., Einaga H., Ibusuki T.: Appl. Catal. B: Environ., 46, 333-340 Fig. Capillary electropherograms recorded for 5 mM PFOA (2003). solution prior to and after electron beam irradiation with [13]. Hori H., Hayakawa E., Koike K., Einaga H., Ibusuki 192 kGy dose in solution of pH 2.0 containing 27 mM so- T.: J. Mol. Catal. A: Chem., 211, 35-41 (2004). dium persulfate. Conditions of CE separation: BGE (back- [14]. Hori H., Hayakawa E., Einaga H., Kutsuna S., Koike ground electrolite) – 50 mM sodium phosphate of pH 9.3 K., Ibusuki T., Kiatagawa H., Arakawa R.: Environ. containing 40% isopropanol, 25 kV. Detection UV at 190 Sci. Technol., 38, 6118-6124 (2004). nm. [15]. Moriwaki H., Takagi Y., Tanaka M., Tsuruho K., Okitsu K., Y. Maeda Y.: Environ. Sci. Technol., 39, The perfluorinated surfactants are much more 3388-3392 (2005). difficult to decompose for environmental protec- [16]. Pacansky J., Waltman R.J.: J. Phys. Chem., 95, 1512-1518 (1991). tion than non-fluorinated surfactants. This con- [17]. Szajdzinska-Pietek E., Gebicki J.L.: Res. Chem. In- cerns also the use of ionizing irradiation. termediat., 26, 897-912 (2000). The preliminary results reported above are dif- [18]. Wójcik L., Szostek B., Maruszak W., Trojanowicz M.: ferent from those reported in earlier work [17], Electrophoresis, 26, 1080-1088 (2005). hence they require more detailed confirmation. [19]. Eberson L.: Adv. Phys. Org. Chem., 18, 79-185 (1982).

DOSIMETRIC PROPERTIES OF TWO PVC FILMS PRODUCED FOR PHARMACEUTICAL PURPOSES Zofia Peimel-Stuglik, Sławomir Fabisiak

High dose dosimetry is an important tool for qual- The Institute of Nuclear Chemistry and Tech- ity assurance and quality control of the radiation nology (INCT) has more than 30 years of experi- processing. Thin film dosimeters play an impor- ence in using a PVC film as routine dosimeter for tant role in electron beam routine dosimetry be- electron beam radiation sterilization. Experiment- cause they allow to measure dose distribution with al works done by Bułhak [1] showed that best dosi- a negligible distortion of the radiation field. Poly- metric properties have rigid PVC films produced vinyl chloride (PVC) is a cheap polymeric material for packages of pharmaceutical products. Accord- very sensitive to ionizing radiation. The irradiation ing to our knowledge, such films contain less than colours the initially transparent PCV to olive-brown 5% of plasticizers (probably phthalate), ~0.5% of what can be used for absorbed dose measure- thermal stabilizers (probably Sn compounds) and ment. less than 5% of a lubricant. The main component 54 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES is still PVC and it is responsible for rich optical -state are rather slow and are not finished during spectra generated by ionizing radiation in the vis- the irradiation. Slow radiation chemical reactions ible range. Distinct optical absorbance bands ob- in irradiated PVC can be fasten by increase of served in irradiated and heated PVC films were temperature. The current procedure being in op- attributed by Onishi [2] to conjugated systems of eration in the INCT consists in 30 min heating of –C=C–C=C– double bonds. The absorption band irradiated PVC films at 70oC. at λmax=396 nm was ascribed to structure with five It was established that the thermograwimetric double bonds. An amplitude of the absorption band characteristics of both OLD and NEW films are at 396 nm is commonly used as dosimetric signal. very similar. In particular, the glass transition tem- Unquestionable advantages of PVC films are: perature for both films is ~76oC. Nevertheless, it very low price, high sensitivity to ionizing radiation, was established that it is possible to use for dose high tolerance for environmental conditions (air measurements short (2-3 cm) PVC films heated humidity, liquid water, visible, UV and Cherenkov for 30 min at 90oC. Such a thermal procedure sta- light), slow ageing, rigidity and availability in large bilized the optical signal much better than the 30 sheets. As was said before, ionizing radiation co- min thermal treatment at 70oC (Fig.1). Unfor- lours PVC films to olive-brown what allows for a tunately, in the case of long strips which are fre- rough visual dose evaluation. However, PVC film quently used in the INCT routine dosimetry prac- dosimeters have also some shortcomings which tice, some deformation was observed. limit their common use. First of all, there has been never any company producing PVC films designed especially for dosimetry. They are still technical products with various dosimetric characteristics and only roughly known chemical composition. Thus, dosimetric characteristics of each batch have to be carefully evaluated before use. Actually, the INCT uses PVC films bought from Kunstoffwerke (Staufen, Germany) more than 30 years ago. According to our works, their dosimetric characteristics are practically the same as before. Unfortunately, it is difficult to find actually the same product. Fig.2. Optical absorption spectra of non-irradiated and ir- In this work we present the main dosimetric radiated and heated (30 min, 90oC) OLD PVC film (Kun- properties of two PVC films: an old PVC film for stoffwerke). pharmaceutical use produced many years ago by Kunstoffwerke (Staufen, Germany) and the new In this work we present the optical absorption one – produced in the same place, but by INEOS spectra of both, OLD and NEW PVC films before Company. In this work the first one is called: OLD irradiation (lower curve) and after irradiation with and the second – NEW. Both films were transparent 10 MeV electrons to 28 kGy and 30 min heating at and ~0.25 mm thick. 90oC (higher curve) (Figs.2 and 3). The samples were irradiated with 10 MeV elec- The dosimetric response of both investigated trons from a linear accelerator ELEKTRONIKA. PVC films to electron beam radiation in the range The oven SPT-200 (Zakład Usług Technicznych, Poland) without air circulation was used for heating irradiated films. Optical spectra were measured with a UV/VIS spectrophotometer Cintra 40 (GBC, Australia). The main problem for dosimetric applications is that radiation reactions leading to new steady-

Fig.3. Optical absorption spectra of non-irradiated and irradiated and heated (30 min, 90oC) NEW PVC film (INEOS). 10-35 kGy is presented in Fig.4. The NEW film is more transparent to both, visible and UV light, but at the same time much less sensitive to ioniz- Fig.1. A temperature of 10oC above the glass transition ing radiation. temperature (~76oC) in the investigated PVC films is much Conclusions: more efficient to stabilize the post-irradiation changes than • The OLD PVC film (Kunstoffwerke, Staufen, 70oC used up to now. Germany) is still suitable for electron beam do- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 55

actually used (λmax=396 nm) will be investigated. • Low sensitivity of INEOS, PH 010 2A to ionizing radiation gives a chance to use it as a dosimeter to very high doses (>100 kGy). • In both cases (OLD and NEW films) 30 min thermal treatment at 90oC (~10oC higher than glass transition temperature) stabilize the optical signal (measured at 396 nm) much better than the actually used 30 min thermal treatment at 70oC. Unfortunately, in the case of long strips some deformation was observed. Fig.4. Dosimetric response of both investigated PVC films to electron beam radiation. References [1]. Bułhak Z.: Stosowanie dozymetrów foliowych w eks- simetry in the dose range using for radiation ploatacji wielkiego źródła promieniowania – liniowego sterilization. akceleratora elektronów LAE 13/9. Instytut Badań Ją- • The NEW PVC film (INEOS, PH 010 2A) is less drowych, Warszawa 1975. Ph.D. dissertation (in Polish). sensitive to ionizing radiation. The possibility [2]. Onishi S., Nakaima Y., Nitta I.: J. Appl. Polym. Sci., 6, to use stronger absorption bands instead those 529-531 (1962).

ANALYTICAL ACTIVITY OF THE LABORATORY FOR DETECTION OF IRRADIATED FOOD ACCREDITED BY THE POLISH CENTRE FOR ACCREDITATION Wacław Stachowicz, Kazimiera Malec-Czechowska, Grzegorz P. Guzik, Magdalena Laubsztejn, Katarzyna Lehner

The Laboratory for Detection of Irradiated Food • The method for the detection of irradiated food was created in the Institute of Nuclear Chemistry containing cellulose, i.e. nuts, some spices and and Technology (INCT) in 1994. Its role was to fruits (strawberries) by EPR spectrometry based develop and verify analytical methods for detection on EN 1787:2001 European Standard. Detec- of food treated with ionizing radiation. Basically, tion is based on the observation of two radia- analytical perfection of the Laboratory has its tion-induced satellite EPR lines distanced at 6 roots in the experience gained through those early mT and assigned to cellulose-born radicals [3]. studies, although detection methods presently • The method for the detection of food from adapted are entirely consistent with the corre- which silicate minerals can be separated by a sponding European standards. Having developed thermoluminescence (TL) technique, is based the quality assurance system, the Laboratory re- on EN 1787:2002 European Standard. The ceived its first accreditation certificate in 1999. method is suitable for the examination of herbs, From this time, the accreditation is extended every spices, pharmaceutical preparations, plant ex- 3 years and is followed by a systematic increase of tracts, shrimps. The success of TL examination analytical abilities of the Laboratory. The present depends on the volume of mineral fraction iso- Accreditation Certificate of Testing Laboratory lated from the product by a suitable, sophisti- Nr AB 262 belonging to the Laboratory has been cated separation technique [4]. issued by the Polish Centre of Accreditation and is • The method for the detection of irradiated food, valid until 24.10.2010 [1]. containing crystalline sugar, i.e. candied fruits Nowadays, five accredited methods for the de- as raisins, dates, figs, mangos, papayas, bananas, tection of irradiated food are offered to customers by EPR spectrometry is based on EN 13708:2003 as listed in the Scope of Accreditation, the appen- European Standard. Detection is based on the dix to accreditation certificate. observation of a specific multicomponent EPR These are: signal derived from undefined sugar born para- • •The method for the detection of irradiated magnetic entities (radicals) [5]. food containing bones, i.e. meat, poultry, fish • The photostimulated luminescence method and shells (eggs, molluscs) by EPR (electron (PSL) is suitable for fast detection of irradia- paramagnetic resonance) spectrometry based tion in some spices, herbs and shrimps [6]. on EN 1786:2000 European Standard. The de- The thermoluminescence method, although fol- tection is based on the observation in EPR of a lowing general procedures recommended in the specific and simple (asymmetric singlet) signal EN 1788 European Standards has been enriched assigned to radiation-induced radical ion of in some detailed analytical sub-procedures en- high stability produced by ionizing radiation in abling effective separation of minerals from pow- hydroxyapatite, a mineral constituent of calci- dered samples and further TL examination of the fied tissues [2]. complex product whether irradiated or not [7]. 56 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

Table 1. Total number of samples examined in 2008. Country wide control Foreign samples Domestic samples Total number of samples and monitoring (firms and companies) (firms and companies) 323 150 166 7 Pharmaceutical products and plant extracts sup- Foreign samples originated from Germany, plied today more frequently by our customers for France, Ireland, the United Kingdom, Italy, Hungary, examination met earlier serious analytical prob- Denmark, Switzerland, Israel and China repre- lems. sented 17 food companies and firms. Domestic In total, from 1999 up to now more than 2500 samples, in turn, were delivered from 4 local food samples have been examined in the Laboratory, companies. while about 1500 samples, among them, were de- The assortment of consumable products exam- livered from abroad. The Laboratory answers any ined in 2008 compiles: question raised by the customers regarding ana- • spices, herbs and blends including powdered lytical procedure or qualification of the result of soups, sauces etc., with the content of powdered examination. No complaints concerning examina- spices and seasonings; tion, reliability of the results obtained or any other • fresh vegetables as garlic and potatoes; problem relevant to analysis were stated by the • fresh fruit – strawberries; customers. The customer opinion on analytical • shelled nuts; performance of the Laboratory expressed in ques- • powdered pharmaceutical products and plant tionnaire are positive. extracts; The total number of samples examined in 2008 • poultry; is 323, while 150 of them were analyzed within the • fish; frames of the control and monitoring programme • shrimps; under the Chief Sanitary Inspector of Poland • candied (dried) fruits; (Table 1). 164 samples, in turn, have been supplied • others (red fermented rice, savoury oriental for examination from abroad. seasonings, crystalline cellulose). A predominating number of samples has been The percentage of each group of products is given examined by the TL method which is recognized in Fig.1. as a reliable and suitable method for the examination of spices. However, spices and spice containing powdered products are widely used in food, pharmaceutical and cosmetic industries and for that reason these products are suspected to be preserved with ionizing radiation. Radiation processing of spices is allowed in the EU, but the Table 2. Number of samples examined by TL, EPR and PPSL (pulsed photostimulated luminescence) methods.

TL of mineral EPR spectrometry PPSL separated of dried, crushed Fig.2. Evaluation of consumable products examined in 2008 of whole sample from sample sample whether irradiated or non-irradiated. 257 54 12 Among 323 samples (100%), examined in the Laboratory from the 1st January to 15th December problem lies in the requirement of obligate label- 2008, 95% were detected as non-irradiated, while ling of irradiated foodstuffs not willingly accepted 5% of samples were qualified as being irradiated in the market [8]. Nevertheless, the other two de- (Fig.2). tection methods have been also used for the examination of specific products (Table 2). References [1]. PN-EN ISO/IEC 17025 May 2005: General requirements for the competence of testing and calibration laboratories. [2]. EN 1786 Foodstuffs – Detection of irradiated food containing bone. Method by ESR spectroscopy (PN-EN 1786:2000). [3]. EN 1787 Foodstuffs – Detection of irradiated foods containing cellulose. Method by ESR spectroscopy (PN-EN 1787:2001). [4]. EN 1788 Foodstuffs – Thermoluminescence detection of irradiated food from which silicate minerals can be isolated (PN-EN 1788:2002). [5]. EN 13708 Foodstuffs – Detection of irradiated food containing crystalline sugar by ESR spectroscopy (PN-EN 13708:2003). Fig.1. Assortment of consumable products examined in [6]. EN 13751 Foodstuffs – Detection of irradiated food using 2008. photo-stimulated luminescence (PN-EN 13751:2007). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 57

[7]. Research procedure PB-SLINŻ January 2006, Labo- ment of a Community list of foods and food ingredi- ratory for Detection of Irradiated Food INCT (in ents treated with ionizing radiation Off. J. European Polish). Communities L 66/16-24 (13.3.1999). [8]. Directive 1999/2/EC of the European Parliament and of the Council of 22 February 1999 on the establish-

LONG-LIVED RADICALS IN IRRADIATED GLUCOSE STUDIED AS A FUNCTION OF STORAGE TIME AND ELEVATED TEMPERATURE Grzegorz P. Guzik, Wacław Stachowicz

Introduction • sucrose crystalline, ultra pure (Sigma Aldrich); The EPR (electron paramagnetic resonance) sig- • Sultan raisins commercially available, class I (ex- nals recorded after radiation treatment of dried perience data – 05.2009; the country of origin fruits containing crystalline sugars are composed – IRAN). Table 1. Maximal solubility of sugars in water and ethyl alcohol at 40o C.

Maximum mass of sugar Volume of H O Volume of EtOH Concentration of final solution Sugar 2 [g] [ml] [ml] [%] Glucose 208 100 - 67.5 Glucose 36 10 50 37.5 Fructose 159 50 - 76.0 Fructose 28 25 50 38.4 Sucrose 100 52 - 64.5 of at least two or more EPR spectra correspond- All three sugars were re-crystallized under proce- ing to several radicals. The identity of these radi- dure proposed by a Belgium group from Ghent cals remains still not defined. University [4]. The procedure compiles a single, The present investigation compiles: slow (about one month) crystallization at room • studies of the decay and transformation of radi- temperature from saturated water (sucrose) or ation-induced EPR signals recorded as a func- ethyl alcohol solutions (glucose and fructose). tion of time and temperature. Earlier experi- Table 1 presents the data on solubility of various ments showed that the EPR signal in dates and figs although stable slowly decays in time [1]; • comparative studies on the effectiveness of IR luminescence in non-irradiated and irradiated sugars by pulsed photostimulated luminescence (PPSL). Stability of sugar born radicals in irradiated sugars has been studied at room temperature by EPR and PPSL methods in the period of 12 months. Good stability and specificity of multicomponent EPR signal is a basis of the present utilization of this signal for identification of radiation exposure in nuclear accidents [2]. The EPR spectra recorded in sugars enable to detect radiation treatment Fig.1. Product of crystallization from MeOH and glucose in dried fruits containing crystalline sugars (CEN standard compared. EPR signals normalized. standard EN 13708:2001 E) [3]. Experimental sugars in water and ethyl alcohol at 40oC after one Materials month [2,3,5]. The following materials were examined: Methods • alpha - D(+)glucose, anhydrous, 96% purity The samples were measured by means of EPR (Sigma Aldrich); and PPSL techniques during heating and storing • D(-)Fructose, 98% purity (Sigma Aldrich); at room temperature: Table 2. Crystallization of sugars from evaporated eluents at room temperature – Sultan raisins. Solution Time from the moment of the first crystallization Boiling point of solvent [oC] Methanol 4 weeks 64.7 Ethanol 6 weeks 78.3 Water 14 weeks 100.0 58 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

Table 3. Identification of extracted crystallites. Predominant product of crystallization Solution for extraction and crystallization sugar defined efficiency of the process [%]*

Methanol pure for analysis by POCh irradiated glucose 0.14

Ethanol 95% purity by Polmos irradiated fructose 0.87 Water redistilled irradiated fructose 0.58 * The efficiency refers to the initial mass of raisins (300 g). • Stored samples were examined every 30 days cence within the range 650-730 nm stimulated by for one year, while the first measurement was the pulses of infra-red light. carried out one day after irradiation. e) Kinetics of signal decay • The samples were heated at 20, 40, 60, 75, 85 The EPR signal intensity was measured every and 95oC, each sample during 10 min. 30 days for 1 year. The kinetics data are presented a) Extraction of sugars from raisins in Fig.2 as a function of total intensity of second Commercial raisins were weighed, grinded, derivative signal measured as a distance between treated with appropriate solvent, filtrated on acti- the signal maximum and minimum vs. time. vated charcoal, concentrated and subsequently The intensity of PPSL signals was recorded at crystallized at room temperature. Comparison for the same time intervals as for EPR experiments. glucose is shown in Fig.1. Each portion of fruit was 300 g. The crystallization proceeds up to 14 weeks (Tables 2 and 3). b) Irradiation The isolated crystallites were irradiated with 1 and 3 kGy of gamma rays and then subsequently measured by the EPR method. High purity fructose and glucose irradiated with the same doses were examined in parallel. The crystals removed from saturated solution were dried and then separated from fine powder by sieving with a screen cup, 85 ml by Sigma. c) EPR measurements Fig.2. The EPR signal intensity decay curves as a function Homogeneous crystallites weighing 100 mg were of time of storage, normalized. D-glucose by Aldrich replaced in two EPR sample tubes (each fraction). crystallized, irradiated. The EPR spectra were recorded with an X-band To study the temperature effect on the stability Bruker ESP 300E spectrometer at room tempera- of EPR signals, the samples were heated for 10 ture. min at 20, 40, 60, 75, 85 and 95oC, respectively. d) PPSL measurements The EPR measurements were carried out at room Samples of pure sugars and sugar extracted temperature one day after heating. All measure- from raisins weighing ca. 2 mg were placed in ments were done under the same conditions – the open, plastic Petri dishes with a diameter of 50 samples were kept closed in EPR sample tubes or mm and measured at room temperature with the in PPSL Petri dishes and stored in the darkness at PPSL system [1,4,6,7]. ambient temperature. Preparation of samples for PPSL measure- f) Refractometric measurements ments followed the analytical procedure included The identification of crystalline product gained in European standard EN 13751:2007. PPSL Irra- from the concentrated raisins extract was achieved diated Food Screening System generates lumines- by comparison of the obtained refraction coeffi- Table 4. Composition of crystalline product obtained from the concentrated extract of raisins. The results of measurements were obtained with an automatic refractometer, Rudolph research J 357.

Predominant product of crystallization Solution refraction coefficient [n] at 20oC for crystallization sugar defined reference sample (average of 30 measurements) Methanol pure for analysis n=1.34645 ± 0.00003 irradiated glucose n=1.34761 ± 0.00003 by POCH D(+) glucose Ethanol 95% purity n=1.34494 ± 0.00005 irradiated fructose n=1.34428 ± 0.00003 by Polmos D(-) fructose n=1.34494 ± 0.00005 Water redistilled irradiated fructose n=1.34311 ± 0.00007 D(-) fructose RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 59 cients [n], which were measured with the use of an automatic refractometer, Rudolph research J 357. The results are presented in Table 4. Results and discussion Irradiated raisins The isolated sugar crystallites extracted from raisins with methanol give rise to the EPR spectrum resembling that of irradiated glucose (Fig.1). A similar observation has been done by other authors [8]. The crystallites extracted from ethanol, in turn, give rise to the EPR spectrum that is identical with that of irradiated fructose (Table 3). The EPR spectrum of crystallites obtained from water solution shows the dominate EPR lines typi- Fig.4. The EPR spectra, normalized; D-glucose irradiated cal of irradiated fructose. The efficiencies of crys- with a dose of 1 kGy recorded 7 days after irradiation and 360 days after irradiation, respectively. tallites obtained from ethanol and water solutions are roughly similar and higher than those obtained probably some transformations of glucose born from methanol. radicals slowly proceed in time. However, the Although the results included in Table 1 show that changes are not so much pronounced as in the water is the best solvent to dissolve sugars, ethanol case of fructose [9]. gives the largest efficiency in the course of crystal- The EPR spectra of D-glucose recorded at lization (Table 3). 20oC and those obtained after heating of sample Irradiated recrystallized sugars in a laboratory water bath at 95oC are compared From the comparison of the decay curves re- (Fig.5). Again, some changes of the EPR spectra corded by the PPSL technique (Fig.3) and those after heating are observed, similarly as in the time- obtained by the EPR method (Fig.2) it is clearly -dependent study. Two outer lines, from the low seen that the annealing of shallow energy traps (PPSL) and the decay of long-lived radicals in glu-

Fig.5. The EPR spectra, normalized; D-glucose irradiated with a dose of 4 kGy recorded at 20 and 95oC, respec- Fig.3. Photoluminescence (PPSL) intensity decay curves, tively. normalized as a function of storage time after irradiation D-fructose by Aldrich recrystallized. and high sides of magnetic field intensity distanced cose proceed similarly as a function of time. The by 4.91 mT, are visibly decreased. stability of both shallow energy traps detected by Conclusion PPSL and long-lived radicals recorded by EPR is The EPR and PPSL kinetic results of irradiated relatively high and after 360 days of observation sugar samples show that radiation-induced radi- remains still measurable. cals and shallow traps as measured by PPSL are In both cases the faster decay in preliminary characterized by a similar stability. The changes of stage of storage (30 days) is probably caused by the multicomponent EPR spectra observed for surface effect, i.e. more effective annealing of D-glucose are less clear than those documented these species (radicals and energy traps) which are with D-fructose [9,10]. However, they testified localized near to the surface of micro-crystallites. some transformation of glucose born radicals, as As seen from the comparison giving above proved in both time-dependent and temperature (Fig.4), the EPR spectra recorded after 360 days studies. The decay of radicals (EPR study) and after irradiation are different from those recorded energy traps (PPSL study) in D-glucose in a func- after 7 days of storage. Two outer lines from the tion of time are analogous as for D-fructose. This low and high sides of magnetic field intensity dis- means it proceeds similarly and after 360 days of tanced by 4.91 mT are visibly decreased. In addi- observation remains still measurable. tion, in the middle part of spectrum (346.11-347.54 Slow decay of D-glucose born radicals has a mT) some considerable change appear. Moreover, practical aspect for identification of irradiated in the range between 349.32-350.36 mT the double food containing sugars. This makes it possible to line observed shows some changes of intensity. identify such food products even one year after The conclusion from the above observation is that radiation treatment. 60 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES References [6]. Sokołowska T., Wiśniewski A.: Nomenklatura węglo- wodanów. Zalecenia 1996. Polskie Towarzystwo Che- [1]. Stachowicz W., Burlińska G., Michalik J., Dziedzic- miczne, Komisja Terminologii, Wrocław 2000 (in -Gocławska A., Ostrowski K.: EPR spectroscopy for Polish). the detection of foods treated with ionising radia- [7]. Raffi J., Agnel J-P.: Radiat. Phys. Chem., 34, 6, tion. In: Detection methods for irradiated foods – 891-894 (1989). current status. Cambridge 1996, pp.23-32. [8]. Pauwels E., Speybroeck V., Waroquier M.: Spectro- [2]. Hutt G., Brodski L., Polyakov V.: Appl. Radiat. Isot., chim. Acta, Part A, 63, 795-801 (2006). 47, 11/12, 1329-1334 (1996). [9]. Guzik G.P., Stachowicz W., Michalik J.: Nukleonika, [3]. EN 13708:2001 E: Foodstuffs – Detection of irradi- 53, Suppl.2, s89-s94 (2008). ated food containing crystalline sugar by ESR spec- [10]. Guzik G.P., Stachowicz W., Michalik J.: The study on troscopy. European Committee for Standardisation, stable radicals produced by radiation in dried fruits Brussels 2001. and sugars by electron paramagnetic resonance spec- [4]. Vanhaelewyn G., Jansen B., Callens F.J., Sagstuen E.: trometry (EPR). In: International Conference on Re- Radiat. Res., 162, 96-104 (2004). cent Developments and Applications of Nuclear Tech- [5]. Vanhaelewyn G., Lahorte P., Proft F., Mondelaers W., nologies. Conference Abstracts. Institute of Nuclear Geerlings P., Callens F.: Phys. Chem. Chem. Phys., 3, Chemistry and Technology, Warszawa 2008, p.128. 1729-1735 (2001).

DETECTION OF RADIATION TREATED DRY PLANT EXTRACTS BY THERMOLUMINESCENCE AND PULSED PHOTOSTIMULATED LUMINESCENCE Katarzyna Lehner, Kazimiera Malec-Czechowska, Wacław Stachowicz, Grzegorz Guzik

Plant extracts are widely used in the food industry measured with the use of computer operated TL (modelling of sensoring features of foodstuffs, diet reader, type TL/OSL, model TL-DA-15, Risø supplements) as well as in cosmetics production National Laboratory, Denmark installed in the (new generation cosmetics). Laboratory. Typically, by employing the TL method However, similarly to other foodstuffs, the prod- to identify irradiation in plant extracts, the main ucts with plant extract content, both fresh and problem lies in effective isolation of suitable dried, at moderate temperature to save their unique amount of silicate minerals from the product as properties, may contain living moulds, putrefactive needed to proceed successfully the classification bacteria as well as eggs and larvae of insects. Dry of tested sample. The aim of present study is to test plant extracts themselves can also be contaminat- whether a much simpler and faster PSL method ed with pathogens. could be adapted for the detection of irradiation In order to avoid the spoilage of dry plant ex- in plant extracts. The samples taken for PSL exami- tracts during storage, ionizing radiation is applied nation without any analytical treatments were eval- as an effective tool capable to kill pathogens and uated with the use of a computer operated PSL to accomplish their preservation. Radiation treat- analyzer SURRC PPSL Irradiated Food Screening ment and distribution of irradiated foods are ac- System [4]. cepted in many countries, but in some are not ac- In the present study a total of 52 samples of cepted. The international trade of irradiated food plant extracts (thyme extract, celery seed extract, is progressing slowly, however, the decision whether artichoke extract, citrus aurentium extract and to accept or not accept irradiated food in the mar- others) have been examined. ket depends on local decision of each country. The reference method was TL as the most reli- The European Parliament and the Council adopt- able for the examination of these kind of food- ed the Directives 1999/2/EC and 1999/3/EC to stuffs. Seven samples among the 16 irradiated harmonize the rules concerning the treatment and samples tested by PSL delivered the reliable posi- trade of irradiated foods in EU countries [1,2]. tive results. This means that the method was ef- The actual list of irradiated food products accept- fective in 43.75% in this case. Eighteen samples ed currently for free distribution in the EU mar- identified properly among the 36 non-irradiated ket comprise dried aromatic herbs, spices and ones delivered reliable positive results. Therefore, vegetable seasonings only. In addition, the irradi- the effectiveness of the PSL method was found ated food has to be adequately labelled. slightly higher and equal to 50%. The data com- As to our knowledge, there are not many data plying the results of PSL and TL measurements in available in the literature on the detection of ir- detail are published elsewhere [5]. radiation in dry plant extracts. Samples of plant Some of plant extracts and multicomponent extracts selected to be examined by the PSL (photo- foodstuffs have been examined by TL and PSL in stimulated luminescence) method in the present our earlier study. The obtained results proved the study were delivered to the Laboratory for Detec- earlier observation that the PSL method has limi- tion of Irradiated Food of the Institute of Nuclear tations arising from low PSL sensitivity of some of Chemistry and Technology (INCT) for testing by plant extracts examined [6-8]. the TL (thermoluminescence) method based on Practical aspect of the present study lies in the PN-EN 1788:2002 whether irradiated or not [3]. chance of the earlier pre-selection of suitable de- The thermoluminescence of mineral fraction was tection method for the examination of plant ex- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 61 tracts delivered to analytical laboratories for test- ment of a Community list of food and food ingredients ing whether irradiated. Having a tested, extensive treated with ionising radiation. Off. J. European Com- list of these products with the annotation which of munities L 66/24-25 (1999). plant extracts can be tested by the PSL method, it [3]. PN-EN 1788 Foodstuffs – thermoluminescence detection of irradiated food from which silicate minerals can will be possible to speed up and simplify the exami- be isolated. European Committee for Standardization, nation procedure which is actually accomplished Brussels 2001. by the TL method only. It should be pointed out [4]. PN-EN 13751 Foodstuffs – detection of irradiated that at present plant extracts are more and more food using photostimulated luminescence. European frequently asked to be tested whether irradiated Committee for Standardization, Brussels 2002. and the problem of obtaining efficient, faster and [5]. Lehner K., Malec-Czechowska K., Stachowicz W., Gu- less expensive than TL, but a still reliable method zik G.P.: Detection of radiation treatment of dry plant of examination is of importance today. extracts by thermoluminescence and pulsed photostimulated luminescence. Comparative study. Nukleo- References nika, in press. [6]. Malec-Czechowska K., Strzelczak G., Dancewicz [1]. Directive 1999/2/EC of the European Parliament and A.M., Stachowicz W., Delincée H.: Eur. Food Res. of the Council of 22 February 1999 on the approxima- Technol., 216, 157-165 (2003). tion of the Member States concerning foods and food [7]. Guzik G.P., Stachowicz W.: Nukleonika, 53, Suppl.1, ingredients treated with ionising radiation. Off. J. Eu- 25-29 (2008). ropean Communities L 66/16-23 (1999). [8]. Alberti A., Corda U., Fuochi P., Bortolin E., Calicchia A., [2]. Directive 1999/3/EC of the European Parliament and Onori S.: Radiat. Phys. Chem., 76, 1455-1458 (2007). of the Council of 22 February 1999 on the establish- RADIOCHEMISTRY STABLE ISOTOPES NUCLEAR ANALYTICAL METHODS GENERAL CHEMISTRY RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 65 MACROCYCLIC COMPLEXES OF 44/47Sc AS PRECURSORS OF RADIOPHARMACEUTICALS Agnieszka Majkowska, Aleksander Bilewicz

Two isotopes of scandium, 47Sc and 44Sc, are per- DOTA was obtained from Macrocyclic Com- spective radinuclides for radiotherapy and diag- pany, the other ligands were synthesized by a reac- nostic imaging. 47Sc decays with a half-life of 3.35 tion of triaza rings with bromoacetic acid accord- days and a maximum β– energy of 600 keV. It also ing to the reported method [1]. All the compounds emits low-energy gamma radiation (Eγ=159 keV) were characterized by NMR spectroscopy and MS suitable for simultaneous imaging. The other spectrometry. 44 scandium radionuclide – Sc (T1/2=3.92 h) is an Stability constants of scandium complexes were ideal β+ emitter for PET diagnosis. It can be pro- determined using the HPLC method. Sc complexes duced by the 44Ca(p,n)44Sc nuclear reaction in were prepared by reacting macrocyclic ligands of 44 46 small cyclotrons or as a daughter of long-lived Ti 0.01 M concentration, respectively, with ScCl3 in 44 44 (T1/2=60.4 y) from a Ti/ Sc generator. For rea- ammonium acetate buffer at pH=6.0. The samples sons of availability, we used in our experiments were heated at 70oC. When the reactions reached 46 the Sc (T1/2=83.8 d) – carrier added nuclide in- equilibrium (8 days), small samples of the solution stead of 47Sc and 44Sc. were injected into an HPLC loop to determine the The goal of our work was to find the best ligands concentrations of the complex and free Sc3+. The for attaching scandium radionuclides with biomol- HPLC data were collected using a Shimadzu Coulter ecules. Due to the formation of thermodynami- device coupled with a radiometric detector. This cally stable and kinetically inert complexes macro- method used a Supelco C18 column and a mobile cyclic ligands were choosen. phase gradient starting from 100% solvent A (0.01 The ionic radius of Sc3+ is 74.5 pm (CN=6), M EDTA) to 100% solvent B (0.01 M EDTA in the ion is chemically similar to Ga3+, In3+, Y3+ and acetonitrile) for 26 min at a flow rate of 1 ml/min. to the heaviest lanthanides. Ligands developed for The stability constants were calculated from the these cations should also be suitable for chelating ratio of Sc-L complex to free Sc peaks measured 47Sc, 44Sc. Since the complexation ability of macro- with the gamma detector. Taking into account cyclic ligands depends on the ionic radius of the stepwise protonation constants of the ligands, the cation, we expected that Sc3+ would form strong stability constants were determined. For compari- complexes with the ligands having a cavity size son, in the same way stability constants of 177Lu similar to the ionic radius of Sc3+: 1,4,7,10-tetraaza- complexes were calculated. The results are pre- cyclododecane-1,4,7,10-tetraacetic acid (DOTA), sented in Table. 1,4,7-triazacyclononane-1,4,7 triacetic acid (NOTA), As shown in Table, Sc3+ forms more stable com- 1,4,7-triazacyclodecane-1,4,7 triacetic acid and plexes with a DOTA ligand than Lu3+. Also com- 1,4,7-triazacycloundecane triacetic acid and ana- plexes of Sc with DOTA are stronger by a few or- logs of NOTA with 10, 11 and 12 atoms of carbon ders of magnitude than the complexes with NOTA in the ring (Fig.1). and [10]ane ligands. The radiochemical yield of

Fig.1. Macrocyclic ligands used for Sc3+ complexation. RADIOCHEMISTRY, STABLE ISOTOPES, 66 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY labelling (5.5 nmol of Sc3+ and 55 nmol of ligands) is very important feature of the radiopharma- for Sc-DOTA is about 99% and it is much higher ceuticals. It was found by the HPLC method that than that for the Sc-NOTA complex (80%). Sc-DOTA complex is more hydrophilic than Table. Stability constants determined by the HPLC method. Lu-DOTA and Sc-NOTA, suggesting different coordination spheres in these complexes (Fig.2). The Metal cation DOTA NOTA [10]ane Sc3+ 27.5 17.6 14.8 Lu3+ 26.7 15.8 12.7

The charges of Sc complexes were determined by paper electrophoresis. The Sc-DOTA complex migrates towards the anode, so the charge is negative. The Sc-NOTA complex stays at the start, therefore the charge is neutral. The charges of the complexes were confirmed by the adsorption studies on cation and anion exchangers. Fig.2. Comparison of lipophilicity of DOTA and NOTA The kinetics of Sc-DOTA and Sc-NOTA com- complexes. plexes were measured at pH=6.0. Complex formation was determined by the instant thin layer cation of Sc is smaller than Lu, so the peak of more chromatography method using ITLC-SG strips hydrated Sc-DOTA complex appears before the developed with the mobile phase: H2O/NH3 (25/1). peak of Lu-DOTA complex. The formation of the Sc-NOTA complex under The presented results show that the macrocyclic these conditions is faster than for the Sc-DOTA complexes of 44Sc and 47Sc radionuclides are at- complex. After 10 min, the equilibrium for Sc-NOTA tractive precursors for diagnostic and therapeutic was reached, while for Sc-DOTA 30 min is needed radiopharmaceuticals. for attaining equilibrium. This part of work was carried out in the frame Sc-DOTA and Sc-NOTA complexes exhibit high of grants from Ministry of Science and Higher stability in human serum and PBS buffer at 37oC. Education (Poland) Nos. DWM/N166/COST/2007 After 120 h of incubation in the serum and PBS, and N204 143 32/3547. more than 97% of Sc-DOTA and Sc-NOTA remains in solution. References Since radiolabelled compounds should be easy [1]. Bevilacqua A., Gelby R.I., Hebard W.B., Zompa L.J.: cleared from the blood via the kidneys, lipophilicity Inorg. Chem., 26, 2699-2706 (1987).

THE SUBSTITUTION OF CHLORIDES IN A RHODIUM-BASED DRUG PRECURSOR BY HUMAN PLASMA THIOLS Seweryn Krajewski, Aleksander Bilewicz

Complexes of rhodium-105 are promising precur- to investigating the distribution, stability and me- sors for radiopharmaceuticals for anti-tumor tabolism under physiological conditions. therapy utilizing the radiation in the destruction In our studies the properties of Rh[1,5,9,13-tetra- 105 + + of cancerous tissues. The Rh demonstrates a num- thiacyclohexadecane-3,11-diol]Cl2 (Rh[S4diol]Cl2 ) ber of desirable nuclear characteristics like high (Fig.1) complex in the presence of two key organic specific activity, low gamma emission (0.320 MeV), thiol antioxidants: glutathione (GSH) and cysteine a decay half-life 35.4 h, high linear energy transfer has been evaluated, prefacing the future experi- and emission of soft β–-particles (0.567 MeV – ments with radioactive rhodium. Both thiols are 70%, 0.247 MeV – 30%) [1]. Moreover, rhodium present in biological fluids in milimolar concen- at +3 oxidation number forms d6 low-spin electronic complexes considered as ones of the most inert. To date, several authors have evaluated the number of tetradent thioether S4- or NS3-structur- ed ligands to be complexed with 105Rh and selected 105Rh[1,5,9,13-tetrathiacyclohexadecane-3,11-diol] as the most suitable drug precursor for radiopharmacy. When studying the pharmacokinetic mechanisms that determinate the fate of drug administer- ed externally to a living organism, the identification of the possible chemical modifications of the sub- Fig.1. Structure of Rh[1,5,9,13-tetrathiacyclohexadeca- + stance in the body might be an essential step prior ne-3,11-diol]Cl2 . RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 67

+ trations. First, Rh[S4diol]Cl2 was prepared by mixing rhodium chloride with 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (at 1:1 molar ratio), both dissolved in a H2O:ACN:EtOH (70:20:10) mixture, and heated at 70oC for 24 h. Next, aqueous solutions of either glutathione or cysteine were added + to Rh[S4diol]Cl2 at 1:1, 2:1 and 5:1 molar ratios respectively and heated at 37oC. Formation and yield of the reaction were estimated by HPLC-RP technique conducted in isocratic conditions and Fig.4. The graph presenting the yield of chloride substitu- UV detection at a wavelength of 225 or 275 nm. tion by glutatione (solid line) or cysteine (broken line) in The absorbance value of Rh[S diol]Cl+ de- the function of time. Both thiol ligands were incubated 4 2 with complex at molar ratios of 1:1 (●), 2:1 (■) and 5:1 (▲). clined after incubation with each of thiol ligands + and new peaks were registered in the time range Incubating the Rh[S4diol]Cl2 with glutathione of 3.0-5.0 min, evidencing the reaction has oc- solution at various molar ratios resulted in few re- curred (Figs.2 and 3). Additionally, no peak of un- action product forms seen at the 4.0-4.5, 3.8-4.0 bound thioeter crown was seen in the chromato- and 3.0-3.6 min intervals (Fig.3), that reflects the gram. Considering the axial position of chloride substitution of one chloride ion, two chloride ions ions in the complex structure as well as their weak and probably binding to 1-2 dimeric glutathione binding to rhodium cation, due to Pearson’s Hard molecules (GSSG), respectively. Increase in the Soft Acid Base (HSAB) concept, we deduced the complex-to-ligand molar ratio was accompanied by a linear growth of chloride substitution efficiency, indicating the first order reaction. The phenomenon of few reaction products detected after chloride substitution by glutathione has been further investigated. The increase of glutathione concentration in the reaction mixture (complex-to-GSH molar ratio of 1:20) at 37oC resulted in a change of the peaks’ values in the time range of 3.0-4.5 min. Continuous heating to 70oC caused the higher peak values in the time range of Fig.2. Two applied chromatograms of Rh[S diol]Cl+ com- 4 2 3.0-3.6 min. plex before (bold line) and after 94 h of incubation with As the chloride substitution in the Rh[S diol]Cl+ cysteine at molar ratio 1:5 (thin line; arrows indicate the 4 2 peaks representing different reaction products). precursor-based drug could significantly affect its pharmacokinetics, we attempted to the effective replacement of chloride anions by glutathione’s or blockage of axial positions in the complex. Two cysteine’s thiol groups in our experiments [2]. aliphatic α,ω-dithiols: 1,8-octandithiol and 1,9-no- However, the slow reaction process of chloride re- nandithiol were selected for this purpose, as they placement by cysteine (60% efficiency after 94 h) are soft bases. Samples for experiments were pre- + suggests the low affinity of the drug precursor to pared by mixing Rh[S4diol]Cl2 with ethanolate so- that amino acid in organism. On the contrary, the lution of dithiol at molar ratio 1:10 and heated at 60oC. Afterwards, the reaction mixture was added to aqueous solution of glutathione at molar ratio 1:5 and heated at 37oC. The results of our experiment have confirmed the substitution of chlorides by dithiols. Two peaks seen in the time range of 4.8-6.0 min in the chromatogram might evidence the existence of two different reaction products, + described by the formula: Rh[S4diol][α,ω-dithiol]x (x=1, 2). The Rh[S4diol] core complexed with two dithiols may prove to be an ideal basis for synthesis + Fig.3. Two applied chromatograms of Rh[S4diol]Cl2 com- of a radiophamaceutical drug for targeted therapy, plex before (bold line) and after 26 h of incubation with where both dithiol ligands would link biomolecules glutathione at molar ratio 1:5 (thin line; arrows indicate of interest. In the experiment with glutathione no the peaks representing different reaction products). changes in the chromatogram (after 4.8 min) were rapid reacting rhodium complex with glutathione at noted proving that all axial positions have been 37oC (86% efficiency after 24 h; Fig.4), together successfully blocked and remained unreactive. The with a relatively high level of glutathione and the present results encourage to continue studies on predominance of its reduced form gluthathione in active rhodium complexes. plasma, might be the cause of the unwanted and noxious changes in the pharmacokinetics of such a References radiopharmaceutical drug [3]. We also consider [1]. Pruchnik F.P.: 45Rh Rhodium in medicine. In: Metal- that the higher pKa value of thiol group from glu- lotherapeutic drugs and metal-based diagnostic agents tathione (≈9.4) than cysteine (≈8.0) may partially – the use of metals in medicine. John Wiley & Sons explain the higher glutathione reactivity [4]. Ltd, England 2005, pp.379-397. RADIOCHEMISTRY, STABLE ISOTOPES, 68 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

[2]. Pearson R.G.: J. Am. Chem. Soc., 85, 3533-3539 [4]. Tajc S.G., Tolbert B.S., Basavappa R., Miller B.L.: J. (1963). Am. Chem. Soc., 126, 10508-10509 (2004). [3]. Bilska A., Kryczyk A., Włodek L.: Postępy Hig. Med. Dośw. (online), 61, 438-453 (2007), in Polish.

176 SEPARATION OF Yb AS YbSO4 FROM A Yb TARGET FOR PRODUCTION OF 177Lu VIA THE 176Yb(n,γ)177Yb → 177Lu PROCESS Aleksander Bilewicz, Krystyna Żuchowska, Barbara Bartoś

Radionuclides with medium energy beta-emission ytterbium and lutetium are neighbouring trivalent and a several day half-life are attractive candidates lanthanides and the mass ratio Yb/Lu in the irradi- for radioimmunotherapy. Among the most prom- ated target can be as high as several thousands, Lu-Yb ising in this category is 177Lu, which has favourable separation is a very difficult task. The extraction or decay characteristics. 177Lu decays with a half-life chromatographic separation of 177Lu from the Yb – target has been described by several of 6.71 d by emission of β -particles with Emax of authors, but the 497 keV (78.6%), 384 keV (9.1%) and 176 keV process is efficient only when the amount of Yb (12.2%) to stable 177Hf. 177Lu has a primary gamma macrocomponent does not exceed 2 mg [8-10]. In ray at 113 keV (6.4%) and 208 keV (11%) that is the present work an alternative, more simple pro- suitable for imaging with a gamma camera. The cess of separation of 177Lu from the macro-amount long half-life of 177Lu enables supply of high quan- of ytterbium, based on reduction of Yb3+ to Yb2+ 177 tities of Lu to places far away from nuclear reac- and precipitation of insoluble YbSO4, was investi- tors. Its applicability has been studied, among others, gated. in the treatment of neuroendocrine [1,2], prostate [3], head and leg [4] and metastic bone [5] cancers. Thanks to the rather large cross-section of 2090 b [6], 177Lu can be directly produced with a relatively high specific activity by neutron activation of 176Lu. Enriched target material is required for this production route since the natural abundance of 176Lu is only 2.6%. The specific activity could be further enhanced considerably by using Lu target enriched in 176Lu [7]. Lutetium oxide enriched in 176Lu up to approximately 60-80% is commercially available. Nevertheless, a minimum amount of stable 176Lu cannot be avoided and might cause some problems concerning the labelling of receptor affine biomolecules, especially when receptor numbers are limited. For this purpose, an alternative production route via neutron capture starting with enriched 176Yb targets has been demonstrated. In this method, an isotopically enriched 176Yb target undergoes a (n,γ) reaction to produce 177Yb, which subsequently decays by β–-emission 177 177 (T1/2=1.9 h) to Lu. The specific activity of Lu produced using this route can be much higher, but only when chemical separation of 177Lu from the Yb target material will be very effective. Given that

Table. Some physicochemical data for ytterbium and lute- Fig.1. Installation for YbSO4 separation: 1 – sodium amal- tium. 177 gam, 2 – precipitated YbSO4, 3 – Lu solution, 4 – mercury. Yb Lu The chemical properties of Yb and Lu are very Electronic [Xe]4f146s2 [Xe]4f145d16s2 similar. As shown in Table, the differences were configuration only observed in the existence of a relatively stable Ionic radius of Ln3+ 86.8 86.1 oxidation state +2 for Yb and the high solubility [pm] of metallic Yb in mercury. Unlike in lutetium, due Ionic radius of Ln2+ to the fullfiled 4f subshell, the oxidation state +2 114 - [pm] is relatively stable for ytterbium. The properties of 2+ 3+ Yb are very similar to group 2 metal cations such Eo Ln /Ln [V] -2.267 -2.255 as Ca2+ and Sr2+, and therefore Yb2+ forms inso- 3+ 2+ Eo Ln /Ln [V] 1.05 - luble sulphate, as form Group 2 elements. Sodium amalgam, which is one of the strongest reducing Solubility in Hg high low agents, was used for reduction of Yb3+ to Yb2+. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 69 The separation process was performed in an If expensive isotopically enriched 176Yb is used apparatus presented in Fig.1. Sample of 57 mg in the irradiations, the target material should be Yb2O3 was dissolved in 6 ml of H2SO4 and the so- recovered. The YbSO4 is unstable in air because 177 2+ 3+ lution was spiked with Lu. Next, 5 M of sodium Yb oxidizes slowly to Yb . The YbSO4 can be amalgam was slowly added to the solution. After easily converted to the oxide by heating in air at adding the drops of sodium amalgam to the solu- 300oC for several hours during which the residual 3+ tion of Yb , a green precipitate of YbSO4 was mercury traces are eventually removed. The re- formed according to the reaction: covery of ytterbium is nearly quantitative. This 32+−+ Yb++→+ Na(Hg) SO44 YbSO Na material can be used for subsequent irradiations. 3+ In these conditions Lu remains in solution. Since the Yb2O3 target contains some traces of After separation of YbSO4, the concentration of lutetium before irradiation, inactive separation of ytterbium in solution was measured. The depend- traces of lutetium by the above-described proce- ence of separation efficiency on the added amal- dure is recommended. gam is shown in Fig.2. Production batches of several hundred mCi to several Ci 177Lu radioisotope separated from 50 mg enriched 176Yb target activated in a nuclear reactor of neutron flux 2x1014 n.cm–2.s–1 can be achieved using the above-mentioned separation technique. Further efficient chromatographic separation of carrier-free 177Lu from 1 mg of Yb is relatively easy and is described in several papers [8-10].

References [1]. Nayak T.K., Atcher R.W., Prossnitz E.R., Norenberg J.P., Jeffrey P.: Nucl. Med. Biol., 35, 673 (2008). [2]. van Essen M., Krenning E.P., Kam B.L., Vallabhajosu- la S., Goldsmith S., Milowsky M.I., Morris M.: Eur. J. Nucl. Med. Mol. Imaging, 35, 743 (2008). [3]. Bander N.H., Nanus D.M., Tagawa S.S., Vallabhajosu- la S., Goldsmith M., Milowsky M., Morris M.J.: J. Urology, Suppl., 179, 253 (2008). [4]. Tijink B.M., Neri D., Leemans C.R., Budde M., Din- kelborg L.M., Stigter-Van Walsum M., Zardi L.: J. Nucl. Med., 47, 1127 (2006). Fig.2. Dependence of ytterbium separation efficiency on [5]. Majkowska A., Neves M., Antunes I., Bilewicz A.: the added sodium amalgam. Complexes of low energy beta emitters 47Sc and 177Lu with zoledronic acid for bone pain therapy. Appl. The precipitation of YbSO4 was maximal after Radiat. Isot. (2009), in press. adding 15 mmole of Na (which corresponds to 4.5 [6]. Firestone R.B., Shirley V.S., Baglin C.M., Chu S.Y.F., ml of amalgam with Na concentration 3.5 M). About Zipkin J.: Table of isotopes. 8th ed. Wiley, New York 97% of ytterbium was precipitated from the aque- 1996. ous solution. [7]. Zhernosekov K.P., Perego R.C., Dvorakova Z., Hen- Studies of the dependency of YbSO precipita- kelmann R., Turler A.: Appl. Radiat. Isot., 66, 1218 4 (2008). tion on the concentration of H2SO4 indicate that [8]. Lahiri S., Nayak D., Nandy M., Das N.R.: Appl. 2–5 M H2SO4 is optimal for efficient separation of Radiat. Isot., 49, 911 (1998). 177 Yb. Unfortunately a small amount of Lu co-pre- [9]. Balasubramanian P.S.: J. Radioanal. Nucl. Chem., cipitated with YbSO4. In the process of YbSO4 185, 305 (1994). precipitation about of 25% of total 177Lu is co-pre- [10]. Hashimoto K., Matsuoka H., Uchida S.: J. Radioanal. cipitated with YbSO4. Nucl. Chem., 255, 575 (2003).

DESIGN OF NEW PET RADIOPHARMACEUTICALS BASED ON ACYCLIC COMPLEXES OF 89Zr Magdalena Połosak, Aleksander Bilewicz

The interest in radioimmunoconjugates for tumour sion computed tomography) and may provide more therapy is growing. In the case of cancer therapy precise quantitative data the use of PET for dosi- using monoclonal antibodies or fragments labelled metric studies is preferred. Antibodies have been with  β+ emitters, it is important to measure the labelled with 18F and 68Ga however, the drawback time course of deposition of antibodies in tissue of these radionuclides is their short half-life of or tumor in order to calculate internal radiation 110 and 68 min, respectively. Since the clearance dosimetry and plan radiotherapy. Because PET time of radioimmunoconjugates is relatively high, (positron emission tomography) technique shows good target to blood ratios are not achieved within better resolution than SPECT (single proton emis- 24 h post administration. As a potential PET sur- RADIOCHEMISTRY, STABLE ISOTOPES, 70 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY rogate for 90Y and 177Lu, the positron emitter 89Zr droxybenzyl)ethylenediamine-N,N-diacetic acid is most promising because of its convenient half-life (HBED), a more acidic octadentatate ligand with 89 (t1/2=3.27 d) and availability. Levels of Zr suffi- hydroxypirydinones groups LICAM and for com- cient to provide >50 clinical doses of 89Zr-labelled parison the desferrioxamine (DFO) ligand (Fig.). mAbs could be produced from a single irradiation For reasons of availability of 89Zr, part of the and at a reasonable cost. studies were performed using longer lived 89Zr 88 181 88 For labelling of antibodies, macrocyclic ligands analogs, Zr and Hf. Zr (t1/2=83.4 d) was ob- cannot be used, because complexation reaction retained in 89Y(p,2n)88Zr nuclear reaction at the In-

Fig. Ligands used for 89Zr and 181Hf complexation. quires elevated temperature. Antibodies as pro- stitute of Nuclear Physics (Kraków, Poland) and teins are thermo-sensitive and instead of elevated 181Hf by neutron irradiation of natural Hf target temperature should be applied longer reaction in a nuclear reactor at Świerk. The results were times and high ligand to antibody ratio. In per- re-enact with real 89Zr in Dresden-Rossendorf formed studies [1,2] 89Zr was bounded to biomol- PET-Zentrum. 89Zr was obtained in 89Y(p,n)89Zr ecules using a desferrioxamine ligand. This ligand nuclear reaction in 18/9 MeV CYCLONE. A piece is rather large (M=560.7 g/mol), relatively expen- of yttrium foil (m=95 mg, thickness – 0.15 mm, sive and forms hexadentate complexes with Zr4+ size –25 mm x 25 mm) was irradiated. After irra- (Zr4+ in complexes usually exhibits CN=8). diation, the yttrium target was dissolved in 2 M The aim of our work is to find suitable acyclic HCl. The separation of 89Zr from the Y target was low molecular weight chelators for effective bind- performed using a cation-exchange column (col- ing of 89Zr to biomolecules. For the studies, we umn packing – AccellTM Plus CM Cation Exchange, have chosen the following acyclic ligands: diethyl- Media 300 Å). After adsorption, the 89Zr was elut- enetriaminepentaacetic acid (DTPA), N,N-bis(2-hy- ed with 0.5 M oxalic acid. The solution was evapo- Table 1. Complexation of 89Zr with DFO, DTPA and HBED ligands. Percent of complexation after Ligand Zr:ligand molar ratio 30 min 1 h 3 h 5 h 24 h DFO 1:1 0 1.1 8.6 10 7 DTPA 1:2 100 100 100 100 98.4 1:5 100 100 100 100 99.2 1:10 100 100 100 100 98.6 HBED 1:2 93.8 92.3 94.6 100 91.4 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 71 rated and the dry spot of 89Zr oxalate was dissolved The results presented in Tables 1 and 2 show in 0.5 ml of 0.04 M HCl. The same procedure was that complexation of 89Zr and 181Hf with DTPA used for isolation of 88Zr. In the case of 181Hf, the and HBED is fast and very effective. In the case of 89 neutron irradiated HfO2 target was dissolved in Zr complexation with DTPA 100% of labelling hot concentrated H2SO4, evaporated to dryness was achieved in 30 min, even with 1:2 molar ratio. and dissolved in 0.1 M HCl. Complexation of 89Zr and 181Hf with DFO was Table 2. Complexation of 181Hf with DFO, DTPA and HBED ligands.

Ligand Hf:ligand molar ratio Percent of complexation after 30 min 1 h 3 h 5 h 24 h DFO 1:5 93.45 91.74 89.84 87.12 72.94 1:10 91.85 73.84 87.19 79.04 - 1:50 67.99 - 77.67 78.82 72.75 1:100 81.35 70.94 72.41 61.87 61.87 DTPA 1:5 100 80.75 98.98 91.30 93.99 1:10 92.77 95.96 98.36 98.05 98.52 1:50 98.61 99.57 99.54 99.49 99.69 1:100 99.56 99.28 99.57 99.55 99.50 HBED 1:5 94.04 94.85 90.45 95.69 74.34 1:50 98.82 99.06 98.68 95.03 98.52

The complexes of 89Zr and 181Hf were synthe- much worse, especially in the case of carrier free sized in aqueous solutions at pH=4 in various 89Zr. The preliminary results of our studies indi- metal to ligand ratio. Complexes formation after: cate that both DTPA and HBED ligands could be 30 min, 1 h, 3 h, 5 h and 24 h was determined by used instead of DFO as chelators for 89Zr radio- the instant thin layer chromatography (TLC) isotope. method using ITLC-SG strips developed with the References mobile phase: n-ButOH/CH3COOH/H2O(2:1:1) or MeOH/CH3COONH4(1:1). Labelling yields [1]. Michael M.R., Zalutsky R.: Clin. Cancer Res., 12, were determined by measuring the radioactivity 1958 (2006). using a thin layer linear analyzer. In both solvents [2]. Perk L.R., Visser G.W.M., Vosjan M.J.W.D., Stigter-van 4+ 4+ uncomplexed Zr and Hf remained at the start Walsum M., Tijink B.M., Leemans C.R., van Dongen of the TLC-plates, while complexed zirconium and G.A.M.S.: J. Nucl. Med., 46, 1898 (2005). hafnium migrate to the front. The efficiencies of the complexation are presented in Tables 1 and 2.

PROCESSING OF GENERATOR-PRODUCED 44Sc FOR MEDICAL APPLICATION Marek Pruszyński, Natalia S. Loktionova1/, Frank Rösch1/ 1/ Institute of Nuclear Chemistry, Johannes Gutenberg University of Mainz, Germany

Positron emission tomography (PET) is recently studies. These radionuclides are cyclotron-pro- the most developing part of nuclear medicine. It is duced and because of their short half-lives, label- fast and high-resolution imaging method that offers ling of biomolecules and application of obtained higher sensitivity and quantification over the single radiopharmaceuticals have to be performed in the photon emission computed tomography (SPECT) place of production. It means that hospitals have [1]. The most commonly used positron emitting to be equipped with accelerators. radionuclide is 18F, and 18F-labelled fluorodeoxy- The other way to support hospitals with the PET glucose (FDG) is the dominating PET tracer in radionuclides is the use of generators. The decay oncology [2]. The use of [18F]FDG is supported of long-lived mother nuclide to the short-lived by the supply of 18F through hundreds of cyclo- PET tracer daughter provides an inexpensive and trons located in academic centers and industrial convenient alternative. Recently, the most popular settings worldwide. Other positron emitting radio- PET generator and the only one, which is commer- 11 13 68 68 nuclides, e.g. C (T1/2=20.4 min), N (T1/2=10 min), cially available, is the Ge/ Ga generator. It pro- 15 68 O (T1/2=2 min) etc. could be also used in oncologic vides the Ga (T1/2=68 min) from the long-lived RADIOCHEMISTRY, STABLE ISOTOPES, 72 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

68 Ge (T1/2=270.8 d). A variety of mono- and bifunctional chelators (BFC) have been developed which allow immobilization of 68Ga3+ and convenient coupling to biomolecules. Also many 68Ga radiopharmaceuticals have been used so far for imaging of bone, blood pool, lung, vascular pool, and tumor [3,4]. The short half-life of 68Ga has advantages and disadvantages. It permits application of suitable 68Ga activities, while maintaining an acceptable radiation dose to the patient. But it also requires a rapid method of milking and labelling for efficient utilization. The short half-life of 68Ga also limits applications of 68Ga-labelled tracers to fast biological processes. Application of radionuclide with longer half-life enables also labelling of macromolecules, which require longer time to reach 44 the target. One of these isotopes is Sc (T1/2=3.93 h), a positron emitter (β+ branching 94.3%, EC=4.6%), which is of potential interest for clinical PET. Also, as a β+ analogue could be applied for planning and dosimetric calculations in endo- radiotherapy based on the β– emitting 47Sc radiopharmaceuticals [5]. The aim of this work was to develop a method to concentrate 44Sc solution received from a generator and to reduce the rest of 44Ti amount, both in the interest of product purity and in conservation of the expensive source material. The developed system had to be efficient and simple to perform in order to minimize the possibility of mal-operation that might result in the gross contamination Fig. Scheme of the post-elution processing of 44Sc-eluates of the final product. A strategy for such an approach and generator-associated syntheses of 44Sc-labelled com- relayed on the direct transfer of the initial genera- pounds. tor eluate to a cation exchanger. glass vial – ready for labelling with BFC-peptides. 44Sc was available from a previously prepared The column was reconditioned with 1 mL of 4 M 44 44 Ti/ Sc generator working in “reverse” elution HCl and 1 mL of H2O. The scheme of generator mode and eluted with a 20 mL mixture of 0.005 M with post-elution processing is presented in Fig. H2C2O4/0.07 M HCl [6]. In the first step, several In conclusion, a rapid, simple, and chemically strong acidic cation-exchange resins were investi- efficient post-elution processing of generator-pro- gated: AG 50W-X4 (200-400 mesh), AG 50W-X8 duced 44Sc was developed on the basis of cation-ex- (200-400 mesh) and Chelex 100 (200-400 mesh). change chromatography utilizing acetic buffer as The best retention of 44Sc was observed on the AG an eluant. 50W-X8 resin and this ion exchanger was used in further studies. In the second step, several solutions References at various volumes and concentrations were used 44 [1]. Rahmim A.: Iran. J. Nucl. Med., 14, 1-20 (2006). to elute retained Sc from the cationic column. The [2]. Lucignani G.: Eur. J. Nucl. Med. Mol. Imaging, 35, 44 best recovery elution of Sc was obtained when 2 209-215 (2008). mL of acetic buffer was used. [3]. Al-Nahhas A., Win Z., Szyszko T., Singh A., Khan S., In the third step, a micro-chromatography col- Rubello D.: Eur. J. Nucl. Med. Mol. Imaging, 34, umn was prepared and filled with AG 50W-X8 1897-1901 (2007). (200-400 mesh) resin and directly coupled to the [4]. Pettinato C., Sarnelli A., Di Donna M., Civollani S., 44Ti/44Sc generator via tubing. The 44Sc was eluted Nanni C., Montini G., Di Pierro D., Ferrari M., Maren- with a 20 mL mixture of 0.005 M H C O /0.07 M go M., Bergamini C.: Eur. J. Nucl. Med. Mol. Imaging, 2 2 4 51, 72-79 (2008). HCl and transferred on-line through a micro-chro- [5]. Rösch F, Knapp F.F.: Radionuclide generators. In: matography column where was retained while the Handbook of nuclear chemistry. T.4. Kluwer Academic 44 minimal amount of Ti breakthrough passed the Publishers, The Netherlands 2003, pp.81-118. column. The column was washed with water and 2 [6]. Filosofov D.V., Loktionova N.S., Rösch F.: Annual mL of acetic buffer and was passed slowly through Report 2007, Institute of Nuclear Chemistry. Univer- the column and the 44Sc eluate was collected in a sity Mainz, 2008. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 73 SYNTHESIS AND STRUCTURE OF TETRAKIS(TROPOLONATO)TIN(IV) Krzysztof Łyczko, Krzysztof Woźniak1/ 1/ Department of Chemistry, University of Warsaw, Poland

Tropolone (2-hydroxy-2,4,6-cycloheptatrien-l-one), in which the polymeric compound [Pb(trop)(CF3SO3) hereafter abbreviated as Htrop, is a non-benze- (H2O)]n was crystallized [5]. However, for tin(II) noid compound with aromatic 6 electron system triflate yellow crystals of [Sn(trop)4]·CH3OH were containing a ring of seven carbon atoms and two grown after a few days. This shows that under such neighbouring functional groups: carbonyl and hy- conditions tin(II) is oxidized to tin(IV), what re- droxyl. The tropolonato anion (trop–), formed after sults in the formation of the tetrakis(tropolonato) dislodgement of a proton from the OH group, is a tin(IV) complex. The structure of this compound bidentate ligand forming a five-membered chelate was determined by the single-crystal X-ray dif- ring upon attachment to a metal ion. fraction method using a KUMA KM4 CCD dif- There are a few sets of structural data on tin(IV) fractometer. compounds with tropolone, such as: [Sn(trop)3Cl] The structure of tin(IV) complex with tropolo- – ·CH3OH, [Sn(trop)3OH] [1], [Sn(trop)2Cl2] [2], ne consists of a metal ion chelated by four trop [Sn(trop)4]·CH2Cl2 [3], [Sn(trop)2(CH3)2] and ions (Fig.). In the title compound the tin(IV) ion [Sn(trop)(CH3)3] [4]. The homoleptic complex of has a coordination number eight with the Sn–O tin(IV) ion and tropolonato ligands was synthe- bond distances in the range 2.135(10)-2.206(10) sized by heating at 250-300oC a solid mixture of Å. The mean Sn–O bond length is equal to 2.169 tropolone and a precipitate, obtained in the reac- Å, the same as that for [Sn(trop)4] described pre- tion of tin(IV) chloride with tropolone in a metha- viously [3]. The bite angles in the chelate are equal nol solution at 60oC in the presence of triethyl- to 71.77(4), 71.75(4), 72.29(4) and 71.81(4)o, with amine [3]. The final product was recrystallized the mean value of 71.90o. The geometry around the from dichloromethane. tin centre in the presented structure can be con- In this work another simpler way for prepara- sidered as one of three types: a distorted square tion of the [Sn(trop)4] compound has been devel- antiprism, an irregular bicapped trigonal prism or oped. In this method, tropolone (0.81 mmol) was a distorted dodecahedron [6]. It is difficult to de- added to the solution of tin(II) triflate (0.22 mmol) cide which coordination polyhedron is the most in methanol (1.0 ml). We expected to obtain a tro- probable. However, Kira et al. found that the ar- polonato-tin(II) species, like in the case of water/ rangement around tin(IV) ion is best described as methanol solution of lead(II) triflate and tropolone, a bicapped trigonal prism distorted toward a dodecahedron [3]. Besides the title compound only a few complexes in which tin(IV) ion coordinates eight oxygen atoms have been structurally characterized till now. These are: tetrakis(nitrato)tin(IV), [Sn(NO3)4] (1) [7], tetrakis(acetato)tin(IV), [Sn(CH3CO2)4] (2) [8], tetrakis(N,N-Diisopropylcarbamato)tin(IV), [Sn(O2CN-i-Pr2)4] (3) [9], tetrakis(N-Nitroso-N-phe- nylhydroxylaminato)tin(IV), [Sn(O2N2Ph)4] (4) [10] and tetrakis(N,N-Diethylcarbamato)tin(IV), [Sn(O2CNEt2)4] (5) [11]. The Sn–O distances are in the range 2.139-2.195 Å for complex (1), 2.130-2.296 Å for (2), 2.126-2.219 Å for (3) and 2.156-2.209 Å for (5). In compound (4) there are four Sn–O bonds of the length 2.144 Å and four bonds of the length 2.185 Å. All these distances are similar to those we observed in the tetrakis(tropolonato)tin(IV) complex. References [1]. Park J.J., Collins D.M., Hoard J.L.: J. Am. Chem. Soc., 92, 3636-3644 (1970). [2]. Denekamp C.I.F., Evans D.F., Slawin A.M.Z., Wil- liams D.J., Wong Ch.Y., Woollins J.D.: J. Chem. Soc., Dalton Trans., 2375-2382 (1992).

Fig. Molecular structure of [Sn(trop)4]·CH3OH. Select- [3]. Kira M., Zhang L.Ch., Kabuto C., Sakurai H.: Orga- ed bond lengths [Å] and angles [o]: Sn–O(1) 2.1748(10), nometallics, 17, 887-892 (1998). Sn–O(2) 2.1655(10), Sn–O(3) 2.1559(11), Sn–O(4) [4]. Deak A., Kiraly P., Tarkanyi G.: Dalton Trans., 2.1811(10), Sn–O(5) 2.1920(10), Sn–O(6) 2.1350(10), 234-239 (2007). Sn–O(7) 2.1420(10), Sn–O(8) 2.2057(10), O(1)–Sn–O(2) [5]. Lyczko K., Starosta W., Persson I.: Inorg. Chem., 46, 71.77(4), O(3)–Sn–O(4) 71.75(4), O(5)–Sn–O(6) 72.29(4), 4402-4410 (2007). O(7)–Sn–O(8) 71.81(4). The non-hydrogen atoms are [6]. Muetterties E.L., Guggenberger L.J.: J. Am. Chem. shown as the 50% probability ellipsoids. Soc., 96, 1748-1756 (1974). RADIOCHEMISTRY, STABLE ISOTOPES, 74 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

[7]. Garner C.D., Sutton D., Wallwork S.C.: J. Chem. [10]. Parkanyi L., Kalman A., Deak A., Venter M., Haiduc Soc. A, 1949-1954 (1967). I.: Inorg. Chem. Commun., 2, 265-268 (1999). [8]. Alcock N.W., Tracy V.L.: Acta Crystallogr. B, 35, [11]. Horley G.A., Mahon M.F., Molloy K.C., Haycock 80-83 (1979). P.W., Myers C.P.: Inorg. Chem., 41, 5052-5058 [9]. Abis L., Dell‘Amico D.B., Calderazzo F., Caminiti R., (2002). Garbassi F., Ianelli S., Pelizzi G., Robino P., Tomei A.: J. Mol. Catal. A: Chem., 108, L113-L117 (1996).

“2+1” TRICARBONYLTECHNETIUM(I) AND -RHENIUM(I) COMPLEXES WITH N-METHYL-2-PYRIDINECARBOXYAMIDE AND β-ALANINE tert-BUTYL ISOCYANIDE – POTENTIAL PRECURSORS OF RADIOPHARMACEUTICALS Ewa Gniazdowska, Leon Fuks, Przemysław Koźmiński, Józef Mieczkowski1,2/, Jerzy Narbutt 1/ Department of Chemistry, University of Warsaw, Poland 2/ WAT Military University of Technology, Warszawa, Poland

Progress in radiopharmaceutical chemistry in- ponents. The experimental details are available volves searching for new tissue-specific radiophar- elsewhere [7]. maceuticals for both diagnosis and therapy. A All the species dealt with in the following text have great interest in stable technetium and rhenium been specified in Table 1. complexes with organic ligands has been observed HPLC analyses carried out at different time within the last two decades [1,2]. 99mTc is the radio- intervals after synthesis of the 99mTc-precursor, 1a, nuclide of choice in diagnostic nuclear medicine show that 1a slowly decomposes by re-oxidation 99m – because of its ideal nuclear properties (Eγ,max=140 to Tc O 4 in the deareated reaction mixture (pH keV, t1/2=6 h) and its availability from commercial ~11). Detectable amounts of pertechnetate (ca. 99Mo/99mTc generators [3]. The β–-emitting radio- 6%) were observed after 4 h. The rhenium precur- 186 188 – nuclides of rhenium-technetium congener: Re sor, 1b, is somewhat more stable, and the ReO4 188 (Eγ,max=1.07 MeV, t1/2=90 h) and Re (Eγ,max=2.12 anion could be detected in the reaction mixture MeV, t1/2=17 h) are the logical choice for thera- only after 6 h. A similar behaviour was observed for peutic applications [3,4]. the complexes 2a and 2b. The detectable amounts 99m – 188 – The aim of the present work, the extension of of Tc O 4 and ReO4 were found in the neutral –3 PhD studies of Mrs M. Łyczko of this Laboratory 10 M aqueous solution of L1 after 1.5 and 7 h, [5,6], was to synthesize on a n.c.a. scale fac-tricar- respectively. bonyltechnetium/rhenium complexes which consist Substitution of the water molecule in 2 by the 6 of a low-spin d M(I) cation, three strongly bound isonitrile ligand L2 makes the technetium and rhe- carbonyl molecules, bidentate N-methyl-2-pyridine- nium complexes much more stable. No distinct carboxyamide and monodentate tert-butyl 3-isocy- changes in chromatograms of 3a, either HPLC or anopropionate (β-alanine tert-butyl ester isocya- TLC, were detected within several hours. This in- 99m – nide). The latter compound, a bifunctional ligand, dicated that neither Tc O 4 (to be detected by is a model of radiopharmaceutical linker to a bio- HPLC) nor TcO2 (to be detected by TLC) were molecule. The complexes were tested as potential formed within the time necessary for medical pro- radiopharmaceutical precursors; in particular their cedures. The rhenium compounds (1b, 2b and 3b) physicochemical properties important for radio- appeared more stable than their technetium ana- pharmacy were studied, i.e. lipophilicity and sta- logues. Figure 1 shows some related HPLC chro- bility under conditions of challenge experiments matograms of the technetium compounds studied: 99m – with histidine, cysteine and the blood serum com- Tc O 4, 1a, 2a and 3a. Paper electropherograms of four complexes Table 1. Numbering of the species studied. 2a, 2b, 3a and 3b, isolated by preparative HPLC, Complex Symbol consist of only one single peak each. The shifts of these peaks toward the cathode agree with the ex- N-methyl-2-pyridinecarboxyamide L1 pected positive charges of the complexes. tert-butyl-3-isocyanopropionic acid L The distribution of chemical species between 2 two liquid phases in the octanol/water system is a 99m I + fac-[ Tc (CO)3(OH2)3] 1a common measure of their lipophilicity, in particular the values of their partition coefficients, P, are fac-[188ReI(CO) (OH ) ]+ 1b 3 2 3 being used [8]. The values of logP for [99mTc]- or 99m I + 188 [ Tc (CO)3(OH2)L1] 2a [ Re]-complexes, determined under standard conditions [9] in the systems n-octanol/0.9% NaCl [188ReI(CO) (OH )L ]+ 2b 3 2 1 and n-octanol/aqueous PBS buffer are listed in 99m I + [ Tc (CO)3(OH2)L1L2] 3a Table 2. As expected, when a lipophilic molecule of [188ReI(CO) (OH )L L ]+ 3b 3 2 1 2 tert-butyl 3-isocyanopropionate replaces the water RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 75

99m 99m – Fig.1. HPLC chromatograms of Tc species immediately after syntheses: [ Tc O 4], 1a, 2a and 3a (HPLC: Supelcosil LC-C18 column, 4.6 mm x 250 mm). + 99m 188 molecule in [M(CO)3(H2O)L1] , the formed com- The stability of the [ Tc]- and [ Re]-complexes 3a and 3b are more strongly lipophilic than plexes isolated by preparative HPLC was examin- their substrates 2a and 2b (Table 1). At present, ed in challenge experiments, i.e. in the presence of we are not able to explain why the logP3b value for an extent of one of strongly competitive ligands – the (n-octanol/PBS buffer system) is much lower amino acids appearing in nature – histidine and Table 2. LogP values of the investigated complexes.

Tc-complexes Re-complexes n-octanol/0.9% n-octanol/PBS buffer n-octanol/0.9% n-octanol/PBS buffer NaClaq pH 7.4 NaClaq pH 7.4 + [M(CO)3L1(H2O)] , 2 0.43 ± 0.01 0.56 ± 0.05 0.76 ± 0.02 0.79 ± 0.02 + [M(CO)3L1L2] , 3 1.23 ± 0.02 1.25 ± 0.03 1.24 ± 0.04 0.87 ± 0.03 than the other logP3 values. To answer this ques- cysteine. The results are presented in Table 3, and tion we shall analyze the data comprising a greater some selected values are shown in Fig.2 (the dia- number of similar Tc- and Re-complexes. grams for the 99mTc-complexes present the content

Fig.2. Cysteine (left) and histidine (right) challenge experiments; the percentage of intact 99mTc- and 188Re-complexes remaining after various incubation periods at 37oC. RADIOCHEMISTRY, STABLE ISOTOPES, 76 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY of species which remain intact after incubation in The more stable 3a molecule decomposed only 10–2 M solutions of the amino acids, while for the in part (though also rather rapidly): in ca. 58% for more stable 188Re-complexes the data refer to the cysteine and ca. 44% for histidine solutions of 10–2 amino acid solutions of the concentration by ten M. However, in the 10–1 M cysteine solution 3a times higher). decomposed quickly and almost completely. The Remarkable differences in the stability of parti- analogous rhenium complexes, 2b and 3b, are cular complexes have been observed. The 2a under- more stable. The 3b complex is well stable (>90%) goes fast ligand exchange, even in less concentrated for at least 20 h even in the more concentrated 10–2 M amino acid solutions. The HPLC chroma- cysteine/histidine solutions. Stability of the isolat- Table 3. The percentage of intact 99mTc- and 188Re-complexes in challenge experiments with excess of cysteine or histidine at 37oC.

99m 188 Histidine/cysteine % of intact Tc- and Re-complexes after Compounds concentration 30 min ~3 h ~20 h cyst – 10–2 M 42.6 19.1 0 99m + [ Tc(CO)3L1(H2O)] 2a hist – 10–2 M 38.8 19.7 0

–1 Technetium cyst – 10 M 10.0 1.2 0 complexes cyst – 10–2 M 42.8 41.8 41.5 99m + [ Tc(CO)3L1L2] 3a hist – 10–1 M 37.5 32.8 29.8 hist – 10–2 M 57.3 56.0 55.5 cyst – 10–1 M 51.0 49.2 48.8 cyst – 10–2 M 69.0 61.0 57.6 [188Re(CO) L (H O)]+ 2b 3 1 2 –1 Rhenium hist – 10 M 42.4 23.6 17.3 complexes hist – 10–2 M 63.9 53.8 51.9 cyst – 10–1 M100 100 100 188 + [ Re(CO)3L1L2] 3b hist – 10–1 M93.3 90.3 90.5 tograms show the appearance of large amounts of ed 3a was also studied by HPLC in rat serum at transchelation by-products: ca. 60% of the initial 37oC. The chromatograms obtained at various in- amount of 2a within the first 30 min, over 80% cubation periods have shown the existence of only after 3 h, and full decomposition of 2a after 20 h. one radioactive species characterized by the re- In still less concentrated amino acid solutions 2a is tention time corresponding to 3a (Fig.3, left). In 99m more stable. The amount of Tc(CO)3(histidine) the course of the experiment, a part of 3a inter- complex formed after incubating 2a in 10–3 M his- acted with serum components and precipitated as tidine solution does not exceed 25% of the initial labelled proteins. Measurements of radioactivity amount of 2a after 30 min and only slightly more of both supernatant and precipitate (protein) frac- after 2 h [6]. tions indicated that less than 30% of 3a had been

Fig.3. HPLC chromatograms of 3a after different incubation periods (left), and the percentage of intact complex (right), in rat serum medium. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 77 bonded by serum components after 48 h (Fig.3, [5]. Narbutt J., Zasepa-Lyczko M., Czerwinski M., Schibli 99m + R.: Tricarbonyltechnetium(I) complexes with neutral right). The percent of intact [ Tc(CO)3L1L2] complex in rat serum medium dropped from 93% bidentate ligands – N-methyl-2-pyridinecarboamide after 1 h to 69% after 48 h of incubation (Fig.3, and N-methyl-2-pyridinecarbothioamide. Experimental and theoretical studies. In: Trends in radiopharmaceu- right). ticals (ISTR-2005). Proceedings of an International Tricarbonyltechnetium(I) and tricarbonylrhen- Symposium organized by the International Atomic ium(I) complexes with bidentate N-methyl-2-pyri- Energy Agency and held in Vienna, 14-18 November dinecarboxyamide and monodentate isocyanide 2005. IAEA, Vienna 2007, vol.1, pp.367-374. Proceed- ligands may be considered as promising precur- ings series. sors of radiopharmaceuticals. [6]. Łyczko M., Narbutt J.: In vitro stability of tricarbonyl- The authors acknowledge Tyco-Mallincrodt technetium(I) complexes with n-methyl-2-pyridine- (Petten, the Netherlands) for the gift of the Isolink carboamide and N-methyl-2-pyridinecarbothioamide kits, Biker (Warszawa, Poland) for continuous do- – histidine challenge. In: INCT Annual Report 2006. nation of the 99mTc radionuclide and the Institute Institute of Nuclear Chemistry and Technology, War- szawa 2007, pp.71-72. of Atomic Energy, Radioisotope Centre POLATOM [7]. Fuks, L., Gniazdowska, E., Kozminski, P., Mieczkow- (Otwock-Świerk, Poland) for supplying us with the ski, J., Narbutt, J.: “2+1” tricarbonyltechnetium(I) and 188 188 W/ Re generator. tricarbonylrhenium(I) complexes with N-methyl-2-pyridinecarboxyamide and β-alanine tert-butyl isocyanide References - potential precursors of radiopharmaceuticals. To be [1]. Technetium and rhenium in nuclear medicine and published. chemistry. Eds. U. Mazzi, M. Nicolini. SGEditoriali, [8]. Medicinal chemistry, principles and practice. Ed. F.D. Padova 1995, 1999, 2002, 2006. King. Thomas Graham House, Cambridge 1994, pp. [2]. Comprehensive coordination chemistry II. Eds. J.A. 101-106. McCleverty, T.J. Meyer. Pergamon Press, N.Y. 2004, [9]. Product properties test guidelines OPPTS 830.7550 par- Vol. 5, chapters 5.2 and 5.3. tition coefficient (n-octanol/water), shake flask method. [3]. Handbook of radiopharmaceuticals: radiochemistry and US Environmental Protection Agency, August 1996. applications. Eds. C.S. Redvanly, M.J. Welch. John EPA 712-C-96-038. Wiley and Sons, West Sussex 2003. [4]. Volkert W.A., Hoffman T.J.: Chem. Rev., 99, 2269-2292 (1999).

VASOPRESSIN PEPTIDE (AVP) LABELLED WITH A “4+1” MIXED-LIGAND TECHNETIUM COMPLEX Ewa Gniazdowska, Przemysław Koźmiński, Krzysztof Bańkowski1/, Hans-Jürgen Pietzsch2/ 1/ Pharmaceutical Research Institute, Warszawa, Poland 2/ Institute of Radiopharmacy, Forschungszentrum Dresden-Rossendorf, Dresden, Germany

The more and more important role in the medicine of present days is played by radiopharmaceuticals – the compounds labelled with various short-lived radionuclides, which are being introduced into the body for either diagnostic or therapeutic purposes. Among the most important diagnostic radio-phar- Fig.1. 99mTc labelling of peptides using a “4+1” approach. maceuticals are those labelled with 99mTc – the radionuclide of nearly ideal nuclear properties and of able increase in lipophilicity [4,6] into the hydro- rich coordination chemistry [1]. The development philic biomolecules. of radiotracers based upon peptides as targeting Introduction of the carboxyl group into the peri- moieties for tumours has been a focus of research phery of the NS3 ligand decreases the lipophilicity over the last decade [2,3]. Pharmacological prop- of the complex molecule, which results in the de- erties of radiometal-labelled peptides are highly decrease of the lipophilicity of the whole peptide- pendent on the conjugated metal complex. -radiometal conjugate. The isocyanide species pre- In the paper we describe an approach to “4+1” viously coupled to the biomolecule via an aliphatic mixed-ligand Tc complexes for labelling vasopressin linker (CN-BFCA) bears the appropriate peptide peptide (arginine vasopressin – AVP). The “4+1” within the conjugate. mixed-ligand complexes, M(NS3)(CN-BFCA) Vasopressin also known as argipressin or an (BFCA – bifunctional coupling agent), consist of antidiuretic hormone (ADH) is a cyclic peptide a central metal ion Tc(III)/Re(III) coordinated by containing nine amino acid residues. Two of them 1 6 a tetradentate NS3 tripodal chelator (tris(2-mer- are molecules of cysteine (Cys and Cys ). Because captoethyl)-amine) and a monodentate isocyanide of the disulphide bond between them, vasopressin (Fig.1). These complexes are known to be extreme- forms a cyclic six-membered amino acid ring with ly stable not only in a thermodynamical sense, but 3 amino acid residues hanging off (Fig.2). Vasopressin also towards ligand exchange in vivo [4-6]. However, is a peptide hormone found in most mammals, in- the unsubstituted NS3 ligand can induce undesir- cluding humans. It is derived from a preprohor- RADIOCHEMISTRY, STABLE ISOTOPES, 78 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Fig.2. Peptide: vasopressin, Cys1-Tyr 2-Phe3-Gln4-Asn5-Cys6-Pro7-Arg8-Gly9. mone precursor that is synthesized in the hypo- cyano butyric acid succinimidyl ester) – was synthe- thalamus, from which it is liberated during transport sized according to the procedure described in [15]. to the posterior pituitary. Most of AVP is stored in the posterior part of the pituitary gland to be released into the blood stream. Some of it is also released directly into the brain tissue. AVP regulates the body’s retention of water, being released when the body is dehydrated (antiduretic action of AVP, mediated via V2 type receptors). It causes the kidneys to conserve water (but not salt), concentrating the urine, and reduc- MS (m/z): calcd – 210.2, found – 209.09 [M+H]+. ing urine volume. AVP also raises arteriar blood Synthesis of CN-AVP: The isocyanide linker pressure by inducing moderate vasoconstriction CN-(CH2)3CO- was coupled to the AVP accord- (pressor action of AVP, mediated via V1 type re- ing to the following reaction: ceptor). In addition to its predominantly antidiuretic and pressor activities vasopressin, as a neuro- peptide, demonstrates a variety of neurological effects on central nervous system (CNS). It is involved via different receptor subtypes in higher brain functions, including cognitive abilities and emotionality. In recent years there has been a par- The product was purified by semi-preparative ticular interest in the role of vasopressin in social HPLC and lyophilized. HPLC system consisted of behaviour and in its participation in such diseases a Phenomenex column – Jupiter Proteo, 4 μm, 90 Å, as schizophrenia and autism [7]. The half-live of 250×10 mm (semi-preparative column), 3 ml/min; vasopressin in vivo is about 15 min. Decreased hor- solvent A – water with 0.1% TFA (v/v); solvent B mone level leads to diabetes insipidus, and there- – acetonitrile with 0.1% TFA (v/v); gradient elu- fore the increase of this period (to avoid recognition – 0-20 min 20 to 80% solvent B, 10 min 80% tion by degradating enzymes) is important and solvent B; UV/Vis detection at 220 nm. can be achieved by removing the N-terminal amine MS (m/z): calcd – 1179.35, found – 1179.40 group of Cys1 and using the non-natural D-arginine [M+H]+. instead of natural L-arginine at position 8 [8]. Synthesis of Re(NS3)(CN-AVP): To verify the Arginine vasopressin receptor 2 (AVPR2, also identity of the 99mTc-labelled peptide, the non-radio- called V2 receptor) is a member of the subfamily of active rhenium reference compound Re(NS3) G-protein coupled receptors. Its activity is medi- (CN-AVP) was prepared by ligand exchange start- ated by the Gs type of G protein, which stimulates ing from the precursor Re(NS3)(PMe2Ph): adenylate cyclase [9]. The overexpression of vasopressin receptor V2 has been found on a small-cell lung cancer (SCLC) [10-13]. The essential features of AVP affinity for V2 receptor are: the ring formed via disulphide bond between Cys1 and Cys6, and three amino acid “tail”, the presence of tyrosine residue at position 2 and NH2 blocked C-terminal glycine. (Arg8)-Vasopressin peptide is a commercially available product, Bachem, catalogue number H-1780. Tetradentate NS3 tripodal chelator – tris(2-mercaptoethyl)-amine – and “cold rhenium precursor” – Re(NS3)(PMe2Ph) – were synthesized The final product was purified by semi-pre- at the Institute of Radiopharmacy, Forschuns- parative HPLC system as described above. zentrum Dresden-Rossendorf, Germany, accord- MS (m/z): calcd – 1559.91, found – 1560.08 ing to the described procedure [14]. [M+H]+. Synthesis of CN-BFCA: The aliphatic linker – Figure 3 shows the peak positions of the monodentate isocyanide CN-BFCA ligand (iso- Re(NS3)(CN-AVP) conjugate: RT=11.2 min (ana- RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 79

Fig.3. HPLC chromatograms of the reaction mixture of Re(NS3)(CN-AVP) conjugate: A – analytical column, B – semi- -preparative column. lytical Phenomenex column – Jupiter Proteo, 4 μm, In the first step 0.2 mg of EDTA and 100 μl of 90 Å, 250×4.6 mm, 1 ml/min), and RT=14.1 min propylene glycol were transferred to a vial and the (semi-preparative column defined above); UV/Vis vial was flushed with argon. 40 μg of SnCl2 and 99m – detection at 220 nm. immediately 200-1000 MBq Tc O 4 solution were

99m Fig.4. TLC analysis of Tc-EDTA precursor in acetone (A) and in water (B) mobile phases; silica gel 60 WF254, Merck.

99m Synthesis of Tc(NS3)(CN-AVP): For AVP added. The vial was flushed with argon and incu- labelling with 99mTc a two-step procedure [4] was bated for 20 min at 37oC. The reaction progress applied. was controlled using TLC (silica gel 60 WF254,

Fig.5. HPLC chromatogram (semi-preparative column) of the reaction mixture of 99mTc-EDTA precursor. RADIOCHEMISTRY, STABLE ISOTOPES, 80 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

99m Fig.6. TLC analysis of Tc(NS3)(CN-AVP) conjugate in (A) acetone (silica gel 60 WF254, Merck) and in (B) MeCN/water (4:1, v/v, RP-18, Merck) mobile phases. Merck). The 99mTc-EDTA complex stays at the ori- Determination of distribution coefficient: Lipo- 99m gin using acetone, and moves to the front in water philicity (logD, pH 7.4) of the Tc(NS3)(CN-AVP) (Fig.4). The purity of the complex was checked by conjugate (an important factor affecting the dis- the HPLC system (Fig.5). tribution of drug molecules in the organism) was In the second step the 99mTc-EDTA compound characterized by their distribution coefficient, D, reacted with 300 μg NS3 and ca. 50 μg isocyanide- in the systems n-octanol/PBS buffer pH=7.4. The -modified peptide CN-AVP. The reaction progress logD value obtained for the 99mTc-labelled vaso- was controlled as above by TLC (Fig.6) and HPLC pressin peptide is equal to -0.48±0.02 (average system (semi-preparative column, γ-detection; Fig.7). values from three independent measurements). The yield of 99mTc-labelling reaction was approxi- The 99mTc-labelled vasopressin conjugate ex- mately 75% and can be increased by using a higher hibited to be very stable (Fig.7). Its lipophilicity peptide amount (the work is under progress). The (higher than the lipophilicity of the free vasopres- 99m Tc(NS3)(CN-AVP) conjugate shows a very high sin peptide) can be corrected by introduction a in vitro stability (>98% in PBS after 24 h; Fig.6). hydrophilic group, R’, at the periphery of the NS3

99m Fig.7. HPLC chromatograms (semi-preparative column) of Tc(NS3)(CN-AVP) conjugate: A – reaction mixture, B – the purified product after 24 h. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 81 ligand (with no changes in the stability of the Chapter 9. In: Labelling of small biomolecules using whole molecule conjugate). Experiments on the novel technetium-99m cores. IAEA, Vienna 2007, 99m pp.129-140. IAEA Technical Report No. 459. Tc(NS3)(CN-AVP) stability in the rat serum medium and its biodistribution will be continued. [7]. Frank E., Landgraf R.: Best Pract. Res. Clin. Anaes- thesiol., 22, 265-273 (2008). The work has been financially supported by the [8]. Messer W.S.: Vasopressin and Oxytocin,, April 03, German Academic Exchange Service (PPP-Polen) 1-4 (2000). and the Ministry of Science and Higher Education [9]. Gal C.S.-L., Raufaste D., Derick S., Blankenstein J., (Poland) grant “The synthesis and investigation of Allen J., Pouzet B., Pascal M., Wagnon J., Ventura new technetium(III) and rhenium(III) complexes M.A.: Am. J. Physiol. Regul. Integr. Comp. Physiol., (so-called “4+1”) with dendritically modified tetra- 293 (2), R938-R949 (2007). [10]. Folny V., Raufaste D., Lukovic L., Pouzet B., Rochard dentate ligands NS3 and monodentate isonitrile ligand” (DAAD/48/2007). P., Pascal M., Serradeil-Le Gal C.: Am. J. Physiol. Endocrinol. Metab., 285, E566-E576 (2003). References [11]. Pequeux C., Breton C., Hendrick J.-C., Martens M.-T. H., Winkler R., Legros J.-J.: Cancer Res., 62, 4623-4629, [1]. Volkert W.A., Hoffmann T.H.: Chem. Rev., 99, 2269 15 (2002). (1999). [12]. North W.G., Fay M.J., Longo K.A., Jiniin Du: Cancer [2]. Okarvi S.M.: Med. Res. Rev., 24, 357 (2004). Res., 58, 1866-1871 (1998). [3]. Liu S., Edwards D.S.: Chem. Rev., 99, 2235 (1999). [13]. Pequeux C., Keegan B.P., Hagelstein M.-T., Geenen [4]. Seifert S., Künstler J.-U., Schiller E., Pietzsch H.-J.: V., Legros J.-J., North W.G.: Endocr. Relat. Cancer, Bioconjugate Chem., 15, 856 (2004). 11, 871-885 (2004). [5]. Gniazdowska E., Künstler J.-U., Stephan H., Pie- [14]. Spies H., Glaser M., Pietzsch H.-J., Hahn F.E., Lüg- tzsch H.-J.: Quaterly J. Nucl. Med., 51, 92 (2007). ger T.: Inorg. Chim. Acta, 240, 465-478 (1995). [6]. Künstler J.-U., Ansorge P., Bergmann R., Gniazdo- [15]. Künstler J.-U., Veerenda B., Figueroa S.D., Sieckman wska E., Decristoforo C., Rey A., Stephan H., Pietzsch G.L., Rold T.L., Hoffman T.J., Smith C.J., Pietzsch H.-J.: Technetium-99m labelling of the RGD peptide H.-J.: Bionconjugate Chem., 18, 1651-1661 (2007). c(RGDyK) using the 4+1 mixed ligand approach.

PLATINUM(II) COMPLEXES WITH THE THIOUREA DERIVATIVES Leon Fuks, Nina Sadlej-Sosnowska1/, Elżbieta Anuszewska1/, Sławomir Siekierski 1/ National Medicines Institute, Warszawa, Poland

Platinum-based drugs are among the most active the aim of reducing the platinum-based side ef- anticancer agents available, used for the treatment fects. of a variety of human solid tumors and form the As a result of our previous studies [3,4] a ques- largest class of anticancer drugs. They destroy mation emerges whether complexes containing the II lignant cells by interfering with the DNA, via inter- Pt (R1R2tu)n fragment, where (R1R2tu) denotes dif- and intrastrand crosslinks and via DNA-protein ferently substituted thiourea (tu) molecule, might crosslinks, thereby preventing cell division and exhibit the desired biological activity. Literature growth. The most frequently used Pt-containing data suggest that Pt(II) complexes with certain drugs are cisplatin (CDDP), carboplatin and oxali- thiourea derivatives (in particular containing the platin. They are extremely effective, however cancer acridine fragment, called ACRAMTUs [5,6]) can cells quickly become resistant to the drug. Therefore, really be potential pharmaceuticals. The mode of search for new platinum drugs (called the second- their therapeutic action differs, however, from that and now, the third-generation drugs) has focused established for cisplatin because they combine in on identifying compounds with improved tolera- a single compound both covalent and intercalative bility profiles and, in particular, on those which modes of binding with DNA. Our search for Pt(II) permit to overcome the mechanism of the resist- complexes with ligands containing the thiourea ance against the platinum drugs. derivatives focused on the synthesis as well as the In the last two decades the interest in Pt(II) structural and cytotoxic characterization of the complexes with chelating ligands containing both compounds with the non-acridine thiourea deriva- nitrogen and sulfur donor atoms has increased, be- tives. The most promising ligands may probably be cause these complexes seem to exhibit either higher also used to form complexes with the 99mTc radio- anticancer activity or reduced toxicity in compari- nuclide, which at present is studied in some labo- son with the known metal containing drugs [1]. As ratories as a perspective agent in the cancer chemo- a result of these studies a number of the novel radiotherapy (Auger electron therapy). Pt(II) complexes sufficiently interesting for clinical The main objective of the present study was to trials have been synthesized. However, only a few determine the biological, i.e. cytotoxic activity of of them are superior to the parental drug in their Pt(II) complexes formed by the following ligands: efficacy [2]. On the other hand, several combined N-2-tetrahydrofurfurylthiourea (1), N-2-methylte chemotherapeutic procedures consisting in appli- trahydrothiophenethiourea (2) and N-2-methylte cation of various Pt(II) complexes together with trahydroselenophenethiourea (3) and to compare compounds containing S-donor groups (in this case their activity with selected physicochemical prop- called chemoprotectants) have been tested with erties of the ligands. RADIOCHEMISTRY, STABLE ISOTOPES, 82 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY Title complexes were prepared following the In spite of the fact, that search within the general synthetic procedure [7] based on the reac- Cambridge Structural Database (CSD) has failed tion: in finding structures of (1), (2) and (3), the experi- II K2Pt Cl4 + n⋅[(NHR)-CS-(NH2)] → mentally found molecular parameters of their frag- II Pt [(NHR)-CS-(NH2)]nCl2 + 2KCl ments agree satisfactorily with the values presented Methanolic solutions of the ligands were added in Table 1. X-ray diffraction studies of tetrahydro- dropwise at room temperature to the aqueous so- furane (THF) show the C(11)-O bond length of lutions of K2PtCl4, until the molar ratios of about 1.435 [9] or 1.427 Å [10] and that of the C(11)-C(13) 1:1 were achieved. The yellow or salmon pink solid bond equal to 1.531 [9] or 1.533 Å [10]. Also the Table 1. Selected bond lengths and angles in the ligands (calculated data).

(1)(2)(3) B3LYP MPW1PW B3LYP MPW1PW B3LYP MPW1PW Bond lengths [Å] C(2)-S(1) 1.675 1.732 1.675 1.731 1.676 1.730 C(2)-N(3) 1.375 1.370 1.374 1.368 1.374 1.368 C(2)-N(4) 1.358 1.348 1.358 1.363 1.358 1.364 S(1)-X 4.746 5.322 5.034 5.342 5.128 5.339 C(11)-X 1.433 1.479 1.864 1.907 2.009 2.024 C(18)-X 1.438 1.465 1.849 1.895 1.990 2.013 C(13)-C(11) 1.531 1.536 1.535 1.536 1.534 1.536 C(13)-C(17) 1.675 1.541 1.675 1.539 1.676 1.539 C(17)-C(18) 1.375 1.533 1.374 1.534 1.374 1.534 Angles [o] N(3)-C(2)-N(4) 114.10 115.50 114.21 115.39 114.32 115.47 N(3)-C(2)-S(1) 121.21 120.35 121.26 120.42 121.18 120.49 C(13)-C(11)-X 107.02 105.89 110.01 105.09 110.13 104.80 C(11)-X-C(18) 109.98 109.62 94.02 93.01 89.77 89.43 products, which started to precipitate immediately C(11)-O-C(18) and O-C(11)-C(13) bond angles of after adding the first drop, were washed several 108.2 [9] and 107.4o [9], respectively, are close to times with fresh portions of warm water and dried the calculated values shown in Table 1. Computa- in a vacuum exsiccator until a constant mass of the tions performed for (3) also fit well the experiment- sample was reached. al data. Main bond lengths in the tetrahydroseleno- Computational approach phene (THS) are: C(11)-Se – 1.96 [11] or 1.97 Å Numerous attempts to obtain crystals of (1), [12] and C(11)-C(13) – 1.53 [11] or 1.54 Å [12]. (2) or (3) and their Pt(II) complexes, suitable for The C(11)-Se-C(18) bond angle is 105.5 [11] or X-ray diffraction studies, have failed. Therefore, 105.8o [12] and Se-C(11)-C(13) – 90.3 [11] or 89.1o we decided to check whether quantum chemical [12]. In spite of the fact that inspection of the CSD calculations may serve as a reliable source of in- brings detailed data for about 750 compounds conformation on the structure of these species. It has taining the tetrathiophene-like fragment – not any been already shown that calculations performed describes the tetrathiophene molecule. at the DFT level reflect sufficiently well structural features of Pt(II) complexes with thiourea [3]. Also recently, structure of the Pt(II) and Pt(IV) complexes with histamine were simulated by more than 20 DFT functionals and various basis sets. Comparison with the X-ray diffraction data has shown that the MPW1PW91 functional combined with the 6-311G** basis set gives the best compatibility of structural parameters for the non-metallic part of the Pt(II)(Hist)Cl2 complex and the SDD (ECP) basis set – for the platinum part [8]. The most important bond lengths and angles calculated for the title ligands are presented in Table 1 and Fig.1. Fig.1. Schematic presentation of structure of the ligands. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 83 In our study, taking into account that analyti- only in 2001 [13]. DFT calculations performed at cally found Pt:Cl mol ratio in the complexes is close the B3LYP level on palladium(II) dithiophosphi- to 2, we were looking for the most probable struc- nate four-membered rings of different conforma- tions (palladium(II) is generally accepted as a model for divalent platinum) indicate that the flat ring is slightly lower in energy (~0.05 eV) than the puckered one [14]. This result remains in accordance with the well known square-planar structures of numerous Pd(II)/Pt(II) compounds. Main results obtained in this study (Table 2) can be summarized as follows: • Structure of the Pt-(1-II) complex, which shows the lowest energy is presented in Fig.2 (left). As can be seen, the seven-membered puckered ring is the main feature of the complex. Two short H···Cl distances (2.557 and 2.641 Å) suggest formation of two intra-molecular hydrogen bonds: C-H···Cl(1) and N-H···Cl(2), respectively. Scheme. Possible coordination of THF with PtCl2–. • Optimization of the Pt-(1-III) structure result- 4 ed in preserving the four-membered ring. The tures of the Pt(II) complex. Basing on the structures lowest energy conformer, Pt-(1-IIIa), is shown reported in the literature, three hypothetical con- in Fig.2 (right). The species is presumably sta- figurations have been chosen as the starting points bilized by two hydrogen bonds, N-H···O (1.593 for calculations (Scheme). Acyclic species with (1) Å), and C-H···Cl (2.926 Å). Other conformers bound monodently to the Pt(II)Cl2 synthon are are similar to the Pt-(1-IIIa) and differ only in named (in the following) as Pt-(1-I). The two cyclic positions of the tetrahydrofurane moiety vs. the structures will be called Pt-(1-II) and Pt-(1-III), four-membered ring. In the conformer called respectively. The structure of Pt-(1-II) contains a Pt-(1-IIIb), with an energy higher by ~0.24 eV, seven-membered ring, whereas that of Pt-(1-III) the H···O and H···Cl distances are 2.010 and – a four-membered ring. 3.107 Å, respectively. Hence, hydrogen bonds, In spite of the well known low stability of four- if even exist, are weaker than in Pt-(1-IIIa). -membered rings caused by relatively great bond- • The energy difference between the most stable -tensions, such structures have been found in the ring conformers Pt-(1-IIIa) and Pt-(1-II) is thioplatin – Pt(II) drug proposed for cancer therapy 0.18 eV in favor of the latter. It means that the Table 2. Selected bond lengths and angles in the platinum-THF complex.

Pt-(1-IIa) Pt-(1-IIIa) Bond lengths [Å] Pt-S 2.444 Pt-S 2.515 Pt-Cl(1) 2.359 Pt-Cl(1) 2.385 Pt-Cl(2) 2.396 Pt-Cl(2) 2.343 Pt-C 2.655 Pt-C 2.252

Pt-O 2.145 Pt-NH2 2.142

C-NH2 1.347 C-NH2 1.419 C-NH 1.357 C-NH 1.346 H(1)···Cl(1) 2.641 H(1)···Cl(1) 3.187 H(2)···Cl(2) 2.557 H(2)···Cl(1) 2.926 H(3)···O 2.765 H(1)···O 1.593 Angles [o] Cl(1)-Pt-Cl(2) 90.09 Cl(1)-Pt-Cl(2) 91.87 O-Pt-S 88.79 N-Pt-S 70.44

S-C-NH2 119.25 S-C-NH2 114.22

NH-C-NH2 119.36 NH-C-NH2 122.02 N-H···Cl(1) 120.28 H2N-H(1)···O 158.18 C-H···Cl(2) 115.77 C-H(2)···Cl(1) 125.50 RADIOCHEMISTRY, STABLE ISOTOPES, 84 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Fig.2. Hypothetical structures with seven-membered ring (II, left) and four-membered ring (III, right) formed by

1-(2-tetrahydrofurfuryl)-2-thiourea with K2PtCl4. seven-membered structure is the most stable, at -phase data. This difference may primarily be at- least in the gas phase. The energy gap, however, tributed to crystal packing and other effects in the is not great enough to secure the same order of solid state. conformers in the condensed phase. A great part of modern chemical bonding theory • Optimization of the linear conformer, Pt-(1-I), is based on the concept of frontier orbitals, the on the MPW1PW/LanL2DZ level resulted in lowest unoccupied molecular orbital (LUMO) and its transformation into a ring structure similar the highest occupied molecular orbital (HOMO) to that of Pt-(1-II). Thus, it can be inferred that [18]. In spite of the great popularity in chemical the postulated Pt-(1-II) structure containing a studies, its theoretical basis is not generally ac- seven-membered ring may be considered as be- cepted because of the artificial nature of the mo- ing the closest to the real one. lecular orbitals which are not observables and can It should be noted that structural data on the be defined in different ways. hydrogen bonds involving halogen acceptors in According to the theory of Pearson and Parr the solid state were recently reviewed by Kovacs [19,20], absolute hardness (η, which is a positive and Varga [15]. Their mean value of the H···Cl value) is half the difference between the ioniza- distance in N-H···Cl– was 2.35 Å, and in C-H···Cl tion energy and the electron affinity of the species 2.39-2.64 Å (depending on the C atom environ- (I and A, respectively). ment). The N-H···Cl– distance calculated in this 1 work for the Pt-(1-II) complex of the lowest en- η=()IA − ergy, Pt-(1-IIa), is equal to 2.641 Å. It is in agree- 2 ment with the crystallographic data. For the com- Within the Koopman theorem, the hardness is plexes of higher energy – Pt-(1-IIb) and Pt-(1-IIIb), equal to half of the difference between the energy the H···Cl– distances in N-H···Cl– were larger, name- of the LUMO and HOMO orbitals. Softness, σ, is ly 2.794 and 3.107 Å, respectively. For the C-H···Cl simply the inverse of hardness, σ=1/η. hydrogen bonds, the corresponding H···Cl dis- According to the hard and soft acids and bases tances are 2.557 Pt-(1-IIa), 2.750 Pt-(1-IIb), 2.926 (HSAB) concept [21,22], soft acids are large elec- Pt-(1-IIIa) and 3.107 Å Pt-(1-IIIb). The first three tron-pair acceptor atoms or ions with a low positive values are lower than the sum of the H and Cl van charge density. Complexes of a soft cation, such as der Waals radii (2.95 Å [16]), but only one value Pt(II) is (η≈8 eV [e.g. 23]) prefer reactions with lies in the range reported in [17]. The rest are larger soft reagents and not with hard ones. The differ- by 0.1-0.4 Å than the previously mentioned solid- ence between the frontier orbitals for (1), (2) and

Table 3. The IC50 values of the investigated Pt(II) complexes. IC ± SD IC ± SD IC ± SD 50 IC [mM] 50 IC [mM] 50 IC [mM] [μg/ml] 50 [μg/ml] 50 [μg/ml] 50 Cell line PtII-(1)PtII-(2) PtII-(3)

WS1 (human embryonic skin 64.6±18.8 0.152 42.3±14.6 0.096 78.4±23.3 0.160 fibroblasts) ME18 (human melanoma cells) 81.0±27.3 0.191 100.0±21.0 0.226 75.1±6.8 0.154 ME18/R (human melanoma subline 102.0±20.8 0.239 83.6±9.0 0.189 48.5±13.7 0.099 resistant to doxorubicin) HeLa (human cervix carcinoma cells) 173.0±27.0 0.406 163.6±20.0 0.370 56.5±3.6 0.116 KB-V1 (HeLa subline resistant 114.0±20.0 0.268 110.0±10.5 0.249 52.2±12.7 0.107 to vinblastine) RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 85 (3), determined by calculation at the MPW1PW/ between the Institute of Nuclear Chemistry and LanL2DZ level, is 5.10, 5.05 and 4.93 eV, respec- Technology (Poland) and the Technological and tively. It can be concluded that even if the overall Nuclear Institute – ITN (Portugal). It was financed hardness of the ligands decreases, it does not de- by the Ministry of Science and Higher Education crease significantly. (Poland) as grant called “Transition metal complexes Stability of the Pt-(1), Pt-(2) and Pt-(3) com- as novel agents of expected biological activity directed plexes in the standard aqueous physiological solu- towards Auger electron therapy (AET)” (grant No. tion was checked by recording their UV-Vis spec- 122/N-Portugal/2008/0) and as the statutory work tra (200-800 nm) vs. time. (Commercial solution for of the National Medicines Institute (Poland). peritoneal injections prod. Baxter Terpol, Ltd., Sie- References radz, Poland, contains 154 mmol dm–3 of natrium and 154 mmol dm–3 of chloride ions (pH=6.7).) No [1]. Faraglia G., Fregona D., Sitran S., Giovagnini L., changes in the spectra have been observed within Marzano C., Baccichetti F., Cesellato U., Graziani R.: J. Inorg. Biochem., 83, 31 (2001). about one week. The HPLC chromatograms of [2]. Canetta R., Rozencweig M., Wittes R.E., Shacter samples withdrawn occasionally from the saline L.P.: In: Proceedings of the Fifth Nagaya Interna- solutions of the complexes did not exhibit notice- tional Symposium on Cancer Treatment. Excerpta able changes either. Both methods show that no Medica, Tokyo 1990, pp.318-323. significant difference in stability of the complexes [3]. Fuks L., Sadlej-Sosnowska N., Samochocka K., Sta- has been found. Taking into account the above rosta W.: J. Mol. Struct., 740, 229 (2005). conclusion we can expect, that Pt(II) interacts [4]. Fuks L.: Pt(II) chloride complexed by tetrahydrofuryl- similarly with electron pairs from the donor atoms thiourea or tetrahydrotiophenylthiourea: structural of all the ligands studied in this work. and biological features. In: Proceedings of the 3rd Central European Conference: Chemistry towards Cytotoxicity of the complexes Biology, Kraków-Przegorzały, Poland, 8-12.09.2006, Results obtained for the cytotoxicity of the P-8. Pt-(1), Pt-(2) and Pt-(3) complexes, measured by [5]. Hess S.M., Anderson J.G., Bierbach U.: Bioorg. Med. the half maximal inhibitory concentration (IC50), Chem. Lett., 15, 443 (2005). are shown in Table 3 and Fig.3. It can be conclud- [6]. Choudhury J.R., Bierbach U.: Nucl. Acids Res., 33, ed that cytotoxicity of the Pt-(1) and Pt-(2) is simi- 5626 (2005). lar for all types of the examined cells. However, [7]. Fuks L., Kruszewski M., Sadlej-Sosnowska N.: Struc- tural studies and cytotoxicity assay of platinum(II) for Pt-(3) complexes, IC50 exccept the the WS1 cell line is lower than that for Pt-(1) and Pt-(2). chloride complexed by (tetrahydrothiophene)thiourea. Effectiveness of the Pt-(3) complex in inhibiting In: INCT Annual Report 2005, Institute of Nuclear Chemistry and Technology, Warszawa 2006, pp.68-70. the growth of HeLa cancer cells growth is compa- [8]. Oziminski W.P., Garnuszek P., Bednarek E., Dobro- rable to that for carboplatin (IC50 48 vs. 23 [24]). wolski J.Cz.: Inorg. Chim. Acta, 360, 1902 (2007). Assuming, that the Pt(II) cation is a soft acid [9]. Luger P., Buschmann J.: Angew. Chem. Int. Ed. [e.g. 23] and basing on the HSAB approach one Engl., 22, 410 (1983). could expect that it interacts most strongly with [10]. Rayón V.M., Sordo J.A.: J. Chem. Phys., 122, 204303 (3). If so, then PtII-(3) could be expected to be the (2005). strongest anticancer agent. Results obtained in [11]. Galeev R.V., Gunderova L.N., Mamleev A.Kh., the present work indicate, that except for the WS1 Magdesieva N.N., Pozdeev N.M.: Zh. Strukt. Khim., and ME18 cell lines such assumption may be cor- 33, 48 (1992), in Russian; Russ. J. Struct. Chem., 33, 196 (1992), in English. rect. However, seven-member ring structure of the [12]. Náhlovská Z., Náhlovský B., Seip H.M.: Acta Chem. studied complexes excludes the possibility of their Scand., 24, 1903 (1970). application as the DNA intercalation agent for the [13]. Amtmann E., Zöller M., Wesch H., Schilling G.: Auger electron therapy. Cancer Chemother. Pharmacol., 47, 461 (2001). This work has been in part carried out within [14]. Esterhuysen C., Kruger G.J., Blewett G., Rauben- the Polish-Portuguese bilateral scientific agreement heimer H.G.: Inorg. Chim. Acta, 359, 609-616 (2006). [15]. Kovacs A., Varga Z.: Coord. Chem. Rev., 250, 710 (2006). [16]. Bondi A.: J. Chem. Phys., 68, 441 (1964). [17]. Desiraju G.R., Steiner T.: The week hydrogen bonding. In: Structural chemistry and biology. Oxford Uni- versity Press, Oxford 1999, pp.246-253. International Union of Crystallography Monographs on Crystal- lography No. 9. [18]. Fukui K., Yonezawa T., Shingu H.: J. Chem. Phys., 20, 722 (1952). [19]. Parr R.G., Pearson R.G.: J. Am. Chem. Soc., 105 7512 (1983). [20]. Pearson R.G.: J. Org. Chem., 54, 1423 (1989). [21]. Pearson R.G.: Science, 151, 172 (1966). [22]. Pearson R.G.: J. Am. Chem. Soc., 110, 7684 (1988). [23]. Alfarra A., Frąckowiak E., Beguin F.: Appl. Surf. Sci., 228, 84 (2004). [24]. Takara K., Obata Y., Yoshikawa E., Kitada N., Sa- Fig.3. Activity of the investigated Pt(II) complexes against kaeda T., Ohnishi N., Yokoyama T.: Cancer Chemother. the tumor cells. Pharmacol., 58, 785 (2006). RADIOCHEMISTRY, STABLE ISOTOPES, 86 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY KINETICS OF ION EXCHANGE OF GALLIUM AND INDIUM IONS BETWEEN AQUEOUS HCl SOLUTIONS AND DOWEX 1-X8 ANION EXCHANGER Irena Herdzik, Jerzy Narbutt

Isotope effects of gallium and indium have been washed with aqueous HCl solutions: 0.5 and 2.5 M, discovered in this Laboratory in the systems con- to constant concentration of Cl– ions in the effluent, sisting of dilute aqueous HCl solutions and ion and then dried at 45oC to constant weight. Distri- exchange resins Dowex 50W-X8 [1] and Dowex bution of gallium and indium ions between the 1-X8 [2]. Isotope ratios of gallium (69/71Ga) and in- resin and HCl solutions was studied in static ex- dium (113/115In) were determined using an ICP-MS periments. Two different stock solutions were pre- (inductively coupled plasma-mass spectrometry) pared: (i) 2.5 M HCl containing gallium ions la- 72 technique [3] in the head and tail fractions of the belled with either carrier-containing Ga (t1/2=14.9 effluent from the respective chromatographic col- h, [Ga]=4.2×10–4-6.2×10–2 M) or 68Ga (n.c.a.) 68 68 umns, collected in dynamic experiments using the eluted from a Ge/ Ga generator (t1/2=68 min, merry-go-round method of elution [1,2]. The signs [Ga]=10–5-10–4 M), and (ii) 0.5 M HCl containing 114m of the effect differ for the same metal ion on the indium ions labelled with In (t1/2=49 d, cation and anion exchanger, and also for the two [In]=4.2×10–4-6.2×10–2 M). The samples of 4 ml of metals on the same ion exchange resin. The lighter a given solution and ~400 mg of the resin were isotope of indium and the heavier one of gallium shaken in glass test-tubes fixed on a rotary mixer accumulated in the phase of the cation exchanger, at 25 ±2oC. Samples of the aqueous phase were Dowex 50W-X8, [1], while the opposite effects were collected at various time intervals t, centrifuged to separate small resin beads, and then the radioac- tivities of their aliquots were measured using a scintillation counter with a NaI(Tl) well-type detector. The distribution ratios of the metal ions have been calculated using the formula:

(A0t−⋅ A ) V Kd = Amt ⋅

Fig.1. Elution of indium from the anion exchanger bed where: A0, At – specific activities of the solutions, (Dowex 1-X8), using 1.0 M HCl [2]. initial and at time t, corrected for the radioactive decay of short-lived gallium radiotracers [cpm]; V observed for the anion exchanger, Dowex 1-X8 – volume of the HCl solution [ml]; m – mass of the [2]. The shapes of chromatographic bands of both resin sample [g] in the test-tube. metals eluted from the cation exchanger bed, and The experiments carried out at various con- that of indium eluted from the anion exchanger centrations of indium in the stock solution, in the (Fig.1), approached the normal distribution, there- range of 4.2×10–4 to 6.2×10–2 M, show that the fore the results could be discussed basing on the kinetics of ion exchange of indium in the system Glueckauf theory [4]. On the contrary, the band 0.5 M HCl/Dowex 1-X8 is fast as expected. The of gallium eluted from the anion exchanger bed equilibrium at 25oC is being reached earlier than was very broad and asymmetric, with a significant in 10 min (Fig.3). The distribution ratio of indium diffusion of the tail part (Fig.2) [2]. To find the in the system is independent of indium concen- reason for this difference, studies on the kinetics tration in the whole range of the concentrations of the ion exchange process of both metal ions studied. were undertaken, using the anion exchange resin. On the contrary, the experiments carried out at The strong alkaline anion exchange resin, Dowex various concentrations of gallium in the stock so- – 1-X8, analytical grade, in the Cl form, 400 mesh lution, in the range of 1.0×10–5 to 6.2×10–2 M, (the small powder fraction being removed by re- show that the kinetics of ion exchange of gallium peating sedimentation), was swelled with twice-dis- in the system 2.5 M HCl/Dowex 1-X8 is slow. The tilled water. Samples of the swelled resin were equilibrium at 25oC is being reached not earlier

Fig.2. Elution of gallium from the anion exchanger bed (Dowex 1-X8), using 2.5 M HCl [2]. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 87 ing step of the reaction is the slow transformation of an octahedral cationic or neutral chloroaqua- -complex of gallium into the tetrahedral [6] anion. In fact, gallium forms very weak chloride com- – plexes, in particular GaCl4 of logβ4=-5.8 [7]. On the contrary, the analogous indium complexes are strong; the prevailing form of indium in the 0.5 M HCl solution is the adsorbable octahedral anion – [In(H2O)2Cl4] for which logβ4=3.35 [8], therefore no slow transformation with the change in the co- Fig.3. Kinetics of ion exchange of indium in the system ordination number is required. 0.5 M HCl/Dowex 1-X8 at initial indium concentrations of 2.0×10–3 M (■) and 6.2×10–2 M (◊). The data point to To check the above hypothesis kinetics of ion 4.2×10–4 M and 1.0×10–2 M are not shown for clarity. exchange of gallium was studied from HCl solutions of higher concentrations (8 and 10 M HCl) – that after a couple of hours (Fig.4). It is of interest where the prevailing form of gallium was GaCl4 that the distribution ratio of gallium in the system [5]. Because of very high Kd values expected, sam- studied is independent of the concentration of ples of 20 mg of the Dowex 1-X8 resin were equili- gallium in the system only below the initial con- brated with 8 ml of HCl solutions at a gallium –3 –4 centration of 10 M. At higher concentrations of concentration of 2.0×10 M (Fig.6). The logKd gallium, the Kd value decreases with increasing gal- values at equilibrium were equal to 4.54 and 4.32, lium concentration (Fig.5). The low Kd=8.9 cor- respectively, and the loading of the resin was less responding to the initial concentration of gallium than 2.3% of the loading capacity each. The equi- of 6.2×10–2 M can be due to the high loading of librium was reached after ca. one hour each. The – the resin, ~0.25 meq GaCl4/g (~8.4% of the load- kinetics of gallium adsorption significantly improved,

Fig.4. Kinetics of ion exchange of gallium in the system Fig.6. Kinetics of ion exchange of gallium in the systems 2.5 M HCl/Dowex 1-X8 at gallium concentrations in the 8 M HCl/Dowex 1-X8 and 10 M HCl/Dowex 1-X8 at gallium range of 4.2×10–4 to 6.2×10–2 M. The data point to the concentration of 2.0×10–4 M. concentrations of 1.0×10–5, 6.2×10–5 and 1.0×10–4 M – very close to those for that of 4.2×10–4 M – are not shown but not as much as expected – it still remained for clarity. much slower than the kinetics of indium adsorption. However, this difference may be due to the ing capacity, ~1.8% for the 1×10–2 M solution), much higher HCl concentrations in the gallium though there is no decrease in Kd of indium even systems studied than that in the case of indium for the 6.2×10–2 M solution where the loading ap- (0.5 M HCl). The increase in the HCl concentra- – proaches to 5.7% of the loading capacity of the tion increases the rate of GaCl4 desorption from resin. the resin, making the total process of ion exchange The slow kinetics of ion exchange of gallium in of gallium slower. the system studied may be due to the fact that in The reason of the concentration-dependent Kd the 2.5 M HCl solution only a very small fraction values of gallium in the system 2.5 M HCl/Dowex of gallium (less than 0.1%) is in the form of adsorb- 1-X8 remains unknown. Ion-pair formation by – – able anions GaCl4 [5], and that the rate-determin- GaCl4 with the great excess of cationic forms of gallium (asssociation) in 2.5 M HCl may be an op- tion. However, experiments on the gallium-concentration dependence of Kd at high HCl concen- – trations with the prevailing GaCl4 form of gallium seem impossible. Very high Kd values of gallium at 8 and 10 M HCl require experiments with very small amounts of the resin, which makes it impossible the use of higher gallium concentrations at which the loading capacity of the resin could be exceeded. References Fig.5. Distribution ratio of gallium in the system 2.5 M

HCl/Dowex 1-X8 at equilibrium, Kd, as a function of the [1]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wy- total concentration of gallium in the system. socka A.I.: Nukleonika, 51, 217-220 (2006). RADIOCHEMISTRY, STABLE ISOTOPES, 88 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

[2]. Herdzik I., Dembiński W., Skwara W., Bulska E., Wy- [4]. Glueckauf E.: Trans. Faraday Soc., 51, 34-44 (1955). socka A.: Gallium and indium isotope effects in the [5]. Kraus K.A., Nelson F.: In: The structure of electrolytic Dowex 1-X8/HCl system. In: INCT Annual Report solutions. Ed. W.J. Hamer. John Wiley & Sons, New 2006. Institute of Nuclear Chemistry and Technology, York 1959, pp.340-364. Warszawa 2007, pp.81-82. [6]. Siekierski S., Burgess J.: Concise chemistry of the ele- [3]. Herdzik I.: ICP-MS as a method for determining iso- ments. Horwood Publishing, Chichester 2002, p.90. tope ratios of gallium and indium in chromatographic [7]. Kraus K.A., Nelson F., Smith G.W.: J. Phys. Chem., 58, systems. Institute of Nuclear Chemistry and Technology, 11-17 (1954). Warszawa 2006. Raporty IChTJ. Seria A, nr 5/2006 (in [8]. Kondziela P., Biernat J.: Electroanal. Chem. Interfac. Polish). Electrochem., 61, 281-288 (1975).

CHEMICAL CHARACTERIZATION OF SEVERAL SAMPLES OF IRON TYPE METEORITES Zbigniew Samczyński, Rajmund Dybczyński, Jan Kučera1/, Jiři Mizera1/, Ewelina Chajduk, Bożena Danko 1/ Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Řež, Czech Republic

Meteorites play an important role in researches diation in a nuclear reactor. As regards the second aimed at the origin and evolution of the solar system. mode, it concerns elements, whose determination The most useful criteria, on the basis of which me- is feasible via radionuclides having longer half-life. teorites can be classified are chemical data. Neutron In the case of some elements, however, their de- activation analysis (NAA) due to its valuable ad- termination is possible with comparable detection vantages, such as low detection limits for many limits using both modes. elements as well as minimization of the blank and Determination of short-lived radionuclides in the possibility to analyze small samples, is very suit- the meteorites was carried out at the Nuclear able and frequently applied an analytical technique Physics Institute (Řež, Czech Republic). This part for the chemical characterization of meteorites. of research was supported by the European Com- The subject of this study are the following me- munity under the 6th Framework Program (con- teorites: “Jankowo Dolne”, “Coahuila IIA”, “Campo tract No. RII3-CT-2003-505925). The Nuclear del Cielo”, “Konopiska pr. M.C.”, “Morasko Physics Institute possesses a laboratory for the de- Typical”, “Morasko III CD” and “Gibbon IA”. All termination of short-lived isotopes situated at the of them belong to the group of iron type meteor- nuclear reactor building, equipped with a pneu- ites. The instrumental version of NAA was used in matic post system. It enables to transport samples order to establish their chemical characteristics. to and from the core of the reactor. Activated radio- In order to achieve this purpose two different ana- nuclides can afterwards be counted directly by lytical modes were applied. The first one comprises gamma-ray spectrometry. The meteorites and stand- elements determined on the basis of their short- ards were irradiated with Au monitors (1 μg of -lived isotopes (half-life of the order of seconds Au), by means of which the neutron flux gradient and minutes), formed as a result of neutron irra- was monitored. Neutron activation was performed Table 1. Analytical results of the meteorites via short-lived isotopes.

Element, isotope, half-life, unit Co Ga Ge Mn Ni Rh Meteorite (60mCo) (72Ga) (75Ge) (56Mn) (65Ni) (104mRh) 10.5 m 14.3 h 11.3 h 2.58 h 2.54 h 4.4 m mg kg–1 mg kg–1 mg kg–1 mg kg–1 wt% mg kg–1 1809 95.0 420 6.40 6.35 Konopiska pr. M.C. 1.32 1942 123 438 7.20 5.91 3123 59.6 184 6.99 5.60 1.63 Coahuila IIA 2946 68.2 180 6.91 5.50 1.99 91.9 380 7.35 6.72 1.22 Campo del Cielo 2412 95.8 295 11.0 5.69 0.87 4186 103 511 7.14 6.94 1.31 Jankowo Dolne 4588 105 509 6.99 6.99 1.05 2430 104 496 7.07 6.85 1.49 Morasko Typical 2804 103 443 7.47 6.06 1.03 2955 100 481 7.08 7.27 1.58 Morasko III CD 3133 112 476 6.65 7.21 1.22 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 89 –1 W) W 1.13 0.87 0.99 1.12 1.39 1.77 1.42 0.32 0.24 1.68 0.56 0.42 1.24 1.12 187 24.0 h ( mg kg –1 Sb) – – Sb 0.22 0.22 0.34 0.28 0.48 0.60 0.34 0.21 122 66.0 h ( mg kg –1 Re) – –– – Re 0.03 0.05 0.02 0.03 0.85 1.15 0.14 0.17 186 3.80 d ( mg kg –1 Pt) Pt 7.54 7.15 9.70 7.35 7.05 7.42 7.09 5.89 6.61 7.78 7.87 7.59 199 24.78 19.13 3.15 d ( mg kg –1 Os) – – – Os 0.81 0.55 2.05 1.43 7.99 7.23 2.32 2.22 191 14,6 d ( mg kg –1 Ir) Ir 192 1.09 0.92 1.19 1.18 1.10 0.89 2.38 2.56 1.14 1.14 3.35 3.20 16.77 13.71 ( 74.4 d mg kg –1 Ga) Ga 130 127 156 139 128 113 130 133 122 119 88.4 78.2 25.2 22.6 72 14.3 h ( mg kg Fe) Fe 51 wt% 75.96 76.96 85.60 82.82 76.95 73.76 85.40 89.48 67.67 67.83 84.17 84.34 76.27 74.59 ( 45.1 d Element, isotope, half-life, unit –1 Cr) Cr 154 144 51 8.54 6.25 6.57 4.64 4.55 6.20 14.42 18.72 20.14 16.80 13.11 11.88 ( 27.8 d mg kg –1 Co) Co 60 3427 3497 3342 3311 4315 3852 3802 3675 4460 4340 3727 3909 4383 4436 5.24 y ( mg kg –1 Ba) – – – Ba 243 232 187 228 4435 4255 4697 3823 131 11.5 d ( mg kg –1 isotopes of longer half-life. Au) Au 1.22 1.18 0.46 0.48 1.14 1.09 0.99 0.87 1.39 1.46 1.37 1.29 1.24 1.27 198 via 64.8 h ( mg kg –1 As) As 76 8.57 8.74 17.05 13.24 19.64 18.44 13.27 11.15 22.69 24.48 20.83 20.19 23.98 23.53 ( 26.3 h mg kg Meteorite Gibbon IVA Coahuila IIA Jankowo Dolne Morasko III CD Morasko Typical Campo del Cielo Konopiska pr. M.C Table 2. Analytical results of the meteorites Table RADIOCHEMISTRY, STABLE ISOTOPES, 90 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY both with the thermal and epithermal neutrons (in formed: approximately 1 day, 1 month, and 4 a Cd cylindrical box). Gamma-ray spectra were mea- months after neutron activation. Analytical results sured using a coaxial HPGe detector (Canberra). obtained via radionuclides of longer half-life are In order to determine as many as possible short- -lived radioisotopes, several modes of activation analysis (with thermal or epithermal neutrons) were employed, varying in irradiation, decay and counting time. As a result, the following elements were determined: Rh, Ge, Ga, Ni, Mn, and Co. Analytical results are summarized in Table 1. The main difficulty, which made it impossible to determine more short-lived radionuclides (e.g. 109mPd, 197mPt, 105Ru, 52V, 51Ti, 66Cu, 87mSr, 111mCd and 239U) was a quite high content of cobalt in the meteorites. Very high activity produced by its short-lived radionuclide 60mCo raised largely the Compton background, what strongly interfered with the gamma-ray photo-peaks of other elements. Fig. Gamma-ray spectrum of the meteorite sample “Janko- Determination of trace elements concentra- wo Dolne” obtained after 2 days cooling. Time of measure- tion in meteorites via isotopes of longer half-life ment – 50000 s. was accomplished at the Institute of Nuclear Chemistry and Technology. Analytical results of a presented in Table 2. As it was observed in the test sample of the meteorite “Morasko Typical” case of short-lived isotopes, very high photo-peaks revealed that there is a possibility to determine originating from 60Co and 59Fe (Fig.) and resulting with a sufficiently good accuracy the following Compton’s background posed problems with count- group of elements: Ga, Ba, W, Ir, Au, Cr, Os, Pt, ing of micro-constituents. Nevertheless, the activ- Ru, Sb, Re, As, Co and Zn. The irradiation pack- ity of practically all of the analytes listed above age consisting of samples of meteorites, multi-ele- could be measured according to the outlined mea- ment standards and neutron flux monitors (Au surement mode. It is worth mentioning that the standards) was irradiated in the nuclear reactor determination of several noble metals in the in- MARIA (Świerk, Poland, 0.5 h, neutron flux – 1014 vestigated samples of meteorites turned out to be n cm–2 s–1). In order to obtain maximum informa- feasible. Their content is a very important criterion tion on trace elements from gamma-ray spectra of in the classification of iron type meteorites. the examined meteorites, three series of measure- Further work on analysis of meteorites is in ments (using coaxial HPGe detector) were per- progress.

PROFICIENCY TESTING SCHEME PLANTS 8: DETERMINATION OF As, Cd, Cu, Hg, Pb, Se AND Zn IN DRY CAROOT ROOT POWDER Halina Polkowska-Motrenko, Ewelina Chajduk, Jakub Dudek, Elżbieta Czerska

Proficiency testing (PT) schemes are one of the Test material parts of quality assurance and quality control sys- Preparation of test material tem in chemical measurements. Participation in Testing material was prepared from the home- PT enables laboratories to demonstrate the relia- -grown carrots which were air dried in a dryer ac- bility of the data they are producing. It is also one cording to the procedure commonly used by the of the requirements of the international standard food concentrate producers (mainly 25oC, from ISO/IEC 17025:2005 [1] and can be used by ac- time to time 60oC), milled in a centrifugal mill creditation bodies in acreditation decisions. The made of stainless steel and sieved by stainless steel Institute of Nuclear Chemistry and Technology sieves. Particle fraction below 0.5 mm was collect- (INCT) has been involved in providing PT since ed, homogenized by mixing and bottled in 20 g 2003. PT schemes PLANTS has been designed for test samples. Care was taken to avoid contamina- the purposes of laboratories from Poland and tion. In order to ensure long-term stability of the Central and Eastern Europe determining trace ele- test samples radiation sterilization was carried ments in food of plant origin. PT PLANTS 8: out. All bottles with the test material were irradi- Detemination of As, Cd, Cr, Cu, Hg, Pb, Se and ated with an electron beam (energy 10 MeV, 9 kW) Zn in dry carrot root powder has been conducted from a linear accelerator LAE-13/9 (Department in 2008. The adopted strategy of the PT scheme of Radiation Chemistry and Technology, INCT). complies with the ISO/IEC Guide 43-1:1997 [2], The sterilization dose was 28 kGy. ISO 13528:2005 [3] and IUPAC harmonized pro- The procedure of moisture determination was tocol [4]. established on the basis of water desorption curves RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 91

Table 1. Results of As, Cd, Cr, Cu, Hg, Pb, Se and Zn determination provided by the reference laboratories.

Result (mean value) X u (k=2) Element Method Laboratory [mg kg–1] [mg kg–1]

0.038 0.008 HG-AAS IBPRS definitive RNAA As 0.042 0.006 IChTJ [5] 0.040 0.009 ICP-MS IChTJ 0.329 0.004 ET-AAS IBPRS 0.391 0.044 ET-AAS WIChiR Cd 0.368 0.023 ET-AAS IChTJ 0.343 0.034 ICP-MS IChTJ 0.235 0.040 ET-AAS IBPRS Cr 0.211 0.017 INAA IChTJ 0.240 0.035 ICP-MS IChTJ 5.38 0.38 ET-AAS IChTJ 5.61 0.65 ET-AAS WIChiR Cu 4.47 0.10 FAAS IBPRS 5.28 0.69 ICP-MS IChTJ 0.0046 0.0013 CV-AAS IChTJ Hg 0.0035 0.0004 CV-AAS IBPRS 0.0043 0.0005 AAS WIChiR 0.19 0.03 ET-AAS IChTJ 0.093 0.006 ET-AAS IBPRS Pb 0.21 0.04 ICP-MS IChTJ 0.12 0.03 AAS WIChiR 0.019 0.002 HG-AAS IBPRS Se definitive RNAA 0.028 0.005 IChTJ [5] 26.9 0.39 FAAS IBPRS 28.3 2.4 ET-AAS WIChiR Zn 26.4 2.5 ICP-MS IChTJ 28.2 1.7 ET-AAS IChTJ determined at different temperatures. The refer- were obtained during ICP-MS analysis were com- ence point has been chosen on a plateau that en- pared. Content of Zn was determinated by the sures satisfactory reproducibility of the results. It atomic absorption spectromety (AAS) method. has been recommended to dry subsamples of the Mean value (Xmean), standard deviation of mean o material for 20 h at 70 C. In this case, the uncer- value (Sx), repeatability standard deviation (Sr) tainty associated with moisture content determi- and between samples standard deviation (Ss) were nation was evaluated to be ≤1%. calculated using the following equations: Homogeneity testing Xmean = ∑Xaverage (1) Homogeneity testing was carried out accord- Xaverage = (Xt,1 + Xt,2)/2 (2) ing to the ISO 13528:2005 standard [3]. Contents of the elements in question in 10 randomly selected 2 S(XX)/(g1)X=−∑ mean average − (3) bottles were determinated by the inductively cou- 2 pled plasma-mass spectrometry (ICP-MS) method. S(XX)/(2g)=− (4) rt,1t,2∑ Two samples of 250 mg were taken from each bottle 22 and analyzed. The ICP-MS method allowed to de- SS(S/2)sxr=− (5) terminate Cd, Cr, Cu, Pb and Zn in samples. Due where: Xaverage – avarage result for t bottle, t – bottle to the very low concentration of Se, signals which number (t=1, 2, ..., g). RADIOCHEMISTRY, STABLE ISOTOPES, 92 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY Table 2. Assigned values and their uncertainties. ratories. The obtained results are summarized in Table 1. The assigned values and their uncertainties Element Unit Assigned value ± uncertainty* (Table 2) were calculated as the robust average of As mg kg–1 0.040 ± 0.004 the results reported according to the procedure recommended by the ISO 13528:2005 standard [3]. Cd mg kg–1 0.358 ± 0.015 Calculation of performance statistics For the purpose of performance evaluation, the Cr mg kg–1 0.229 ± 0.022 z-score, En numbers [2] and zeta-score [4] have Cu mg kg–1 5.19 ± 0.31 been employed. En-test was used only when a par- ticipationg laboratory reported its own estimation Hg mg kg–1 0.0041 ± 0.0006 of uncertainty.

–1 The value of the z-score was calculated using Pb mg kg 0.15 ± 0.02 the equation (7): –1 xx− Se mg kg 0.024 ± 0.007 z= lab ref (7) σˆ Zn mg kg-1 27.5 ± 1.2 where: xlab – result reported by the participating * Expanded standard uncertainty (k=2). laboratory, xref – assigned value, σˆ – standard deviation for proficiency assessment calculated from The material is considered to be homogeneous if: Horwitz`s formula [6]: S≤σ 0.3 ˆ (6) s −7 where σˆ is the standard deviation for proficiency ⎧0.22 c for c<1.2⋅ 10 assessement. ⎪ 0.8495− 7 σ=0.02 c for 1.2 ⋅ 10 ≤ c ≤ 0.138 (8) On the basis of the obtained results, it has been ⎨ ⎪ 0.5 found that the material could be considered as ⎩0.01 c for c>0.138 homogeneous for the sample mass ≥250 mg for all the determined elements. where c is the concentration of the element in g g–1. Table 3. Number of PT participating laboratories determining individual elements, number of applied methods and number of accepted results.

Number of results provided (labs) Number Number z-score zeta-score En numbers Element of methods of labs applied satisfactory questionable unsatisfactory accepted satisfactory satisfactory

|z|≤2 2<|z|<3 |z|≥3 |z|<3 |zeta|<3 |En|≤1

As 16 4 8 2 3 10 7 6 Cd 23 5 22 1 0 23 15 13 Cr 6 3 3 1 1 4 3 3 Cu 19 4 18 1 0 19 17 15 Hg 17 4 12 2 3 14 14 10 Pb 18 5 12 1 2 12 10 9 Se 4 2 0 0 2 0 0 0 Zn 18 3 18 0 0 18 15 13

Assigning property values For As, Cd, Cr, Cu, Hg and Se σˆ =σ. In the case Some of the test samples were selected ran- of Pb and Zn the standard deviation for profi- domly and analyzed by a group of reference labo- ciency assessment was calculated form the formula:

Fig.1. Results of laboratories participating in PT (z-score) Fig.2. Results of laboratories participating in PT (z-score) for As determination. for Cd determination. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 93

σ=ˆ σ22 +S (9) Twenty five laboratories participated in the PT. s Twenty four laboratories provided the results. The The σˆ values are equal to 0.010 mg kg–1 for As, number of PT participating laboratories, the num- 0.069 mg kg–1 for Cd, 0.046 mg kg–1 for Cr, 0.648 ber of applied methods and the number of accept- mg kg–1 for Cu, 0.0010 mg kg–1 for Hg, 0.035 mg ed results are summarized in Table 3. kg–1 for Pb, 0.005 mg kg–1 for Se and 2.91 mg kg–1 for Zn.

Fig.4. Results of laboratories participating in PT (z-score) for Zn determination. Fig.3. Results of laboratories participating in PT (z-score) for Hg determination. As can be seen, the performance of the participating laboratories can be recognized as satis- The value |z| < 3 has been set as an acceptance factory. Only 11 from among 121 provided results level for this PT. are not accepted on the basis of z-score value. The values of the En numbers are calculated Some examples of summary results are shown in from the following equation: Figs.1-4. xx− E = lab ref (10) References n 22 UUlab+ ref [1]. ISO/IEC 17025:2005 – General requirements for the where U is the expanded standard uncertainty competence of testings and calibration laboratories. (k=2). ISO, Geneva 2005. The value |En|≤1 has been set as an acceptance [2]. ISO/IEC Guide 43-1:1997 – Proficiency testing by in- level for this PT. terlaboratory comparison. Part 1: Development and The value of the zeta-score was calculated us- operation of proficiency testing schemes. ISO, Geneva ing the equation: 1997. [3]. ISO 13528:2005 – Statistical methods for use in profi- xx− zeta = lab ref (11) ciency testing by interlabratory comparisons. ISO, uu22+ Geneva 2005. lab ref [4]. Thompson M., Ellison S.L.R., Wood R.: Pure Appl. where u is the expanded standard uncertainty Chem., 78, 1, 145-196 (2006). (k=1). [5]. Dybczyński R.S., Danko B., Polkowska-Motrenko H., The value |zeta|<3 has been set as an accep- Samczyński Z., Talanta, 71, 529-536 (2007). tance level for this PT. [6]. Thompson M.: Analyst, 125, 385-386 (2000).

INTERLABORATORY COMPARISON ON THE DETERMINATION OF 137Cs AND 90Sr IN WATER, SOIL AND LIQUID MILK Halina Polkowska-Motrenko, Leon Fuks, Ewelina Chajduk, Marta Pyszynska

Reliability of measurements of radioisotope radio- soil and liquid milk was organized by the NAEA activity concentrations are of primary importance of Poland in 2008 with the participation of ten for the laboratories dealing with radioactivity de- laboratories from Polish research institutes and terminations. It is also of great importance for universities and two laboratories from abroad. The protection of the environment against radioactive ILC was conducted by the Institute of Nuclear contaminants. Laboratories should demonstrate Chemistry and Technology (INCT) in accordance their competence to produce reliable results. This with ISO standards [3,4]. can be done by the participation in interlaboratory Test materials, i.e. drinking and surface waters comparisons (ILC) or proficiency testing schemes have been prepared by spiking appropriate raw (PT). The participation in ILC/PT is either required materials with known amounts of 137Cs and 90Sr to by ISO/IEC 17025 standard [1]. In keeping with obtain required radioactivity concentration. Liquid the Polish legislate [2], since 2002, it is obligatory milk and soil were used as test materials without for the National Atomic Energy Agency of Poland spiking with radioisotopes (Table 1). Radioactivity (NAEA) to organize every two years national ILC concentration of 137Cs and 90Sr in test materials were on the determination of selected radionuclides in determined using the following methods. food and environmental samples. Sequent of such For 137Cs measurements, the samples were placed ILC on the determination of 137Cs and 90Sr in water, in Marinelli vessels and analyzed using a gamma-ray RADIOCHEMISTRY, STABLE ISOTOPES, 94 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Table 1. Composition of samples.

Assigned value ± uncertainty (k=2) Sample Preparation 137Cs 90Sr Water 1C1 spiking 0.073 ± 0.007* Water 1S1 spiking 0.076 ± 0.005* Water 1C2 spiking 0.763 ± 0.025* Water 1S2 spiking 0.170 ± 0.012* Milk natural content 0.436 ± 0.039* 0.056 ± 0.030* Soil natural content 7.73 ± 0.41** - * Bq.dm–3. ** Bq.kg–1 d.m. spectrometer. Solid samples were measured in the of the accuracy of results obtained by the partici- same way as liquid samples. The measuring time pating laboratories. The uncertainties of the as- varied from 24 h to 7 days, depending on the spe- signed values were evaluated taking into account cific radioactivity of the samples. all possible sources of uncertainty according to Water samples containing 90Sr were introduced ISO Guide to the Expression of Uncertainty in onto the column with a cation exchanger AG 50W Measurements (GUM) [7-8] and EURACHEM X8 [H+] (100-200 mesh). Retained 90Sr was washed Guides [9]. In the case of 137Cs and 90Sr content in 137 out with 50 ml of 8 M HNO3. The resulting solu- milk and Cs in soil, assigned values were calcu- tion was deposited to arrange equilibrium with the lated as participants consensus values according 90Y isotope. Next, Y and Ba carriers were added and to [4]. Results obtained by the INCT were also the solution was evaporated to dryness. Obtained taken into account. Assigned radioactivity concen- 90 residue was dissolved in HNO3; Y was isolated tration values of the prepared samples are sum- by solvent extraction using TBP as extractant solu- marized in Table 1. tion, next, the analyte was reextracted to the aque- Individual laboratory performance was evaluat- ous phase. Activity concentration of 90Y in water ed using z and zeta-scores from the following equa- was measured using the LSC (liquid scintillation tions [3,4,10]: counting) method [5]. xx− Milk samples were evaporated to dryness and z = lab ref (1) burned. Obtained ash with carriers of Sr, Y, Ba σˆ was dissolved in hot HNO . The further steps of xx− 3 zeta = lab ref (2) analytical procedure were the same as for water uu22+ samples [6]. ref lab Homogeneity of test materials is of crucial im- where: xlab, xref – the result reported by the partici- portance for the comparability of the results and pant and assigned value, respectively; uref, ulab – consequently for a successful assessment of labo- standard uncertainty of assigned values and report- ratory performance. All prepared samples were ed by the participant, respectively; σ – the standard homogeneous due to the way of their preparation. deviation for proficiency assessment. However, homogeneity was tested and con- xlab is the mean of the individual measurement re- firmed by measuring 137Cs activity concentration. sults as reported by the participant. The z-score Water test materials were spiked using certified value |z|<3 has been set as an acceptance level standard radionuclide solutions, traceable to SI. for this PT [3,4,10]. In that case, assigned values of the 90Sr and 137Cs The zeta-score provides information whether the radioactivity concentration have been calculated laboratory uncertainty estimation is consistent with from formulation [3,4], i.e. considering the way its deviation from reference value. The zeta-score the test materials were prepared. In such a case, should be analyzed together with the z-score value the test materials used for the studies have trace- calculated for the same laboratory result. The in- able assigned values, and ILC provides evaluation terpretation of zeta-score value is similar to that of z-score value [3,4,10].

Fig.1. Results of 137Cs determination in water. Fig.2. Results of 90Sr determination in water. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 95 The participants’ results were also evaluated according to the criteria for trueness and precision pro-

Fig.4. Results of 90Sr determination in liquid milk.

Results reported by the laboratories as smaller than Fig.3. Results of 137Cs determination in liquid milk. the limit of detection (≤LOD) were assumed to be acceptable if the radioactivity concentration was posed by the International Atomic Energy Agency below the detection limit of the analytical method (IAEA) [11]. The criteria are as follows: applied by the laboratory. Results obtained by par- • result passes trueness criterion, if: ticipating laboratories are summarized in Tables 2 22 and 3. xref−≤ x lab 2.58 ⋅ u ref + u lab (3) • result passes precision criterion, if: 22 ⎛⎞⎛⎞uu ⎜⎟⎜⎟ref+⋅≤σ lab 100% ˆ[[%] (4) ⎝⎠⎝⎠xxref lab where σ [%] is the target value used in calculation of z-score value or a maximum value of uncertainty which can be accepted. The following values for σ have been established: 137 90 • 15-30% for Cs and Sr in water samples, de- Fig.5. Results of 137Cs determination in soil. pending on radioactivity concentration; 137 • 15% for Cs in sand samples; Presented results show that the procedures of 137 • 25-60% for Cs in liquid milk. assigning value and preparation of homogeneous Figures 1-5 present the examples of the results re- material have been done properly. ported by the participanting laboratories in com- Moreover, it could be concluded that the major- parision with the assigned values and z-score values. ity of the results provided by laboratories remains Obtained curve shapes do not show any deviation in good agreement with the assigned values and from the normal distribution. with the results obtained by other laboratories. Such Table 2. Results obtained within laboratories – 137Cs determination.

Result of 137Cs determination 1C1 1C2 liquid milk soil Laboratory code X ± u (k=1) X ± u (k=1) X ± u (k=1) X ± u (k=1) [Bq·dm–3] [Bq·dm–3] [Bq·dm–3] [Bq·kg–1] 1 0.379 ± 0.027 7.06 ± 0.35 2 ≤0.80 1.14 ± 0.26 8.59 ± 0.43 3 7.91 ± 0.33 4 0.49 ± 0.12 7.93 ± 0.31 5 0.089 ± 0.009 0.71 ± 0.03 0.47 ± 0.04 8.11 ± 0.44 6 0.076 ± 0.0048 0.700 ± 0.045 0.43 ± 0.03 7.46 ± 0.39 7 0.078 ± 0.003 0.791 ± 0.029 0.404 ± 0.047 7.15 ± 0.21 8 0.75 ± 0.02 9 0.060 ± 0.008 0.74 ± 0.03 1.04 ± 0.05 7.77 ± 0.31 10 0.081 ± 0.015 0.772 ± 0.031 0.525 ± 0.087 6.38 ± 0.23 11 0.786 ± 0.039 7.18 ± 0.25 12 A 0.45 ± 0.01 8.78 ± 0.28 12 B 8.76 ± 0.13 13 ≤0.0784 0.709 ± 0.0355 0.413 7.97 ± 0.12 RADIOCHEMISTRY, STABLE ISOTOPES, 96 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Table 3. Results obtained within laboratories – 90Sr determination.

Result of 90Sr determination 1S1 1S2 liquid milk Laboratory code X ± u (k=1) X ± u (k=1) X ± u (k=1) [Bq·dm–3] [Bq·dm–3] [Bq·dm–3] 1 0.089 ± 0.012 0.185 ± 0.022 2 0.065 ± 0.026 0.145 ± 0.028 3 4 5 0.038 ± 0.003 0.18 ± 0.03 0.15 ± 0.02 6 0.088 ± 0.008 0.19 ± 0.02 0.012 ± 0.004 7 0.058 ± 0.005 0.153 ± 0.008 0.04 ± 0.004 8 9 0.088 ± 0.010 0.163 ± 0.012 10 11 0.156 ± 0.016 12 13 0.05 ± 0.007 0.16 ± 0.008 0.08 ± 0.009 agreement means that the performance of the labo- [5]. Tri-Carb. Liquid Scintillation Analyser. Reference ratories is good. manual. Packard Instrument Company, 1995. [6]. Tait D., Haase G., Wiechen A.: J. Radioanal. Nucl. References Chem., 226, 1-2, 225-228 (1997). [7]. ISO Guide to the Expression of Uncertainty in Mea- [1]. ISO/IEC 17025:1999 General requirements for the surements. International Organization for Standard- competence of testing and calibration laboratories. ization, Geneva 1993. www.iso.org/iso/en/. [8]. EURACHEM-CITAC Guide on Quantifying Uncer- [2]. Rozporządzenie Rady Ministrów z dnia 17 grudnia tainty in Analytical Measurement. 2nd ed. EURACHEM, 2002 roku w sprawie stacji wczesnego wykrywania ska- Teddington 2000. żeń promieniotwórczych i placówek prowadzących po- [9]. Thompson M., Ellison S.L.R., Wood R.: Pure Appl. miary skażeń promieniotwórczych. Dz. U. z 2002 r. Chem., 78, 1, 145 (2006). nr 239, poz.2030 (in Polish). [10]. Radecki Z., Burns K.I.: Assessing laboratory perfor- [3]. ISO/IEC Guide 43-1:1997 Proficiency testing by inter- mance for radionuclide measurements – the IAEA laboratory comparisons – Development and opera- approach. In: Proceedings of the Interregional Train- tion of proficiency testing schemes. Geneva 1997. ing Course on Organizational, Reporting and Certi- [4]. ISO 13528:2005 Statistical methods for use in profi- fication Aspects of Proficiency Tests, Seibersdorf, ciency testing by interlaboratory comparisons. Geneva Austria, 08-19.03.2004. 2005.

RADIOCHEMICAL SCHEME FOR IRON DETERMINATION IN BIOLOGICAL MATERIALS BY NEUTRON ACTIVATION ANALYSIS Bożena Danko, Marta Pyszynska, Rajmund Dybczyński, Monika Sadowska-Bratek, Elżbieta Czerska

Iron is the most commonly used metal in all civili- great importance. Determination of iron in bio- zations. As the element content in the lithosphere logical materials often pose analytical problems, is concerned, iron is considered as the intermediate which is confirmed by the difficulties in obtaining between macro- and micro-constituents in plants, certified values for this element in numerous cer- animals and humans [1]. Iron belongs to essential tification processes, regardless of the iron level in elements to most forms of life, including humans. candidate materials. Among six certified referenced The amount of iron needed for optimal health re- materials of plant origin for inorganic trace ana- flects a delicate balance between deficiency and lysis, issued by the Institute of Nuclear Chemistry excess. Since iron stimulates generation of free radi- and Technology (INCT), only in three cases the cals it can be potentially toxic, as well [2]. process of certification for iron has been success- Therefore, the reliable method for iron deter- ful. (It seems surprisingly that it has been possible mination in biological materials appears to be of to obtain certified values for iron in the case of RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 97 low level corn flour (INCT-CF-3), opposite to tobacco (CTA-OTL-1) or tea leaves (INCT-TL-1) with much higher iron content.) For the development of simple radiochemical procedure for selective iron separation from a biological matrix, the method of ion exchange column chromatography has been used. Iron chloride complexes have high affinity to strongly basic anion exchanger Dowex 1X4 in 9 M HCl, whereas iron shows an anomalous behaviour towards strongly acidic cation exchanger Dowex 50 WX4 in concentrated HBr solution [3]. In the first stage of the procedure, after elution of impurities, the iron has been quantitatively eluted from the anion exchange resin using 0.01 M HCl. In the second stage of the procedure, for further purification of 59Fe from accompanying radionuclides, the phenomenon: of the “anomalous sorp- – tion” of anionic iron bromine complexes [FeBr4 ] on a strongly acidic cation exchanger has been utilized. The remainder of impurities was removed with 8 M HBr solution. Then, rapid elution of iron with 3 M HBr solution was carried out. The efficiency of the procedure (98 ±2%) has been obtained for different kinds of biological Fig.2. Gamma-ray spectrum of analyte fraction received materials, i.e. of plant and animal origin in the 59 after passing the whole procedure A – CTA-VTL-2, 133 presence of radioactive tracer Fe as well as for mg; B – NIST Bovine Liver, 111 mg. the radioactive plant and animal samples. The proposed radiochemical scheme is illustrat- Gamma-ray spectrum of the analyte fraction, ed in Fig.1. obtained after passing the whole procedure and showing a high selectivity of the separation is illustrated in Fig.2. Iron determination by neutron activation analysis (NAA) is based on the convenient, long-lived radionuclide – Fe-59 (46 days), therefore, one can take advantage of the unique feature of the NAA, so called “self validation” of the method. The results obtained in the course of radiochemical NAA (RNAA) were compared with those obtained with the instrumental mode (INAA) and to the certified values (Fig.3).

Fig.3. The results of iron determination in plant material obtained by RNAA. RNAA and INAA compared to the certified values. Mean value and confidence limit, for α=0.95. The agreement of the two different approaches is a proof of the reliability of the proposed radiochemical procedure in the case of the material under this study. The procedure should be further tested on different kinds of samples of biological origin and fine- ly, it is intended to be used as reference method in the certification process of new certified materials Fig.1. Radiochemical scheme for isolation of iron from bio- prepared by the Department of Analytical Chemistry logical samples. of the INCT. RADIOCHEMISTRY, STABLE ISOTOPES, 98 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY References [2]. McCord J.M.: J. Nutr., 134, 3171S-3172S (2004). [3]. Minczewski J., Chwastowska J., Dybczynski R.: Anali- [1]. Kabata-Pendias A., Mukherjee A.B.: Trace elements za śladowa. WNT, 1973 (in Polish). from soil to human. Springer Verlag, 2006, 209 p.

FULLERENE AS SORBENT FOR SEPARATION AND DETERMINATION OF TOXIC ELEMENTS BY GF AAS Jadwiga Chwastowska, Witold Skwara, Monika Sadowska-Bratek, Jakub Dudek, Maria Dąbrowska, Leon Pszonicki

Nanostructures attract a great deal of interest be- fullerene C60 were compared with those of active cause their mechanical, electrical, optical and also carbon and silica gel C18 carring out the sorption chemical properties are often more advantageous of cadmium and lead complexes with APDC. For than those of macrostructures. The carbon nano- both elements, fullerene was the best sorbent from structures – fullerenes – the third allotropic form the point of view of sorption efficiency, selectivity of carbon, particularly C60 and C70, are the subject and pH interval [5,6]. Fullerenes found also the of investigation from the point of view of their po- application in the speciation analysis of mercury tential application in many fields, e.g. supercon- [6,7] and lead [8,9] in combination with gas chro- ductivity, photooptic, biochemistry, material engi- matography and mass spectrometry. neering or catalysis. The geometric structure of the It results from the literature data that fullerenes molecule C60 is composed of 12 pentagonal and 20 applied as sorbents have significantly better prop- hexagonal rings. The structural investigation indi- erties than chelating sorbents, however, in all de- cates that in the pentagonal rings the carbon atoms scribed works they were used in the flow-injection are bound by the single bonds whereas in the hexa- method and in a closed system. The aim of our gonal rings they are bound by the single and double work was to test the usefulness of the fullerene C60 bonds alternately. On the surface of pentagonal for the separation of heavy metals in the column rings one observes a slight deficiency of electron process in the open system. In such a case same dif- and, therefore, it becomes an acceptor of them. ficulties concerning the filling of column and sta- In the last years there appeared some publica- bility of the sorption process appeared and a seri- tions concerning the application of fullerenes as ous improvement of the procedure was necessary. sorbents of organic compounds (aromatic hydro- Two fullerenes were tested: C60 99.5% of Aldrich carbons, phenols, amines) and organometallic com- and C60 99.95% of American company SES Re- pounds. Heavy metal ions were sorbed in the form search. The first of them was dusty, hydrophobic of complexes with organic ligands [1-3]. The de- and it behaved as soot. For elimination of this be- rivatives of dithiocarbamates are used usually as haviour, it was necessary to remove the gases by complexing agent because of their good solubility sink the fullerene in a liquid and heating it at a in water. Most commonly, it was ammonium pyro- temperature of 40oC. The following liquids were lidinedithiocarbamates (APDC) [4]. Organic sol- tested: water, 80% ethyl alcohol, dioxane and 4 M vents, such as methylisobutyl ketone, ethanol and HNO3. Water was completely ineffective. Alcohol methyl acetate, or solutions of inorganic acids, caused formation of bubbles in the fullerene bed mainly of nitric acid were used as eluent. This re- on the column. Only dioxane and 4 N HNO3 elimi- sults from the mentioned publications that the nated the mentioned fullerene shortcomings. Al- fullerenes C60 and C70 have very good sorption prop- though dioxane dissolves slightly fullerene, how- erties such as stability, very large sorption surface ever, the quick heating up to 40oC, transfer into the and the possibility to interact with the sorbed com- column and washing with water does not change pound by π-electrons. The sorption properties of its sorption properties. Another serious shortcom- A x100 B x3000

Fig.1. Scanning microscope picture of fullerene C60 Aldrich (prepared by Dr. Bożena Sartowska). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 99

A x100 B x3000

Fig.2. Scanning microscope picture of fullerene C60 SES Research (prepared by Dr. Bożena Sartowska). ing was observed during the sorption process. The enabled to choose pH 5 as optimum for group sep- flow of sample trough the column causes that the aration of all elements. fullerene bed becomes more compact, suppresses Elution: As eluents there were tested various con- the flow rate and changes the sorption kinetics. To centrations of HNO3, a mixture of MIBK (methyl avoid this problem, a mixture of fullerene with a isobutyl ketone) and ethyl alcohol 1:1, 80% ethyl neutral material as a bed carrier was applied. The alcohol, various mixtures of 2 M HNO3 and ace- following carriers were tested: macro-porous silica tone, and dioxane. The flow rate during desorption –1 gel, gauze and quartz wool. The best results were was 0.5 ml·min . 6 M HNO3 and dioxane were most obtained for a mixture 50 mg of quartz wool and effective from the point of view of the desorption 100 mg of fullerene. On such a bed the sorption efficiency and as the medium for GF AAS deter- process occurs with a well repeated kinetics and mination. The total amounts of eluents necessary with the quantitative efficiency. for full desorption was 5 and 20 ml for 6 M HNO3 The second tested fullerene C60 99.95% SES and dioxane, respectively. Research differs significantly from the first one. Under the above described conditions, the ef- The differences in their structures are demonstrat- ficiency of the separation process oscillates in the ed in Figs.1 and 2 obtained by a scanning micro- interval 95-100% for all tested elements: cadmium, scope. The size of SES fulleren particles is more lead, copper, nickel and cobalt. Taken into account homogeneous (Figs.1A and 2A) and the surface of the nanogram concentration level such results may grains is much more developed and covered with be considered as quantitative and satisfactory. a layer of regular pores (Figs.1B and 2B). Its be- Although fullerenes applied as sorbents in the haviour as a sorbent was essentially similar to that open system do not demonstrate so many advan- of Aldrich fullerene, however, all observed short- tages as those used in the flow-injection closed sys- comings was significantly weaker and easier for tem, however, they keep their main advantage in elimination. Therefore, for further investigations comparison with chelating sorbents, i.e. stability in this material was accepted. the time and the possibility of the multiple appli- The optimal conditions for group separation of cation. The main shortcomings there are the dif- five elements – cadmium, lead, copper, nickel and ficulty at the preparation of the column and the cobalt – in the form ready for graphite furnace necessity to use as sorbent the fullerene settled on atomic absorption determination (GF AAS) were a bed carrier, e.g. quartz wool. established as follows: Preparation of column: 100 mg of fullerene was References added to few millilitres of dioxane and mixed care- [1]. Ballesteros E., Gallego M., Valcárcel M.: J. Chromatogr. fully till the fullerene particles settle on the bottom, A, 869, 101 (2000). then, 50 mg of quartz wool, cleaned in 7 N HNO3 [2]. Baena J.R., Gallego M., Valcárcel M.: Trends Anal. and rinsed by water, was added and mixed till Chem., 21, 187 (2002). fullerene covered steadily the wool fibres. So pre- [3]. Valcárcel M., Cárdenas S., Simonet B.M., Moliner-Mar- pared sorbent was transferred to the column and tínez Y., Lucena R.: Trends Anal. Chem., 27, 34 (2008). rinsed few times by water. [4]. Pereira M.G., Pereira-Filho E.R., Berndt H., Arruda Complexation and sorption of metallic ions: 2 ml of M.A.Z.: Spectrochim. Acta, Part B, 59, 515 (2004). 0.05% APDC solution was added to 20 ml of water [5]. Gallego M., Petit de Peña Y., Valcárcel M.: Anal. solution with a chosen pH and, then, the standard Chem., 66, 4074 (1994). [6]. Petit de Peña Y., Gallego M., Valcárcel M.: J. Anal. solutions of five tested elements was added in the At. Spectrom., 12, 453 (1997). amounts between 40 to 400 ng. So prepared solu- [7]. Muñoz J., Gallego M., Valcárcel M.: Anal. Chim. Acta, tion was mixed 10 min and transferred to the col- 548, 66 (2005). umn. The sorption process was carried out at the [8]. Muñoz J., Gallego M., Valcárcel M.: J. Chrom. A, flow rate 1-2 ml·min–1 and after sorption the col- 1055, 185 (2004). umn was washed twice with the primary solution. [9]. Baena J.R., Cárdenas S., Gallego M., Valcárcel M.: The tested pH interval was between 1 and 6.5 and Anal. Chem., 72, 1510 (2000). RADIOCHEMISTRY, STABLE ISOTOPES, 100 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

SYNTHESIS OF TiO2 THIN FILMS ON POROUS Ni OR Ni/NiO CATHODES FOR MCFC BY SOL-GEL PROCESS Wiesława Łada, Andrzej Deptuła, Danuta Wawszczak, Tadeusz Olczak, Elisabetta Simonetti1/ 1/ Italian National Agency for New Technologies, Energy and the Environment (ENEA), C.R.E. Casaccia, Rome, Italy

The subject of this study was to elaborate a method the cathode and the electrolyte at a cell working o for obtaining titanium dioxide (TiO2) layers on temperature of 600-700 C, the result of which are metallic substrates, particularly on nickel cathodes products that cause cathode short-circuit, and con- used in fuel cells where fused lithium-potassium sequently shortening of electrode lifetime. carbonates (Li0.62K0.38)CO3 are electrolytes in mol- There exist methods that prolong cathode life- ton carbonate fuel cell (MCFC) The most serious time in cells of this type by means of covering them problem in industrial implementation of fuel cells with a protective layer of, e.g. lithium cobaltite in order to obtain electricity is the reaction between (LiCoO2) [1]. In the Institute of Nuclear Chemistry a’ a’’

b’ b’’

c’ c’’

Fig.1. SEM images for sample A before and after thermal treatment at 650oC. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 101

o Fig.2. SEM-EDX images of TiO2-Ni after conductivity measurements at 650 C. and Technology (INCT) layers of lithium cobaltite (a”, b”, c”) after conductivity measurements in o doped with magnesium Li(Mg0.05)Co0.95O2 were MCFC at 650 C for several hours. obtained by the dipping sol-gel method [2]. The images for sample A show that before ther- Recently [3], titanium dioxide was proposed in mal treatment an amorphous layer covered the search for more innovative methods of cathode surface of the cathode that disappears during heat protection. According to [3], titanium-ammonium treatment. Also morphological changes can be ob- oxalate was deposited on a nickel powder. After served: an improvement of the porosity and the heat treatment, cathodes were prepared from a growth of grains on the surface. It can be assumed mixture TiO2/Ni. In [4], TiO2 films were formed that these grains are related to the TiO2-coated directly by spin coating. NiO formation on the surface. Also, in sample B, The goal of this work was the formation of thin it could be noted the growth of grains and more o films of TiO2 on Ni cathode by a method elabo- crystalline materials after heat treatment at 650 C. rated earlier in the INCT [2]. Preliminary experi- From the EDX (energy dispersive X-ray analysis) ments have shown that Ni plates strongly reacts study it is evident that Ti is quite homogeneously with a strongly acidic (pH<0) nitrate-stabilized ti- distributed on the grains structure (Figs.2 and 3). tania sol with an addition of 0.1 M of ascorbic acid, To test the stability of the materials with time prepared according to the original INCT process we have heated NiO and both samples A and B of [5]. To protect from dissolving the cathodes were TiO2 on NiO in air for many hours. To compare impregnated by ethyl alcohol (96%) for 1 h (sample the different materials, results are plotted together A) or 2 min (sample B) according to the original (Fig.4). From this figure it is possible to point out procedure [6]. After impregnation, the Ni plates the values of NiO resistance which are constant were subjected for dipping in a sol with a viscosity after about 20 h, while TiO2 on NiO samples tend of 7-10 cSt. Dipping and pulling speed were iden- to a constant resistance value in about 100 h: 476 tical and equal to 1.7 cm/s, the immersion time was Ω (sample A), 561 Ω (sample B). equal to 1 min. Then gelation took place in one On the other hand, it can be noticed it is im- hour at room temperature. possible to predict, by these measures, what will Additionally, the layers deposited on cathodes be the behavior of the materials in a molten car- did not undergo heat treatment and bypassed this bonate fuel cell where LiCO3 are present and time-consuming and expensive stage, which causes probably will take place the reaction: a decrease in cathode mechanical strength. TiO2 + LiCO3 → Li2TiO3 + CO2 In Figure 1 are shown the SEM (scanning elec- A fast change of the electronic conductivity on tron microscopy) images of freshly prepared TiO2 TiO2 on Ni cathode (sample B) was observed in a on Ni (sample A) cathodes (a’, b’, c’) and cathodes CO2 atmosphere in which the electrode resistance

o Fig.3. SEM-EDX images of TiO2-Ni after conductivity measurements at 650 C. RADIOCHEMISTRY, STABLE ISOTOPES, 102 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY Summing-up, it has been found that thin films of TiO2 can be formed on Ni porous cathodes for MCFC by the dipping technique elaborated earlier using titania-nitrate–ascorbate sols [2], but only if the substrates are impregnated by ethanol before processing [6]. Results of conductivity measurements in MCFC were satisfactory.

References [1]. Kuk S.T., Song Y.S., Kim K.: J. Power Sources, 54, 403 (1995). [2]. Łada W., Deptuła A., Olczak T., Chmielewski A.G., Moreno A.: Method for obtaining Ni/NiO cathodes. Polish Patent 199551. Fig.4. Electrical resistance nickel covered with TiO at 650oC 2 [3]. Ming Zi Hong, Hyun Suk Lee, Min Hyuk Kim: J. Power in air as a function of time. Sources, 156, 158-165 (2006). increase from 561 to 646 Ω. Probably, a selective [4]. Truien I., Van Bael M.K., Van den Rul H.: J. Sol-Gel Sci. Technol., 41, 43-48 (2007). interaction of CO2 on active sites used for the hop- ping of the charge carriers took place, with the [5]. Deptuła A., Łada W., Olczak T., Chmielewski A.G., Casadio S., Alvani C., Croce F.: Method for obtaining consequence to block the conduction mechanism. titanium dioxide and titanates of lithium and barium Anyway, when the air atmosphere is fluxed again, from titanium tetrachloride. Polish Patent 198039. the resistance starts to decrease towards lowest [6]. Łada W., Deptuła A., Wawszczak D., Simonetti E.: values (or lower than the corresponding ones in Method for obtaining protective coatings on nickel the initial air), the behavior of this sample is quite cathodes. Patent Application P.384062. unusual and not proper.

SYNTHESIS AND TESTING OF GEL METAL-OXIDE COMPOSITES AS FILLING MATERIALS FOR 188W/188Re GENERATOR COLUMNS Edward Iller1/, Andrzej Deptuła, Fabio Zaza2/, Wiesława Łada, Tadeusz Olczak, Danuta Wawszczak, Marcin Brykała 1/ Institute of Atomic Energy, Radioisotope Centre Polatom, Otwock-Świerk, Poland 2/ Italian National Agency for New Technologies, Energy and the Environment (ENEA), C.R.E. Casaccia, Rome, Italy

Rhenium-188 (188Re) has recently emerged as use- nology [4]. The syntheses of zirconium-tungstate ful therapeutic radioisotope in clinical trials such as (Zr/W), titanium-tungstate (Ti/W) and zirconium- cancer radioimmunotherapy, palliation of skeletal -silicate-tungstate (Zr:Si/W) composites using the bone pain, endovascular brachytherapy to prevent sol-gel method were performed. The initial stage restenosis after angioplasty as well as in the pre- of the process is the preparation of ascorbate + clinical development of novel radiopharmaceuti- NH4 -tungsten sol [5], next, the separately pre- cals. Rhenium is a chemical analogue of technetium pared zirconyl, titanium or silicon sols are added and exhibits practically identical chemical and bio- gradually to the reaction mixture. After gelation distribution properties. Emission characteristics step, the gels were thermally treated according to and physical properties make it suitable for appli- temperatures indicated by thermal analysis (ther- cation in radionuclide therapy. The high energy mogravimetry – TG, differential thermal analysis 188 o beta-particles of Re (Eaverage=0.764 MeV) are – DTA), i.e. at 500, 650 and 800 C. effective over a several mm range, which is suffi- The elemental composition of nanocomposites cient to eradicate medium or large tumors, while was determined by the neutron activation analysis its low energy and low abundance of gamma pho- (NAA) method. Samples of nanocomposites (20 tons (155 keV, 15% abundance) are suitable for mg), substratum (10 mg of WO3, ZrO2, TiO2 and imaging. SiO2) and standards prepared from appropriate At present, the carrier-free 188Re is obtained amounts of spectral purity metals or oxides placed from a 188W/188Re radionuclide generator in which in polyethylene vials were irradiated at a thermal the tungsten-188 (188W) in the form of sodium-tung- neutron flux of 9.7x1013 cm–2 s–1 for 1 h in the nu- state 188W solution is adsorbed on the alumina fill- clear reactor MARIA (Institute of Atomic Energy, ing of generator column. An alternative method is Otwock-Świerk, Poland) and cooled for one week. a gel generator system, which utilizes the gel pre- The gamma-ray spectra of the samples and stan- pared from a mixture of zirconium, titanium or dards were measured using a high resolution HPGe other metal sols with tungstate sol [1-3]. A specific (well type) spectrometer. Then, the nanocomposite method for the synthesis of these components was samples were transferred into chromatographic performed by complex sol gel process elaborated columns and elutions of 188Re using 0.9% NaCl so- at the Institute of Nuclear Chemistry and Tech- lution were carried out. Purity of the 188Re frac- RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 103 tion and efficiency of elution were determined by both cases the results are presented in form of the gamma-ray spectrometry for different samples of plots of intensity of scattered neutrons vs. the scat- nanocomposites and compared. It has been found tering vector length Q. that the best results of elution (profile and effluent The atomic ordering of the composites was studied by a wide range scattering angle (10-110o) neutron diffraction. The measurements were carried out with a double crystal monochromator diffractometer employing Cu single crystals with (200) reflection planes. Since the maximum of the reactor neutron spectrum is close to the 0.1 nm wavelength region, the neutrons of wavelength λ=0.09925 nm were applied to minimize the contribution of the second order diffraction effects. It was found that the diffraction patterns for samples annealed at 500oC do not reveal any Bragg peaks but only a broad halo centered near the scattering vector of 40 nm–1 (Fig.2). Fig.1. Elution profile of neutron irradiated nanocomposite o WO -ZrO (1:2, 500oC) with 0.9% NaCl. For samples annealed at 650 C, a few distinct 3 2 maxima were observed for each composition. purity) appeared in the case of filling of chromato- The strongest maximum is centered near Q=32 –1 –1 graphic column by WO3-ZrO2 in which the molar nm and the second one near Q=15 nm . Some ratio of oxides was 1:2 and the calcination tempera- signs of other maxima are present near 49 and 60 o –1 ture was 500 C and WO3-TiO 2 with the molecular nm . ratio 1:2 and calcination temperature 650oC. The The diffraction patterns of samples annealed o samples containing WO3-ZrO2-SiO2 did not dis- at 800 C consist of several Bragg peaks charac- tinguish by a good elution profile. teristic of fully fledged crystalline structure. In the elution of neutron irradiated nanocom- The nanoscale structure of the composites was o 188 posite WO3-ZrO2 (1:2, 500 C) with 0.9% NaCl Re determined by the small-angle neutron scattering is eluted in the first fraction and no impurities were (SANS) in 0.1 nm–1

400 Intensity [counts] 20 Intensity [counts] 200 Intensity [counts]

wzr_08 wzr_07 0 0 0

020406080 020406080 020406080 Q [nm-1] Q [nm-1] Q [nm-1]

Fig.2. An example of wide-angle neutron diffraction measurements (WO3-ZrO2 annealed at different temperatures) observed in the rhenium fraction (Fig.1). However, was studied with the λ=0.237 nm neutrons mono- the elution efficiency was rather low ~15%. chromatized with a double PG monochromator The atomic ordering and the nanoscale struc- and filtered with a 3 cm thick PG filter. ture of the WO3-ZrO2 composites were studied by The SANS patterns depend on the annealing a wide and small angle neutron diffraction. In temperature. The differences between the SANS

4 4 1:2 500°C 5h 1:2 650°C 5h 1:2 800°C 5h 3.2 α = 3.0 3 α = 1.6 3 2.8 α = 2.4 log I log I 2 log I 2.4 2

2 1

c505 c 517 c 516 1.6 1 -1.2 -0.8 -0.4 0 -1.2 -0.8 -0.4 0 -1.2 -0.8 -0.4 0 log Q [nm-1] log Q [nm-1] log Q [nm-1]

Fig.3. Examples of SANS patterns for a 1:2 mixture of WO3-ZrO2. RADIOCHEMISTRY, STABLE ISOTOPES, 104 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY curves are made more visible if plotted in the log- Table 1. Activity of eluate before purification. arithmic variables (Fig.3). For samples annealed at 500oC, the smooth monotonic dependence of Isotope Activity [kBq] the intensity of scattered neutrons on scattering 188Re 10950 vector was observed. The most diversified SANS 186 curves were obtained for 650oC annealed samples. Re 170 For zirconium rich composites, a kind of ridge is 185W 93.3 –1 revealed at Q=0.4 and 0.6 nm , for 1:1 and 1:2 95 composition, respectively. The existence of similar Zr 84.7 ridge at Q=0.15 nm–1 can be only presumed in the 60Co 76.6 o case of 3:2 composite annealed at 650 C. The an- 95m nealing at 800oC produces a SANS pattern with Nb 49.2 two discernible regions of different slope of inten- 65Zn 6.2 sity of scattering vector dependence. The composites were analyzed by an X-ray dif- further investigations. A 2.9 g sample was placed fraction (XRD) technique using a Rigaku Miniflex in a quartz ampoule and irradiated at the MARIA diffractometer with Cu-Kα radiation (tube output nuclear reactor in a thermal neutron of flux 1.7x1014 voltage – 30 kV, current – 25 mA) and scanning cm–2 s–1 for 400 h. After irradiation, the target was range from 2Θ=10o to 2Θ=90o (step – 0.02o and “cooled down” for three weeks. The gamma spec- rate – 2o/min). The gels annealed at 500oC are trometry measurements of the sample performed practically amorphous, but on the XRD patterns with the Ge(Li) detector revealed the following 95 95m 188 188 181 60 of WO3-ZrO2 (1:1, 1:2, 3:2) composites annealed radionuclides: Zr, Nb, Re, W, Hf, Co, at 650oC, few peaks beyond the background level 186Re. The cooled gel was packed into the generator were observed. The gels annealed at 800oC are chromatographic column that was washed up with fully crystalline and contain both oxides in separate 30 ml of saline and 20 ml of 1 M HCl. After that 188 crystalline phases: ZrO2 in two high symmetry forms treatment, the elution of Re with 10 ml of saline 188 – cubic and tetragonal, and WO3 in monoclinic was performed. To evaluate Re profile 1 ml por- phase. An example of XRD patterns for WO3-ZrO2 tion of the generator eluate were collected and (1:2) is shown in Fig.4. measured with an ionization chamber. The radio- The zirconium-tungstate gel with 1:2 molar ratio isotope composition of the eluate was determined of the oxides annealed at 500oC was selected for with gamma spectrometry (Table 1). In some experiments the eluate was purified in a small 1.8 g alumina column for the purpose of purification of the generator eluate. The results of the experiments are shown in Table 2. Table 2. Activity of eluate after purification.

Isotope Activity [kBq] Content [%] 188Re 8289 99.66 60Co 23.6 0.28 95mNb 2.2 0.03 95Zr 2.1 0.03

It has been found that from all the investigated systems (WO3-ZrO2, WO3-TiO 2, WO3-ZrO2-SiO2) the best elution characteristic appeared in the amorphous composite ZrO2-WO3 with a molar portion 1:2 annealed after synthesis at 500oC. Long irradiation time (400 h) of the ZrO2-WO3 gel and elution performance confirmed its applicability as filling material for a chromatographic column of 188W/188Re gel isotope generator. In the future use of semi-enriched target material with 188W would be beneficial for the development of this type of tungsten-rhenium gel generator.

References [1]. Dadachov M.S., Lambrecht R.M., Hetherington E.: J. Radioanal. Nucl. Chem. Lett., 188, 267 (1994). [2]. Dadachov M.S., Lambrecht R.M.: J. Radioanal. Chem. Lett., 200, 211 (1995).

Fig.4. XRD analysis of WO3-ZrO2 (1:2) nanocomposites [3]. Dadachov M.S., Le Van So, Lambrecht R.M., Dada- after different thermal treatments. chova E.: Appl. Radiat. Isot., 57, 641 (2002). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 105

[4]. Deptuła A., Łada W., Olczak T., Lanagan M.T., Dorris [5]. Deptuła A., Łada W., Olczak T., Sartowska B., Giorgi S.E., Gorett K.C., Poeppel R.B.: Method for obtaining L., Moreno A., Di Bartalomeo A.: J. New Mater. high-temperature superconductors. Polish Patent No. Electrochem. Syst., 6, 71 (2003). 172618.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXVIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF PYRIDAZINE-4-CARBOXYLIC ACID HYDROCHLORIDE Wojciech Starosta, Janusz Leciejewicz

The structure of 4-carboxypyridazin-1-ium chlo- in the range 3.254(2) to 3.497(2) Å make coplanar ride is built from chloride anions and protonated layers. The shortest distance between pyridazine pyridazine-4-carboxylate cations. Chloride anions rings belonging to adjacent layers is 3.339(2) Å. The pyridazine ring is planar (r.m.s. 0.0060 Å) and forms with the carboxylate group (C7/O1/O2) a dihedral angle of 27.7(1)o. Figure 1 shows the cation and anion with atom labels, Fig.2 – the packing diagram. X-ray data collection was carried out on a KUMA-KM4 four circle diffractometer at the Institute of Nuclear Chemistry and Technology. Structure solution and refinement was performed using SHELXL-97 program package.

References [1]. Part LXVI. Starosta W, Leciejewicz J.: Hydrazinediium bis(6-carboxypyridazine-3-carboxylate) dihydrate. Acta Crystallogr., E64, o461, Sup-1–Sup-7 (2008). [2]. Part LXVII. Starosta W., Leciejewicz J.: Three-dimensional polymeric molecular pattern in the crystal structure of a Ca(II) complex with pyrazine-2,3,5,6-tetra- Fig.1. A cation and an anion of 4-carboxypyridazin-1-ium carboxylate and water ligands. J. Coord. Chem., 61, chloride with atom labels and 50% probability displace- 490-498 (2008). ment ellipsoids. [3]. Part LXVIII. Starosta W., Leciejewicz J.: 4-Carboxy- pyridazin-1-ium chloride. Acta Crystallogr., E64, o-1553, bridge the cations via hydrogen bonds O2-H2…Cl1 (I) Sup-1–Sup-6 (2008). and N1-H1…Cl1 with lengths 2.9464(14) and [4]. Part LXIX. Starosta W., Leciejewicz J.: The crystal 3.0373(15) Å respectively, to form ribbons (sym- and molecular structures of hydrazine adducts with metry code: (I) x+1/2, -y+3/2, z+1/2). The rib- isomeric pyrazine dicarboxylic acids. Open Crystallogr. bons linked by van der Waals forces with lengths J., 1, 31-36 (2008).

Fig.2. The packing diagram of 4-carboxypyridazin-1-ium chloride structure. RADIOCHEMISTRY, STABLE ISOTOPES, 106 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXIX. THE CRYSTAL AND MOLECULAR STRUCTURES OF HYDRAZINUM ADDUCTS OF THREE ISOMERIC PYRAZINE DICARBOXYLIC ACIDS Wojciech Starosta, Janusz Leciejewicz

The structure of bis(hydrazineH)pyrazine-2,3-dicarboxylate is composed of singly-protonated hydrazine cations and doubly-deprotonated pyrazine-2,3-dicarboxylate anions. Atoms forming the

Fig.3. Hydrazine cation and pyrazine-2,5-dicarboxylate anion with atom numbering scheme. The unit cell of hydrazine adduct with pyrazine-2,5-dicarboxylate contains four singly-protonated hydrazine cations and two doubly-deprotonated pyrazine-2,5-dicarboxylate anions with their geometrical centres at the inversion centres at Fig.1. The content of the asymmetric unit cell of bis(hydra- zineH)pyrazine-2,3-dicarboxylate with atom labelling scheme. ½,0,½ and 0,½,0. Thus, the cation to anion ratio is as 2:1. Figure 3 shows a cation and an anion with hydrazine cations belong to two symmetry-inde- atom labels. The interatomic distance N-N within pendent sites. Consequently, the cation to anion the cation is 1.440(2) Å, commonly observed in hy- ratio is as 2:1. Figure 1 shows the atom labelling drazine adducts with carboxylate compounds. Atoms scheme, Fig.2 – the packing diagram with hydro- forming the pyrazine ring are coplanar [r.m.s. gen bonds marked by broken lines. N-N distances 0.0009(1) Å], the carboxylic groups deviate from the within both protonated hydrazine cations are close ring plane by 11.7(1)o. The observed interatomic to those observed in all up to now reported hydra- distances and bond angles do not differ from those zine adducts with dicarboxylic acids The carboxylic reported in the structure of the acid. The alignment group deviates from the pyrazine – ring plane by of the cations and anions in the unit cell is shown 1.7(1)o, while the (C8/O3/O4) group – by 89.3(2)o. in Fig.4. The cations form catenated assemblies The latter values, as well as the bond distances bridging the anions through hydrogen bonds with lengths in the range from 2.755(2) to 2.934(2) Å in which the cations are the donors and the carboxylate O and hetero-ring N atoms are the acceptors. The structure of the adduct with pyrazine-2,6-dicarboxylic acid is also monoclinic. Its characteristic

Fig.2. Packing diagram of bis(hydrazineH)pyrazine-2,3-dicarboxylate. Broken lines show the hydrogen bonds. and bond angles within the anion agree with those observed in the structures of both modifications of pyrazine-2,3-dicarboxylic acid dehydrate. Hydrazine cations act as donors in a system of rather weak hydrogen bonds. The acceptors are hetero-ring N and carboxylate O atoms of the anions, forming a Fig.4. Packing diagram of hydrazine adduct to pyrazine- three-dimensional network. 2,5-dicarboxylic acid. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 107 the hetero-ring nitrogen atom situated between the carboxylate groups. The structural units are shown in Fig.5; their alignment in the unit cell – in Fig.6. The pyrazine ring atoms are coplanar (r.m.s.

Fig.6. The alignment of molecules in the unit cell of an hy- Fig.5. Molecules constituting the structure of hydrazine ad- drazine adduct with pyrazine-2,6-dicarboxylic acid. duct with pyrazine-2,6-dicarboxylic acid with atom labelling. 0.00TT); carboxylate groups deviate from it by feature is the positional disorder of one of the car- 9.99o (C7/O1/O2) and 8.88o (C8/O3/O4). boxylate hydrogen atoms resulting in two alterna- X-ray data collection was carried out on a tive molecular patterns: either ionic with singly KUMA-KM4 four circle diffractometer at the protonated hydrazine cation and singly deproto- Institute of Nuclear Chemistry and Technology. nated pyrazine-2,6-dicarboxylate anion or hydra- Structure solution and refinement was performed zine molecule and zwitterionic pyrazine-2,6-di- using SHELXL-97 program package. carboxylate molecule with a proton attached to

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXX. THE CRYSTAL AND MOLECULAR STRUCTURE OF A DIOXOURANIUM COMPLEX WITH PYRIDAZINE-3-CARBOXYLATE AND WATER LIGANDS Janusz Leciejewicz, Wojciech Starosta

The structure of bis[(μ-pyridazine-3-carboxylato-O,O’) gonal bipyramid. Hetero-ring N21 atom deviates (pyridazine-3-carboxylato-N,O)aquo-dioxouran- from its equatorial plane [r.m.s. 0.0674(2) Å] by ium(VI)] dihydrate [UO2(C4H3N2COO)2H2O]2·2H2O +0.1228(2) Å, the carboxylate O21 atom by is composed of centrosymmetric dimeric molecules -0.1056(2) Å. The U-O and U-N bond distances 2+ in which each UO2 ion is coordinated by two ligand and bond angles in the coordination polyhedron molecules and a water molecule. The ligand mol- fall in the range commonly observed in uranyl com- ecules act in different coordination modes. One of plexes with carboxylate ligands. The O-U-O angle them chelates the uranyl ion using its N,O bonding moiety consisting of a hetero-ring N atom and an O atom of the nearest carboxylate group, the other donates for coordination only both its carboxylate O atoms. The latter acting as bidentate bridge two different adjacent cations and give rise to a dimeric molecular assembly. A water O atom completes the number of coordinated atoms around the uranyl ion to five. Figure 1 shows a dimer with atom labels. Uranium atoms, ligand molecules and coordinated water O atoms form a plane [r.m.s. 0.1063(2) Å] with the coordinated water O atoms and the hetero-ring C14 atoms showing the shifts of -0.4749(2) and +0.2002(2) Å, respectively. The coordination polyhedron of the U ion is a penta- Fig.1. A dimer of [UO2(C4H3N2COO)2H2O]2·2H2O with atom labels and 50% probability displacement ellipsoids. RADIOCHEMISTRY, STABLE ISOTOPES, 108 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Fig.2. Packing diagram of [UO2(C4H3N2COO)2H2O]2·2H2O structure. 2+ o in the UO2 ion is 178.4(3) . Also the bond distances are held together by hydrogen bonds operating and angles within the ligand molecule do not dif- between the coordinated and solvation water mol- fer from those reported for the molecule of the ecules and carboxylate oxygen atoms in the adja- parent acid. The dimers interact through hydrogen cent sheets. The packing diagram of the structure bonds and form molecular sheets in which coordi- is shown in Fig.2. nated (O3) and solvation (O4) water molecules act X-ray data collection was carried out on a as donors and carboxylate O22 atoms as acceptors. KUMA-KM4 four circle diffractometer at the An intra-dimer bond of 2.749(9) Å operating be- Institute of Nuclear Chemistry and Technology. tween the coordinated water molecule O3 and the Structure solution and refinement was performed hetero-ring N11 atom is also observed. The sheets using SHELXL-97 program package.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXXI. THE CRYSTAL AND MOLECULAR STRUCTURES OF TWO CALCIUM(II) COMPLEXES WITH PYRIDINE-2,3-DICARBOXYLATE AND WATER LIGANDS Wojciech Starosta, Janusz Leciejewicz

The asymmetric unit cell of triclinic catena-tetra- dine rings of both ligand molecules are planar: quo(μ-pyridine-2,3-dicarboxylato-N,O;O’)calc- r.m.s. is 0.0065(1) Å in the case of the ligand coor- ium(II) contains two symmetry independent struc- dinated to Ca1 ion and 0.0081(1) Å in the case of tural units, each composed of a Ca(II) ion coordi- the ligand coordinated to the Ca2 ion. Carboxylate nated by a ligand molecule via its N,O bonding moiety, four water oxygen atoms and a carboxylate oxygen atom donated by an adjacent structural unit. In this way, the structural units form molecular ribbons propagating in the [010] crystal direction bridged by O atoms donated by the second carboxylate groups of the adjacent ligands. Figure 1 shows the two symmetry independent structural units with atom labels, Fig.2 – a fragment of a ribbon and its alignment in respect to the unit cell. Pyri-

Fig.2. The alignment of a molecular ribbon in the unit cell of catena-tetraquo(μ-pyridine-2,3-dicarboxylato-N,O;O’)calcium(II).

Fig.1. Molecular unit constituting the structure of catena-te- groups make the following dihedral angles with traquo(μ-pyridine-2,3-dicarboxylato-N,O;O’)calcium(II) the pyridine rings: (C17/O11/O12) – 9.4(1)o, (C18/ with atom labelling. O13/O14) – 91.1(1)o and (C27/O21/O22) – 6.4(1)o, RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 109 (C28/O23/O24) – 82.9(1)o. The observed bond distances and bond angles within the ligand molecules do not differ from those reported for the parent acid. The coordination geometry of both Ca(II) ions is pentagonal bipyramidal with strongly distorted pentagonal equatorial planes, bridging carboxylate O atoms and water O atoms forming the apices of the bipyramids. In the case of Ca1 coordination polyhedron, the deviations from the mean equatorial plane [r.m.s. 0.2340(1) Å] range from -0.3691(1) Å for the O11 atom to +0.4181(1) Å for the O1 atom while for the coordination polyhedron around the Ca2 ion the relevant parameters are: r.m.s. 0.2285(1) Å, maximum and minimum deviations from the mean equatorial plane +0.3082(1) Å for the O5 atom and -0.1375(1) Å for the O7 atom. Coordinated water molecules act as donors in an extended network of hydrogen bonds with lengths ranging from 2.68 to 3.00 Å. The accep- Fig.4. A structural unit of catena-trisaquo[(μ-2,3-dicar- tors are carboxylate and coordinated water O atoms. boxypyridin-1-ium-O,O’;O’’)(H pyridine-2,3-dicarboxyla- to-N,O)] calcium(II) with atom labels.

atom N11. Three water oxygens (O1, O2, O3) complete the coordination around the Ca(II) ion to eight atoms. The resulting coordination polyhedron is a bicapped on one side pentagonal bipyramid with a strongly distorted equatorial plane (r.m.s. 0.3992 Å) composed of the following atoms (with shifts from the mean plane): O13 (-0.6865 Å), O11(+0.2713 Å), O12(+0.6433 Å), N21(-0.5110 Å) and O21(+0.0495 Å), the O3 atom forming a single apex on one side and O1 and O2 atoms – two apices on the other. The observed bond distances and bond angles within both ligand molecules are close to those reported for the parent acid. The pyridine ring of ligand (1) is planar (r.m.s. 0.0113 Å); the carboxylate groups (C17/O11/O12) and (C18/O13/14) make with it dihedral angles of 86.6(2)o and 4.7(2)o, respectively. The pyridine ring Fig.3. The alignment of molecular ribbons in the structure of ligand molecule (2) is also planar (r.m.s. 0.0123 of catena-trisaquo[(μ-2,3-dicarboxypyridin-1-ium-O,O’;O’’) Å), its carboxylate groups form with it dihedral (H pyridine-2,3-dicarboxylato-N,O)] calcium(II). angles of 21.8(2)o (C27/O21/O22) and 17.0(2)o The polymeric structure of catena-trisaquo[(μ- (C28/O23/O24). The pyridine-rings of ligands (1) 2,3-dicarboxypyridin-1-ium- O,O’;O’’)(H pyridine- and (2) are inclined each to the other by 63.1(2)o. 2,3-dicarboxylato-N,O)] calcium(II) is also com- The protonated carboxylate O23 atom acts as a posed of molecular ribbons. They propagate in the donor and forms a strong intramolecular hydrogen c direction of the unit cell, as illustrated in Fig.3. bond of 2.423(12) Å to the carboxylate O22 atom The ribbons are built up of structural units. One of belonging to the same ligand molecule. Weaker them is shown in Fig.4 with atom labelling scheme. hydrogen bonds with distances in the range from Each Ca(II) ion is chelated by a N,O bonding moiety 2.713(8) to 2.906(8) Å are also observed as operat- of the ligand molecule denoted as (2) – atoms N21 ing between coordinated water O atoms and car- and O21, the second oxygen atom of this carboxy- boxylate O atoms of the same structural unit. Co- late group O22 does not participate in coordinat- ordinated water molecules participate as donors in ing, similarly as the other carboxylate group of a hydrogen bond network in which the acceptors this ligand (C28/C23/C24) which remains proto- are carboxylate O atoms of the adjacent ligand nated. The bridging of Ca(II) ions occurs through molecules. The hetero-ring N11 atom and the at- the ligand molecule denoted as (1) which uses its tached to it H111 atom are active in two bonds: carboxylate group (C17/O11/O12) acting in a bi- one to a coordinated water molecule O1(iv), the dentate mode: O11 – Ca and O12 – Ca(i). In addi- other – to the carboxylate O14(ii) atom, each be- tion, the carboxylate O13 atom donated by the longing to a different adjacent ligand. (C18/C13/C14) group of this ligand is also coordi- X-ray data collection was carried out on a nated to the Ca ion while the O14 atom does not KUMA-KM4 four circle diffractometer at the take part in coordination. As a whole, the ligand Institute of Nuclear Chemistry and Technology. molecule (1) is also univalent, since a proton has Structure solution and refinement was performed been detected to be attached to the hetero-nitrogen using SHELXL-97 program package. RADIOCHEMISTRY, STABLE ISOTOPES, 110 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXXII. THE CRYSTAL AND MOLECULAR STRUCTURE OF Pb(II) COMPLEX WITH PYRIDAZINE-4-CARBOXYLATE AND WATER LIGANDS Wojciech Starosta, Janusz Leciejewicz

The triclinic structure of a Pb(II) complex with pyridazine-4-carboxylate and water ligands is composed of dimeric assemblies in which two symmetry related Pb(II) ions are bridged by a pair of two symmetry related pyridazine-4-carboxylate ligand molecules through their both hetero-ring N atoms [N11-Pb 2.888(7) Å, N12-Pb(i) 2.893(7) Å] and two symmetry related coordinated water O3 atoms [O3-Pb 2.706(6) Å, O3-Pb(i) 2.849(7) Å]. The coordination geometry around each Pb(II) ion involves also two carboxylate O atoms [Pb-O21 2.647(7) Å, Pb-O22 2.591(6) Å] and three coordinated water molecules [mean Pb-O 2.633 Å]. Figure 1 shows a dimer with atom labels, Fig.2 – the alignment of the dimers in the unit cell. A highly irregular coordination environment of the Pb(II) ion with C.N. 9 Fig.1. A structural unit of dimeric Pb(II) complex with py- is observed. The bond distances and bond angles ridazine-4-carboxylate and water ligands showing the atom of the Pb(II) fall reasonably in the range observed labelling scheme. in the structures of other Pb(II) complexes with carboxylate ligands. Both pyridazine rings are almost of hydrogen bonds operating between unbonded planar with r.m.s. of 0.0135 Å (ligand 1) and 0.0038 hetero-ring N21 and N22 atoms and carboxylate Å (ligand 2). The plane of the coordinated carbo- O11 and O12 atoms and coordinated water mol- xylic group (C27/O21/O22) makes with the relevant ecules in adjacent dimers.

Fig.2. The alignment of dimers in the structure of a Pb(II) complex with pyridazine-4-carboxylate and water ligands. pyridazine ring a dihedral angle of 11.8(1)o; the X-ray data collection was carried out on a non-coordinated carboxylic group (C17/O11/O12) KUMA-KM4 four circle diffractometer at the – an angle of 5.5(1)o. Bond distances and bond an- Institute of Nuclear Chemistry and Technology. gles within both pyridazine rings are in fair agree- Structure solution and refinement were performed ment with those reported for pyridazine-4-carbo- using SHELXL-97 program package. xylic acid chloride. The dimers interact via a system RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 111 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXXIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF A LEAD(II) COMPLEX WITH A 2,2’-DIPYRIDINE-5,5’-DICARBOXYLATE LIGAND Wojciech Starosta, Janusz Leciejewicz

The crystal structure of a Pb(II) complex with a 2,2’-dipyridine-5.5’-dicarboxylate ligand is composed of molecular network in which Pb(II) ions are bridged by both O atoms of two carboxylate groups of a ligand [Pb-O1 2.398(15) Å, Pb-O2 2.885(22) Å]. Both hetero-ring N atoms and bi-

Fig.1. A structural unit of a Pb(II) complex with 2,2’-dipyridine-5,5’-dicarboxylate ligand with atom labels. dentate carboxylate oxygens act also in a bridging mode. A three-dimensional molecular network is formed in this way. Figure 1 shows a structural unit with atom labelling scheme, Fig.2 – a fragment Fig.3. The coordination geometry of a Pb(II) ion in the of the molecular pattern. Each Pb(II) ion is coor- structure of its complex with a 2,2’-dipyridine-5.5’-dicarboxylate ligand. Symmetry code: (A) -x+1, y, z; (B) -x+1/2, -y+2, z-1/2; (C) -x, y, z. dinated by four carboxylate O atoms, two bridging carboxylate O atoms and two hetero-ring nitrogen atoms situated at the apices of a distorted cube. Figure 3 shows the coordination geometry around a Pb(II) ion. An empty hole formed by O(1A), O(1C), N(1A) and N(1B) atoms is clearly visible. Such a distortion of coordination polyhedron around a Pb(II) ion is often observed in its coordination compounds with organic ligands. It is usually interpreted as due to the stereochemical action of the Pb(II) ion 6s2 lone electron pair. The observed Pb-O and Pb-N bond distances fall in the range reported for Pb(II) complexes with carboxylate ligands The pyridine ring is planar: r.m.s. is 0.0225 Å. The pyridine rings in the ligand molecule make a dihedral angle of 56.9o each to the other. Carboxylate planes deviate from the pyridine rings each by 12.0o. X-ray data collection was carried out on a KUMA-KM4 four circle diffractometer at the Fig.2. A fragment of a molecular alignment in the struc- Institute of Nuclear Chemistry and Technology. ture of a Pb(II) complex with 2,2’-dipyridine-5,5’-dicarboxy- Structure solution and refinement were performed late ligand. using SHELXL-97 program package. RADIOBIOLOGY RADIOBIOLOGY 115 BIOLOGICAL EFFECTIVENESS OF 12C AND 20Ne IONS WITH VERY HIGH LET Joanna Czub1/, Iwona Buraczewska, Andrzej Wójcik 1/ Institute of Physics, the Jan Kochanowski University of Humanities and Sciences, Kielce, Poland

Knowledge of the radiobiological effects of heavy need to be well characterized. Therefore, we de- ions at the cellular and molecular level are of fun- termined the relationship between the RBE for damental importance in the field of radiation cell inactivation and LET in the Bragg peak re- therapy (for example C ions) and space radiation gion of 12C and 20Ne ions. biology (for example Ne ions). One of the issues that require deeper investigations is the determination of the relative biological effectiveness (RBE) values for a wide range of linear energy transfer (LET), for all relevant doses, for many cell types and various kinds of radiations [1]. In the tissue exposed to heavy ions the RBE is low in the entrance at high energy and increases at the end of the particle range [2]. It is known that RBE increases as a function of LET up to a maximum value which, for high Z high energy (HZE) charged particles, is found at LET values between 100 and 250 keV/μm; however, cell killing caused by heavy ions strongly depends on the cell and ion type [1]. The LET, which is equal to the stopping power of heavy particles, increases sharply at the end of the particle’s path, forming the Bragg peak. The shape of the Bragg peak depends on the type Fig.2. RBE values at a survival levels of 0.5, 0.1 and 0.01 for CHO-K1 irradiated by 12C and 20Ne ions. The error of RBE was calculated by error propagation from the errors on photon and ion doses.

Chinese hamster ovary (CHO-K1) cells were exposed to high LET 12C (33.2 MeV, 20.3 MeV, 9.1 MeV at cell entrance) and 20Ne ions (56.2 MeV, 34.7 MeV, 15 MeV at cell entrance) and to low LET γ-rays. RBE has been measured for LET values close to the Bragg peak maximum, i.e. 440-830 keV/μm for 12C and for 1020-1600 keV/μm for 20Ne ions. Figure 1 shows the survival curves of CHO-K1 cells as a function of irradiation dose for 12C, 20Ne ions and 60Co γ-rays. The LET-RBE relationships estimated for survival values of 0.5, 0.1 and 0.01 following exposure to the two types of ions form a single line when plotted together and Fig.1. Survival curves of CHO-K1 cells as a function of ir- were found to decrease with increasing LET radiation dose for 12C, 20Ne ions and 60Co γ-rays. The lines (Fig.2). This points towards the LET and not any represent linear-quadratic or linear fits using Trust-Region physical characteristics of the ions as the single algorithm (Matlab 7.1). Results for ions are from single ex- determinant of RBE. periments. In these cases error bars represent 10% of sur- The work partly supported by the statutory grant viving fraction. Vertical error bars for γ-rays 60Co indicate of the Ministry of Science and Higher Education the standard error of the mean (SEM) from 6 independent (Poland). experiments. Horizontal error bars: 3% of dose. of particle. Because overlying beams with different References energies and components of primary and second- [1]. Kraft G.: Prog. Part. Nucl. Phys., 45, 473-544 (2000). ary particles are used in radiotherapy, the knowl- [2]. Kramer M., Weyrather W.K., Scholz M.: Technol. edge of RBE values of very high LET radiation Cancer Res. Treat., 2, 427-436 (2003). 116 RADIOBIOLOGY EXCESS PCC FRAGMENTS IN UNIRRADIATED HUMAN LYMPHOCYTES Sylwester Sommer, Sylvia Ritter1/, Elena Nasonova2/ 1/ GSI Gesellschaft für Schwerionenforschung mbH, Darmstadt, Germany 2/ Joint Institute for Nuclear Research, Dubna, Russia

Premature chromosome condensation (PCC) is al PCC fragments were situated in line with their often used in cytogenetic experiments or biodo- origin chromosome or in its close proximity (Fig.1). simetry [1]. Premature chromatin condensation is This observation suggests that such a PCC frag- caused by virus infection, fusion with mitotic cells ment is not formed as a result of a “real” chromo- or action of phosphatase inhibitors like okadaic acid or calyculin A [2]. The result is condensation of chromatin in G1, S and G2 phases of the cell cycle. In biodosimetry, the PCC method is used because of its simplicity and because the conventional dosimetry method, the dicentric assay, is not applicable after doses higher than 5-6 Gy, whereas there is no dose limitation for PCC [1]. For example, the yield of PCC-rings was successfully used after the Tokaimura radiation accident to estimate the delivered dose [3].Technically, the PCC assay is based on counting of excess PCC fragments. Radiation induces DNA breaks and, therefore, in irradiated human cells there should apparently be more than 46 chromosomes. The increase in the number of PCC fragments is radiation dose dependent. In the reported experiments we aimed at estimation of the level of PCC fragments in unirradiated cells. Our own experiments as well as data from some other laboratories indicate that in different cell types, e.g. hu- Fig.1. Forty nine PCC fragments in a control human lym- man lymphocytes or fibroblasts there are additional phocyte, 48 h sampling time, DAPI staining. All chromo- PCC fragments in unirradiated control cells. In an somes were painted; therefore, it was possible to show that experiment performed at GSI (Gesellschaft für 3 additional PCC fragments are situated in a close proxim- Schwerionenforschung mbH) we examined PCC ity to their origin chromosomes. fragments in the control peripheral human lymphocytes. Lymphocytes were cultured according to some break. Probably, it represents the distal part the standard cytogenetic method and 50 min be- of the origin chromosome and is a result of imper- fore fixation calyculin A to the final concentration fect condensation of the region located between of 50 μM was added to the medium in order to the PCC fragment and the remaining part of the induce PCC. After hypotonic treatment and fixa- chromosome (Fig.2). Individual chromosomes tion, each prepared slide was hybridized with fluo- were involved in formation of excess acentric frag- rescent probes for each chromosome (m-FISH) ments or were imperfectly condensed to a differ- and counterstained with DAPI. PCC fragments ent degree. Chromosomes 9 and X were most often were scored using a fluorescent Olympus micro- involved in formation of excess acentric frag- scope in the DAPI channel. Identification of each ments, whereas chromosomes 9 and 13 were most chromosome was made by means of m-FISH and often imperfectly condensed. It is plausible to as- the position of each additional fragment was de- sume that PCC fragments observed in unirradiat- termined. Only PCC in G2-shaped spreads were ed cells are generated due to partial chromosome scored. decondensation because it is known that inactive Eighty one G2 cells were scored in the DAPI chromosomes X can be condensed late during channel and 18 additional PCC fragments were G2/M phase and chromosomes 9 have weakly con- found (frequency 0.22/cell). We found 0.1, 0.25 and 0.32 excess PCC fragments per first cycle G2/M cell at 48, 72 and 96 h sampling time, respectively. In the majority of studies no PCC fragments in the controls are listed (e.g. [1,4]). Some chromosomes were found to be not fully condensed. The m-FISH technique allows to iden- A B C tify all pairs of chromosomes and the origin of each additional fragment, a task not possible with Fig.2. Explanation of the mechanism of formation of a conventional Giemsa staining or DAPI counter- PCC fragment (A) from the distal part of a chromosome staining. Therefore, we could reveal that addition- (C) with imperfectly condensed region (B). RADIOBIOLOGY 117 densed heterochromatin region named by cyto- [2]. Gotoh E., Durante M.: J. Med. Genet., 13, 103-122 genetists a “fussy centromeric region” [5]. (2006). The work was carried out in GSI and INCT [3]. Hayata I., Kanda R., Minamihisamatsu M., Furokawa (statutory grant of the Ministry of Science and S., Sasaki M.: J. Radiat. Res. Suppl., 42, 149-155 (2001). Higher Education, Poland). [4]. Tsuruoka C, Suzuki M, Hande M, Furusawa Y, Anzai References K, Okayasu R.: Radiat. Res., 170, 163-171 (2008). [5]. Zhang A., Lin M., Wilson M., Fujimoto A.: Cytogenet. [1]. Wang Z., Li W., Zhi D., Jing X., Wei W., Gao Q., Liu Cell Genet., 52, 79-82 (1989). B.: Radiat. Environ. Biophys., 46, 229-235 (2007).

ESTIMATION OF GENOTOXICITY OF A HISTIDINE DINITROSYL IRON COMPLEX WITH AN IN VITRO PLASMID TEST Tomasz Stępkowski, Grzegorz Wójciuk, Kamil Brzóska, Marcin Kruszewski

Dinitrosyl iron complexes (DNIC), which can be trol of plasmid cleavage, instead of DNIC, we used described by general formula Fe(NO)2(L)2, where hydrogen peroxide at 180 and 18 mM concentra- L is a carbonyl-, nitrosyl- or imino-complexing li- tions in the same conditions. In order to obtain a gand, are natural transducers of nitric oxide, a free linear form of the plasmid, we cleaved it with a radical that is strongly deleterious towards the cell BamHI restriction enzyme (Fermentas). components. There is a lack of reports on the inter- After incubation and adding 2 μL of bromo- action of DNIC with DNA. The report on apoptosis phenol blue tracking dye to every sample, we load- induction by DNIC [1] indicates a DNA damage- ed them to a 0.7% agarose gel containing 0.25 μg -independent mechanism, involving nitrosation-de- of ethidium bromide for electrophoresis at 60 mA pendent modification of multiple cell surface com- current. The DNA bands were visualized under ponents. On the other hand, DNIC induce the SOS UVC light. Photographs were taken using a Biometra DNA repair response in Escherichia coli [2]. Biodoc CA camera. The results are shown in Fig. In order to estimate the extent of DNA dam- It can be seen that low molecular His-DNIC at age caused by different concentrations of histidine 4 and 1 mM concentrations is able to damage dinitrosyl iron complex (His-DNIC) we carried out plasmid DNA, although DFO controls indicate a plasmid cleavage test similar to those previously that free ferrous ions in the buffer partially mimic described [3,4]. In this test, the proportion of abun- this DNIC-mediated DNA damage. Intensive DNA dance of DNA bands, corresponding to superheli- bands corresponding to OC forms and the lack of cal (CCC), linear (L) and open circle (OC) forms those related to linear forms of the plasmid (lanes of the plasmid, visualised after electrophoresis is 6 and 8), indicate that His-DNIC in the presence directly related to DNA damage. of DFO has the ability to produce DNA nicks 1 2 3 4 5 6 7 8 9 10 11 12

Fig. Electrophoretic separation of plasmid DNA after treatment as follows. Lanes: (1) linear form of plasmid obtained by BamHI cleavage; (2) control: plasmid+PBS, 65 min, 37oC ; (3) 180 mM hydrogen peroxide; (4) 18 mM hydrogen peroxide; (5) 4 mM DNIC; (6) 4 mM DNIC+DFO; (7) 1 mM DNIC; (8) 1 mM DNIC+DFO; (9) 10 μM DNIC; (10) 10 μM DNIC+DFO; (11) 1 μM DNIC; (12) 1 μM DNIC+DFO. Plasmid pEGFP-N2 (Clontech) was incubated rather than double-strand breaks. This effect of at 37oC for 65 min in a 4 mM phosphate-buffered plasmid damage was observed only after incuba- saline with different concentrations of DNIC. tion with relatively high-milimolar concentrations Incubation mixtures in a total volume of 10 μL of DNIC. We did not see any plasmid damage when contained 250 ng of pEGFP-N2 plasmid DNA and we used low DNIC concentrations – 10 or 1 μM. DNIC at concentrations ranging from 4 mM to 1 Our observations are consistent with the re- μM. For each density of DNIC, we set a control port [2] showing the role of iron ions in reactivity reaction with an equal molar concentration of de- and toxicity of the NO-donating agents in the SOS ferroxamine (DFO), a selective iron chelating DNA repair response of Escherichia coli. This reagent, to ensure that the observed DNA damage sponse may be activated directly by DNIC-mediated was not a result of the presence of free ferrous DNA lesions. On the other hand, it was recently ions in the incubation mixture. As a positive con- found that reactive radicals can modify iron-sul- 118 RADIOBIOLOGY phur cluster redox state in Fe-S transcription fac- Munzel T.: Free Radical Biol. Med., 40, 1340-1348 tors and in that way regulate transcription of genes (2006). coding proteins of the DNA repair pathways [5,6]. [2]. Stupakova M.V., Lobysheva I.I., Mikoyan V.D., Vanin One such factor is [2Fe-2S] oxidative-stress sensor A.F., Vasilieva S.V.: Biochemistry (Moscow), 65, 690-695 (2000). SoxR of Escherichia coli [6]. Recent studies show [3]. Ahmad S., Agrawal R., Agrawal D.K., Rao G.S.: Toxi- that SoxR is a global regulator of transcription in- cology, 150, 31-39 (2000). volved in activating multiple stress induced operons, [4]. Di Mascio P., Teixeira P.C., Onuki J., Medeiros M.H., also those involved in DNA repair [7]. Modification Dörnemann D., Douki T., Cadet J.: Arch. Biochem. of such transcription factors by DNIC may present Biophys., 373, 368-374 (2000). another mechanism by which DNICs indirectly [5]. Vasil’eva S.V., Stupakova M.V., Lobysheva I.I., Mi- activate the SOS response in Escherichia coli. koyan V.D., Vanin A.F.: Biochemistry (Moscow), 66, Work supported by a statutory grant to the INCT 984-988 (2001). by the Ministry of Science and Higher Education [6]. Lo F.C., Chen C.L., Lee C.M., Tsai M.C., Lu T.T., Liaw (Poland). W.F., Yu S.S.: J. Biol. Inorg. Chem., 13, 961-972 (2008). [7]. Blanchard J.L., Wholey W.Y., Conlon E.M., Pom- References posiello P.J.: PLoS ONE, 14, 1186 (2007). [1]. Kleschyov A.L., Strand S., Schmitt S., Gottfried D., Skatchkov M., Sjakste N., Daiber A., Umansky V.,

DINITROSYL IRON COMPLEX FORMATION IN K562 CELLS: EFFECTS OF AMMONIUM CHLORIDE AND OVEREXPRESSION OF THE HEAVY CHAIN OF FERRITIN Karolina Rumianek, Jarosław Sadło, Marcin Kruszewski

Dinitrosyl iron complexes (DNIC) are a group of physiologically important transducers of nitric oxide [1,2]. Previously, we have shown [3] that depletion of lysosomal LIP (labile iron pool) by either chelation with deferoxamine (DFO) or lysis inhibition (by treatment with 10 mM NH4Cl) in K562, human myelogenous leukemia cells leads to a considerable decrease (down to 50%, depending on the incubation time) of DNIC formed in the cells treated with 70 μM nitric oxide donor, DEANO. The aim of this study was to investigate the role of high-molecular weight (HMW) ligand, ferritin and inhibitor of lysosomal acidification, NH4Cl in Fig. Inhibition of EPR signal induction in K562 cells (over- formation of DNIC. Experiments were conducted expressing a hybrid protein consisting of heavy chain of fer- on human erythroid K562 cells overexpressing ritin and GFP, K562 GPF+FERH or overexpressing GFP heavy chain of ferritin (K562 FERH) and the re- protein alone, K562 GFP) incubated with 10 mM NH4Cl sults compared with those for K562 cells overex- for time intervals indicated and with DEANO for 15 min at 37oC. Mean values from 3 experiments, standard error pressing empty vector (K562 GFP). The cells were indicated. treated with 10 mM NH4Cl for 2, 4 or 6 h or with a nitric oxide donor (the final nitric oxide concen- intensity of DNIC specific EPR signal. Further ex- tration in the medium was 100 μM). periments (not shown) revealed that this decrease The formation of DNIC was monitored by elec- is time-dependent. Similar, but less pronounced tron paramagnetic resonance (EPR). Each sample time-dependent decrease in DNIC formation was was placed in a 4 mm diameter quartz tube and observed in K562 expressing vector containing fer- frozen in liquid nitrogen (77 K). DNIC formation ritin heavy chain DNA (K562 GFP+FERH). The was recorded using EPR. The EPR spectra were results suggest that iron containing proteins with- recorded on Bruker ESP 300 at 77 K, microwave out [Fe-S] cluster are important ligands for DNIC power – 1 mW, microwave frequency – 9.31 GHz, formation in vivo. modulation amplitude – 3.027 G and time con- Work supported by the Ministry of Science and stant – 41 ms. In order to estimate the values of g Higher Education (Poland) grant No. N204077833. coefficients computer simulation was performed References on SimFonia 1.25 software (Bruker Analytische Messtechnik, DE). [1]. Vanin A., Kleschyov A.: In: Lukiewicz S., Zweier J.L. Once the EPR signal intensity was measured, Nitric oxide in transplant rejection and anti-tumor defence. Kluwer Academic Publishing, Boston 1999, the protein concentration in each sample was as- pp.49-82. sayed by the Bradford method and the results pre- [2]. Ueno T., Yoshimura T.: Jpn. J. Pharmacol., 82, 95-101 sented per mg protein. (2000). As shown in Fig., overexpression of GFP pro- [3]. Męczyńska S., Lewandowska H., Kruszewski M.: Acta tein and cell treatment with NH4Cl decreased the Biochim. Pol., 55, Suppl. 1, 192 (2006). RADIOBIOLOGY 119 DINITROSYL IRON COMPLEX FORMATION IN K562 CELLS: EFFECT OF N-ACETYL-Leu-Leu-Nle-ALDEHYDE (ALLN) Karolina Rumianek, Jarosław Sadło, Marcin Kruszewski

We have observed a pronounced effect of ammo- cathepsin D [3]. Since lysosome acidification is nium chloride, inhibitor of lysosomal acidification, necessary for cathepsin activity and hence, for pro- on dinitrosyl iron complexes (DNIC) formation [1]. tein degradation in the lysosomes, it could be ex- We further studied DNIC formation using N-ace- pected that proteolysis inhibition by cathepsin in- tyl-Leu-Leu-Nle-aldehyde (ALLN) which inhibits hibitor will exert a similar effect to that described the activities of Ca(2+)-dependent neutral cysteine for treatment with ammonium chloride [1]. proteases (e.g. calpain) [2] as well as lysosomal K562 human erythroid precursor cells and proteases, including cathepsin L, cathepsin b and K562 cells expressing empty vector (K562 GFP) used in the previous experiments [1] were used in the present study. As shown in Fig., 50 μM ALLN caused a time-dependent decrease in DNIC formation similar to that observed with NH4Cl [1]. Work supported by the Ministry of Science and Higher Education (Poland) grant No. N204077833. References [1]. Rumianek K., Sadło J., Kruszewski M.: Dinitrosyl iron complex formation in K562 cells: effects of ammonium chloride and overexpression of the heavy chain of ferritin. In: INCT Annual Report 2008. Institute of Nu- clear Chemistry and Technology, Warszawa 2009, p.118. Fig. Inhibition of EPR signal induction in K562 cells (not [2]. Inoue S., Bar-Nun S., Roitelman J., Simoni R.D.: J. transfected or overexpressing empty vector, K562 GFP, see Biol. Chem., 266, 13311-13317 (1991). [1]). incubated with 50 μM ALLN for time intervals indi- [3]. Murray E.J., Tram K.K., Murray S.S., Lee D.B.: Me- cated and with nitric oxide donor (DEANO) for 15 min at tabolism, 44, 141-144 (1995). 37oC.

DINITROSYL IRON COMPLEX FORMATION IN K562 CELLS: EFFECT OF HEMIN Sylwia Męczyńska-Wielgosz, Jarosław Sadło, Hanna Lewandowska-Siwkiewicz, Marcin Kruszewski Dinitrosyl iron complexes (DNIC) are generated in cells that produce NO, e.g. macrophages, spinal cord, hepatocytes, endothelial cells. Biological functions of DNIC are a matter of discussion; it is postulated, that they are a form of NO storage and may play the role of cellular NO stabilizers [1,2]. The sources of iron forming DNIC in vivo are still not precisely defined; one source is the labile iron pool (LIP) and another – iron-containing proteins [3-5]. In the present report we investigated the con- Fig.1. EPR signal intensity in K562 cells incubated with tribution of heme and heme-containing proteins protoporphyrins prior the treatment with NO donor. to the formation of DNIC in vivo. The human myelogenous leukemia K562 cells (45 ml of culture the formation of DNIC, as shown in Figs.1 and 2. of density approximately 1x106 cells/ml) were pre- We conclude that heme-containing proteins con- treated with hemin (100 μM, 3 h, 37oC), protoporphyrin IX (100 μM, 3 h, 37oC) or protoporphyrin IX zinc(II) complex (10 μM, 3 h, 37oC). After pretreatment, cells were subjected to treatment with 70 μM DEANO (nitric oxide donor) for 15 min at 37oC to generate DNIC. The final concentration of NO was 100 μM. DNIC content was estimated from the intensity of the characteristic EPR (electron paramagnetic resonance) signal. The signal intensity of each sample was normalized to the amount of protein. Fig.2. EPR signal intensity in K562 cells pre-incubated with Pretreatment with hemin, but not protopor- protoporphyrin IX zinc(II) complex prior the treatment phyrin IX or protoporphyrin IX(Zn) increased with hemin and then NO donor. 120 RADIOBIOLOGY tribute in the DNIC formation in vivo, whereas Nitric oxide in transplant rejection and anti-tumor de- iron ions released from heme do not significantly fence. Eds. S. Lukiewicz, J.L. Zweier. Kluwer Aca- contribute to the DNIC formation in vivo. demic Publishing, Boston 1999, pp.49-82. Taken together, our results indicate that the [2]. Ueno T., Yoshimura T.: Jpn. J. Pharmacol., 82, 95-101 (2000). heme and heme-containing proteins are an impor- [3]. Męczyńska S., Lewandowska H., Kruszewski M.: Acta tant source of iron for DNIC formation, however Biochim. Pol., 55, Suppl. 1, 192 (2006). the precise form of heme-derived iron involved in [4]. Lewandowska H., Meczyńska S., Sochanowicz B., Sadło DNIC formation is yet unknown. J., Kruszewski M.: J. Biol. Inorg. Chem., 12, 345-52 Work supported by a statutory grant to the INCT (2007). by the Ministry of Science and Higher Education [5]. Meczynska S., Lewandowska H., Sochanowicz B., Sad- (Poland). lo J., Kruszewski M.: Hemoglobin, 32, 157-63 (2008). References [1]. Vanin A., Kleschyov A.: EPR studies and biological implications of nitrosyl nonheme iron complexes. In:

NO EFFECT OF TEMPERATURE DURING IRRADIATION ON THE LEVEL OF CYTOGENETIC DAMAGE IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES EXPOSED TO NEUTRONS Kinga Brzozowska, Günther Obe1/, Andrzej Wójcik 1/ Department of Genetics, University of Duisburg-Essen, Germany

It has been reported that the level of cytogenetic meter – 7.2 cm, height – 15 cm) that were filled damage in human peripheral blood lymphocytes with water at 37 and 0oC. The Eppendorf cups (PBL) is higher following irradiation at 37oC than were positioned horizontally in the water wells. at 0-4oC [1]. The mechanisms of this cytogenetic The phantom was covered with a 1 cm thick A-150 temperature effect are not fully known. Our pre- plate and irradiated from above with a dose of 1 vious report [2] indicated that with PBL exposed Gy, dose rate – 0.3 Gy/min. The dose was calcu- to X-rays at increasing temperature between 0 lated with the help of the code MCNPX (Monte and 37oC, the highest frequency of micronuclei Carlo Neutrons Protons X-rays, Los Alamos was scored following exposure of PBL at 37oC. No National Laboratory). The calculated gamma com- effect of temperature was seen when PBL were ponent of the dose was 3.4%. exposed in the presence of dimethyl sulphoxide The frequencies of dicentrics (dics) in PBL ex- (DMSO), indicating that the indirect radiation ef- posed to neutrons are shown in Table. No dicentrics fect was temperature dependent. Here, dicentric were observed in non-irradiated cells, hence the chromosome frequency was taken as the end-point, table only contains data for the irradiated cells. In to see whether the temperature effect will be present PBL of no donor we did observe a statistically sig- in PBL exposed to neutrons (expected to damage nificant difference in the frequency of dicentrics cells by the direct action of radiation). between cells exposed to neutrons at 0 and 37oC. Table. Frequency of dicentric chromosomes in PBL exposed to 1 Gy of neutrons.

Dose Temperature Number of cells with dics Dics Cells Donor o DI [Gy] [ C] 0123 per 100 cells scored 1 0 33 14 0 0 0.71 29.8 47 5 1 37 47 12 1 0 0.92 23.3 60 1 0 70 27 3 0 0.86 33.0 100 6 1 37 68 28 3 1 0.96 37.0 100 1 0 60 23 1 0 0.79 29.8 84 7 1 37 87 35 13 0 0.98 45.2 135 PBL were kept at 37 or 0oC for 20 min and ex- Dispersion indices (DI) were calculated by dividing posed to 1 Gy of neutrons. The exposure to neu- the variance by the mean values; they were gener- trons was performed with 6.0 MeV (average) neu- ally below 1, and there was no indication that the trons generated by the TCC CV 28 cyclotron temperature at exposure influenced the distribu- (deuterons on beryllium reaction, University Hos- tion of dics in a particular way. pital of Essen). Eppendorf cups were filled with These results support our previous conclusion blood and positioned in a wax phantom (30x30x27 that the temperature effect is due to the indirect cm). The phantom had two separated wells (dia- action of radiation. RADIOBIOLOGY 121 Work supported by a statutory grant to the INCT [2]. Brzozowska K., Johannes C., Obe G., Hentschel R., by the Ministry of Science and Higher Education Mirand J., Moss R., Wittig A., Sauerwein W., Liniecki

(Poland). J., Szumiel I., Wójcik A.: Chromatin status and the response of hypothermic cells to X-rays and neutrons. References In: INCT Annual Report 2007. Institute of Nuclear Chemistry and Technology, Warszawa 2008, pp.91-92. [1]. Bajerska A., Liniecki J.: Int. J. Radiat. Biol., 16, 483-493 (1969).

NO EFFECT OF TEMPERATURE DURING X-IRRADIATION ON THE LEVEL OF THE INITIAL DNA DAMAGE IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES Kinga Brzozowska, Andrzej Wójcik

The level of cytogenetic damage induced by ion- We used the alkaline comet assay to check izing radiation under in vitro conditions in human whether this method allows to detect differences peripheral blood lymphocytes (PBL) is analyzed in the initial DNA damage after X-irradiation at for the purpose of establishing calibration curves varying temperature. Peripheral blood was col- used in biological dosimetry and for assessing the lected by venipuncture from healthy male or fe- individual intrinsic radiosensitivity of radiotherapy male donors. The exposure to X-rays was per- patients or personnel using devices involving ion- formed with an Andrex X-ray machine running at izing radiation. Irradiation of blood should be 180 kV, equipped with a 3 mm Al filter. The dose performed under strictly controlled physical con- was 2 Gy (dose rate 0.5 Gy/min). Eppendorf cups ditions that allow a high reproducibility of the were positioned in 150 ml plastic cups filled with dose. A factor that is often not regarded is the water at 37 or 0oC (melting ice) and irradiated control of blood temperature during exposure. In from above. Whole blood (WB) or isolated (IL) 1969 Bajerska and Liniecki [1] have shown that PBL were kept at 37 or 0oC for 20 min and subse- the frequency of chromosomal aberrations is low- quently exposed to 2 Gy of X-rays at the respec- er when blood is irradiated at room temperature tive temperature. In some experiments, PBL were than when exposed at 37oC. Our previous report isolated by gradient centrifugation on Gradisol [2] indicated that with PBL exposed to X-rays at (Poland), kept at 37 or 0oC for 20 min and 0.5 M increasing temperature between 0 and 37oC, the DMSO was added for 5 min before exposure. highest frequency of micronuclei was scored fol- Comet assay was carried out as described in [6]. lowing exposure of PBL at 37oC. No effect of tem- Table presents the results of the comet assay perature was seen when PBL were exposed in the with the average values of the tail moments per presence of dimethyl sulphoxide (DMSO), indicat- experiment and the mean value from 5 indepen- ing that the temperature dependence concerns the dent experiments. The results considerably vary, indirect radiation effect. possibly due to individual characteristics of the Table. Results of the comet assay showing the average values of the tail moments per experiment and the mean value from the 5 independent experiments (WB – whole blood, IL – isolated lymphocytes). Standard deviations are shown in brackets. Donor number and state of lymphocytes at exposure Dose Temperature Mean [Gy] [oC] 1 1 2 3 4 IL IL WB WB WB 0 0 8.1 (11.2) 9.4 (7.8) 11.0 (8.2) 54.3 (24.2) 37.1 (20.5) 23.9 (20.8) 0 37 11.3 (13.2) 11.8 (9.8) 11.3 (6.6) 52.9 (21.5) 23.5 (14.9) 22.2 (18.0) 2 0 54.5 (26.2) 25.4 (15.1) 33.7 (18.7) 88.9 (27.8) 56.2 (20.5) 51.7 (24.6) 2 37 42.7 (24.2) 26.9 (16.9) 39.5 (23.3) 69.3 (28.6) 37.1 (20.5) 43.1 (15.8) Consistent with these observation are the re- donors. The data indicate that no temperature ef- ports of Elmroth and coworkers [3,4]. Using the fect could be revealed with this method – the dif- fluorescent halo method, they found a reduced ferences are not statistically significant (Student’s level of DNA supercoil rewinding at 0oC which t-test). they interpreted as resulting from a reduced level Work supported by a statutory grant to the INCT of induced DNA damage due to chromatin con- by the Ministry of Science and Higher Education densation at 0oC. This conclusion was supported (Poland). by the fact that DMSO did not alter the level of radiation-induced damage in cells exposed at 0oC, References whereas it did so following exposure of cells at [1]. Bajerska A., Liniecki J.: Int. J. Radiat. Biol., 16, 37oC [5]. 483-493 (1969). 122 RADIOBIOLOGY

[2]. Brzozowska K., Johannes C., Obe G., Hentschel R., [4]. Elmroth K., Erkell L.J., Nygren J., Hultborn R.: Anti- Mirand J., Moss R., Wittig A., Sauerwein W., Liniecki cancer Res., 19, 5307-5311 (1999). J., Szumiel I., Wójcik A.: Chromatin status and the re- [5]. Elmroth K., Nygren J., Erkell L.J., Hultborn R.: Int. J. sponse of hypothermic cells to X-rays and neutrons. Radiat. Biol., 76, 1501-1508 (2000). In: INCT Annual Report 2007. Institute of Nuclear [6]. Wojewódzka M., Kruszewski M., Iwaneńko T., Collins Chemistry and Technology, Warszawa 2008, pp.91-92. A.R., Szumiel I.: Mutat. Res., 416, 21-35 (1998). [3]. Elmroth K., Erkell L.J., Hultborn R.: Radiat. Res., 152, 137-143 (1999).

EFFECTS OF 1,4-DIHYDROPYRIDINE DERIVATIVE TREATMENT ON MUTATION FREQUENCY IN X-IRRADIATED CHO CELLS Maria Wojewódzka, Iwona Grądzka, Iwona Buraczewska, Kamil Brzóska, Rose I. Goncharova1/, Irena Szumiel 1/ Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk, Republic of Belarus

Derivatives of 1,4-dihydropyridine were described as efficient antimutagens and DNA repair modu- lators in vivo and in vitro (e.g. [1-3]). In particular, alkaline single cell gel electrophoresis (comet) assays showed that DHP (sodium 3,5-bis-ethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-4-carboxylate, previously designated as AV-153 [4]) reduced the number of endogenously generated DNA strand breaks in untreated human lymphocytes and human promyelocytic leukemia HL-60 cells [4]. In HL-60 and Raji (human B-lymphoblastic leukemia) cells exposed to 2 Gy of gamma radiation or 100 μM hydrogen peroxide there was a statistically significant increase in the single strand break rejoining Fig. Treatment with 10 μM DHP prior to and after 3 Gy rate [5]. Another compound of 1,4-DHP series, glu- X-irradiation decreased the mutation frequency level at the HGPRT locus in CHO cells. tapyrone (disodium salt of 2-(2,6-dimethyl-3,5-di- ethoxycarbonyl-1,4-dihydropyridine-4-carbox- locus was induced by 3 Gy X-rays and expressed as amido)-glutaric acid), protected against ethyl colony forming ability in the selective 6-thiogua- methanesulphonate (EMS)-induced mutations in nine-supplemented medium as described by Kinashi Drosophila melanogaster and chromosome break- et al. [7]. age in mouse bone marrow [1]. In contrast with As shown in Fig., DHP has an antimutagenic these data, in our hands DHP did not affect survival activity in CHO-K1 cells in vitro. or DNA strand break repair in CHO-K1 (Chinese References hamster ovary) or xrs6 cells (radiosensitive mu- tant) [6]. [1]. Kuzhir T.D., Dalivelia O.V., Savina N.V.: Genetika, 35, The purpose of the reported investigation has 19-924 (1999), in Russian. [2]. Goncharova R.I., Kuzhir T.D.: Mutat. Res., 214, 257-265 been to study the influence of DHP on mutation (1989). frequency in X-irradiated CHO-K1 cells. The pres- [3]. Kuzhir T.D., Goncharova R.I.: Biochem, Soc. Trans., ent study is part of screening of 1,4-DHP deriva- 25, 139S (1997). tives synthesized in the Latvian Institute of Organic [4]. Ryabokon N.I., Goncharova R.I., Duburs G., Rze- Synthesis. szowska-Wolny J.: Mutat. Res., 587, 52-58 (2005). Exponentially growing cells were incubated with [5]. Ryabokon N.I., Goncharova R.I., Duburs G., Hancock 10 μM DHP at 37oC for 1 h and X-irradiated (3 R., Rzeszowska-Wolny J.: Mutat. Res., 637, 173-181 Gy). X-irradiation (ANDREX, Holger Andreas- (2008). sen, Denmark, 200 kVp, 5 mA) was at a dose rate [6]. Wojewódzka M., Dalivelya O., Savina N., Szumiel I.: of 1.2 Gy/min. Survival of CHO-K1 cells subjected Effects of 1,4-dihydropyridine derivative treatment on DNA damage in CHO cells. XIV Meeting of the Polish to single agent or combined treatment (DHP+X) Biochemical Society, Kielce, 24-26.09.2007. was determined by cloning. Cloning efficiency was [7]. Kinashi Y., Masunaga S., Nagata K., Suzuki M., Taka- about 50%. Mutation frequency at the hypoxan- hashi S., Ono K.: Int. J. Radiat. Oncol. Biol. Phys., 68, thine-guanine phosphoribosyl transferase (HGPRT) 508-514 (2007). RADIOBIOLOGY 123 EFFECTS OF 1,4-DIHYDROPYRIDINE DERIVATIVE TREATMENT ON BASE DAMAGE IN X-IRRADIATED CHO CELLS Maria Wojewódzka, Kamil Brzóska, Irena Szumiel

Derivative of 1, 4-dihydropyridine, DHP (sodium with 1 μM 4’,6-diamidine-2-phenylindole dihydro- 3,5-bis-ethoxycarbonyl-2,6-dimethyl-1,4-dihydro- chloride (DAPI, 50 μl per slide). Image analysis pyridine-4-carboxylate, previously designated as was performed by the Comet version 3 software AV-153 [1]) reduced the number of endogenous (Kinetic Imaging, Liverpool, UK). and X or γ-ray-induced DNA strand breaks in cells Figure 1 shows that in X-irradiated CHO-K1 of human origin [1,2]. Nevertheless, in our hands, cells DHP pretreatment causes a marked decrease this compound had no radioprotective properties in the level of FPG-sensitive sites, whereas the and did not stimulate DNA break repair in Chinese single strand break level (Fig.2) remains unaltered. hamster ovary CHO-K1 and xrs6 cells [3]. In view The previously observed unaltered by DHP pre- of the numerous reports on the antimutagenic ac- treatment survival level and DNA breakage after tivity of the 1,4-dihydropyridine derivatives (review X-irradiation {3] do not contradict reduced oxida- in [2]), we estimated the initial DNA damage in tive base damage induction as this type of damage DHP-treated or sham-treated and X-irradiated does not affect survival. Hence, it is plausible to CHO-K1 cells, using the alkaline comet assay. Al- assume that the antimutagenic activity of DHP though DNA breakage induces mutations [4] we consists in oxidative base damage decrease. The expected that primarily base damage may be responsible for the reported antimutagenic activity of DHP. CHO-K1 cells were X-irradiated with doses ranging from 0 to 2 Gy on ice in the presence of 10 nM DHP. The initial DNA damage was determined by the alkaline version of the comet assay, performed as described by Singh et al. [5]. For the measurement of base damage, iIncubation of irradiated cells with the formamido pyrimidine gly- cosylase (FPG, BioLabs) was carried out as described by Kruszewski et al. [6]. Briefly, after lysis, slides were washed 3 times in enzyme buffer (40 Fig.2. Reduction in FPG-sensitive sites after X-iradiation mM HEPES-KOH, 0.1 M KCl, 0.5 mM EDTA, of CHO-K1 cells with doses ranging from 0 to 2 Gy with or without DHP pretreatment. Control = X-rays alone. 0.2 mg/ml bovine serum albumin, pH 8.0) and 60 μl of FPG in buffer was pipetted onto agarose and mechanism of this activity remains unidentified, incubated at 37oC for 30 min. Slides were stained but direct radical scavenging [2] can be excluded, taking into account the low concentration of the antimutagen. References [1]. Ryabokon N.I., Goncharova R.I., Duburs G., Rze- szowska-Wolny J.: Mutat. Res., 587, 52-58 (2005). [2]. Duburs G.: Chemistry Today, 25, 68-70 (2008). [3]. Wojewódzka M., Dalivelya O., Savina N., Szumiel I.: Effects of 1,4-dihydropyridine derivative treatment on DNA damage in CHO cells. XIV Meeting of the Polish Biochemical Society, Kielce, Poland, 24-26.09.2007. [4]. Rothkamm K., Gunasekara K., Warda S.A., Krempler A., Löbrich M.: Radiat. Res., 169, 639-648 (2008). [5]. Singh N.P., McCoy M.T., Tice R.R., Schneider E.L.: Fig.1. DHP treatment had no effect on the level of SSB in Exp. Cell Res., 175, 184-191 (1988). CHO-K1 cells X-irradiated with doses ranging from 0 to 2 [6]. Kruszewski M., Green M.H., Lowe J.E., Szumiel I.: Gy. Control = X-rays alone. Mutat. Res., 308, 233-241 (1994).

CLA SUPPLEMENTATION – INDUCED CHANGES IN THE PATTERN OF CHOLESTEROL AND EGFR DISTRIBUTION IN THE LIPID RAFTS OF HT29 CELLS Iwona Grądzka, Iwona Buraczewska, Irena Szumiel, Christian Degen1/, Gerhard Jahreis1/ 1/ Institute of Nutrition, Friedrich Schiller University of Jena, Germany

Ionizing radiation-generated reactive oxygen (EGFR) in the plasma membrane. Instead of be- species activate epidermal growth factor receptor ing degraded upon internalization (as it takes place 124 RADIOBIOLOGY after the ligand binding), thus activated EGFR The HT29 human colon cancer cell line was migrates to the nucleus in vesicles formed of cave- maintained in a DMEM medium with 4.5 g/l glu- olin-enriched lipid rafts. Translocation of the re- cose, supplemented with 10% FBS, 100 U/ml peni- ceptor is required for activation of DNA-PK cillin and 100 mg/ml streptomycin, in a humidified o (DNA-dependent protein kinase) – the key enzyme 5% CO2 incubator, at 37 C. Cis-9, trans-11 CLA of the non-homologous end joining (NHEJ), the was dissolved in ethanol and stored in aliquots at main double strand DNA break (DSB) repair sys- -70oC. Before starting the experiment, the com- tem in mammals [1,2]. In search of a compound pound was incubated in the prefiltered medium other than tyrosine kinase inhibitors that could containing 1% BSA, for 1 h at 37oC. Subsequently, prevent this process, we examined the radiosensi- it was diluted to the appropriate concentration and tizing properties of conjugated linoleic acids (CLA), added to the cell cultures for 24 h. especially those concerning the influence on the For isolation and characterization of lipid rafts, rejoining of radiation-induced DSBs. a simplified method was used that allowed to ob- CLA are a mixture of positional and geometric tain detergent-free lipid rafts [6]. The homoge- isomers of linoleic acid (LA, C18:2, cis-9, cis-12), nates of the CLA-treated or untreated cell cul- with two double bonds separated from each other tures were subjected to ultracentrifugation under by one single bond. They are intermediate products the OptiPrep gradient. The lipid rafts were obtain- in the biodegradation of LA by anaerobic bacteria ed by flotation of the cell membrane vesicles through the gradient. After fractionation, they were analyzed for the content of EGFR (ELISA; Santa Cruz Biotech. Inc. USA) and cholesterol (Wako Chemicals Gmbh, Germany). The analyses were performed according to the protocols supplied by the manufacturers. Figure shows the distribution of cholesterol and EGFR in lipid raft fractions. The result (average from 3 experiments) indicates that CLA supplementation of cell culture medium for 24 h alters the pattern of cholesterol and EGFR distribution in the lipid rafts of HT29 cells. It was previously shown that CLA supplementation caused radio- sensitization of HT29 cells accompanied by a reduced rejoining rate of double strand breaks [2]. Although not a definitive proof, these results are consistent with the hypothesis mentioned above. It assumes that CLA incorporation into plasma membrane modifies the properties of lipid rafts and thus, disturbs the activation and nuclear translocation of EGFR. Work partly supported by a statutory grant to the INCT by the Ministry of Science and Higher Education (Poland).

References Fig. Distribution of cholesterol and EGFR in lipid raft fractions obtained by flotation of the cell membrane vesicles [1]. Dittmann K., Mayer C., Fehrenbacher B., Schaller M., through the OptiPrep density gradient. Raju U., Milas L., Chen D.J., Kehlbach R., Rodeman H.P.: J. Biol. Chem., 280, 31182-31189 (2005). in the digestive tract, primarily in ruminants, but to [2]. Grądzka I., Degen C., Jahreis G., Szumiel I.: Radio- a lesser extent in other mammals and some birds. sensitizing effect of conjugated linoleic acid on human In animal models and in cell cultures, CLA was colon adenocarcinoma HT29 cells. XIV Meeting of shown to exert anticancer, antiobese, antiathero- the Polish Biochemical Society, Kielce, Poland, genic, antidiabetic and antiinflammatory activities 24-26.09.2007. [3,4]. In HT29 human colon cells, CLA inhibited [3]. Nagano K., Yanagita T.: J. Biosci. Bioeng., 100, 152-157 (2005). proliferation through down-regulation of EGFR [4]. Aydin R., Turk J.: Vet. Anim. Sci., 29, 189-195 (2005). levels and signalling [5]. Our aim has been to verify [5]. Cho H.J., Kim W.K., Kim E.J., Jung K.C., Park S., Lee the hypothesis predicting that changes in the lipid- H.S., Tyner A.L., Park J.H.: Am. J. Physiol. Gastroin- -protein composition of the cell membranes caused test. Liver Physiol., 284, G996-G1005 (2003). by CLA supplementation can impair the nuclear [6]. Macdonald J.L., Pike L.J.: J. Lipid Res., 46, 1061-1067 transport of EGFR in X-irradiated cells, thus (2005). counteracting and delaying DSB rejoining. NUCLEAR TECHNOLOGIES AND METHODS NUCLEAR TECHNOLOGIES AND METHODS 127

PROCESS ENGINEERING

ELECTRON BEAM DECOMPOSITION OF TOLUENE IN GASEOUS PHASE Yongxia Sun, Andrzej G. Chmielewski, Sylwester Bułka, Zbigniew Zimek

In urbanized area, volatile organic compounds Shimadzu Corporation, Japan) equipped with a (VOCs) are emitted into atmosphere by mainly an- flame ionizing detector (GC-FID). A capillary thropogenic sources. VOCs emission into atmos- column (SupercowaxTM-10, 30 m×0.32 mm×0.25 phere causes serious environmental problem and μm, Supelco Company, USA) was used. Stock so- is adverse to human health. It can cause ozone de- lution AK-101AA-ARO (2000 μg/ml in methanol, pletion in the stratosphere and ozone formation AccuStandard Company, USA) which contained in the troposphere. About 40% of ozone photo- toluene was used for the construction of a calibra- chemically produced might be contributed to the tion curve. By-products formed after EB irradia- emission of aromatics, mainly toluene [1]. Toluene tion of toluene were analyzed by using a GC-MS destruction by using advanced oxidation techno- (Shimadzu GC-17A and a quadruple mass spectro- logies has been studied intensively in recent years, meter Shimadzu QP5050), and a capillary column electron beam (EB) technology is one of the most HP5-MS (Hewlett Packard, 30 m×0.25 mm×0.25 promising technologies among them. In this work, μm). we studied toluene decomposition in an air mix- It was found that more than 80% toluene was ture under EB irradiation, studying the decompo- decomposed at a 20 kGy dose when the initial sition efficiency of toluene vs. dose and identified toluene concentration was between 30 and 80 ppm. by-products. The purpose of this work was to ob- A trace amount of benzaldehyde and acetone was tain a better knowledge of toluene decomposition identified as the degradation products of toluene. in air under EB irradiation on a laboratory scale in Other products might be benzene, ring cleavage etc order to optimize EB operational conditions on a products, CO and CO2 . OH radical decomposi- larger scale in our future work. tion reaction pathway plays the main role in toluene The set up for the preparation of model gas of decomposition. toluene contained in air mixture was similar to This is a preliminary work of toluene decom- that described in our previous work [2]. Toluene position in air by using EB technology. The work model gas was prepared by bubbling synthesized was funded by the Ministry of Science and High- air (≥99.995% purity; 21% O2, N2 as balance gas; er Education (Poland) under the program No. CO2≤1 ppm; BOC Gas Company, Poland) into PBZ-MEiN-3/2/2006. liquid toluene (toluene, purity >99.7% without further purification, provided by J.K. Baker, USA). References The EB irradiation was carried out at an ILU-6 [1]. Derwent R.G. et al.: Atmos. Environ., 30, 181-199 accelerator at 1 atmospheric pressure and ambient (1996). conditions. Concentrations of toluene before and [2]. Sun Y. et al.: Plasma Chem. Plasma Process., 26, 347-359 after irradiation contained in reaction vessels were (2006). measured by a gas chromatograph (GC-17A,

INDUSTRIAL TESTS ON BIOGAS PRODUCTION PROCESSES FROM FERMENTATION OF WASTE MATERIALS FROM THE MILK AND SUGAR INDUSTRIES Piotr Wojciechowski, Andrzej G. Chmielewski, Jacek Palige, Krzysztof Szewczyk1/, Janusz Usidus2/ 1/ Department of Chemical Engineering, Warsaw University of Technology, Poland 2/ EkoPol, Szewnia Dolna, Poland

Industrial development and urbanization of the tion. Possible solution of the problem is the ap- world creates a bigger demand for energy and si- plication of nuclear energy and renewable energy multaneously contributes to the huge degradation sources. The one of the last mentioned techno- of the environment. The biggest damages to the logies is growing of the biomass and then produc- environment are caused by fossile fuel combustion of biogas in the process of the anaerobic 128 PROCESS ENGINEERING methane fermentation. In this process organic the analysis of the acidity of sewage and suspen- (proteins, sugars, fats) matters are transformed sions. The pH-value in the hydrolyzer was cor- into a mixture of methane and carbon dioxide with rected with a solution of lime hydrate. Samples of small traces of ammonia and hydrogen sulphide the biogas for chromatographic measurements (approximately 50 ppm) [1]. were taken during exploatation of the installation. The process of methane fermentation consists of The results of chromatographic measurements are the following stages: presented in Table. • hydrolytic decomposition of the biomass to or- Table. Results of chromatographic measurements. ganic acids, alcohols, hydrogen and carbon dioxide, acidolyse – the decomposition of alco- Composition of biogas [%] Date of measurement hols, high-molecular acids to acetic acid, N CH CO hydrogen and carbon dioxide; 2 4 2 • methanated fermentation in which methanated 28.08.2008 17.35 54.94 24.23 bacteria transformed acetic acid, hydrogen and 22.09.2008 3.35 74.23 13.15 carbon dioxide to methane [1,2]. Laboratory tests on the methanated fermentation 22.10.2008 1.60 79.53 12.62 were carried out using the following media: 20.11.2008 1.21 76.89 15.59 • beet pulp + whey, • silages + whey. The qualitative analyses of the received biogas Processes of the methanated fermentation using show the content of the methane that in the biogas silages of the corn and the grass with an admixture obtained from different tested kinds of the bio- of the whey or beet pulp on a pilot-technical scale mass was about 68-78%. Obtained biogas quality and on experimental installation were made. The allows its application for cogenerative electrical installation consists of: and thermal energy production, and production of 3 • a hydrolyzer with volume Vh=1.5 m , the fuels for the vehicles (CNG – compressed bio- 3 • a bioreactor with volume Vf=8 m , methan, LNG – liquified biomethan). The efficiency 3 • a tank with volume Vb=15 m for biogas storage. of biogas-production in tested installation was 3 3 Research of the methanated fermentation con- 0.0395 to 0.059 m CH4/(m ·h) of the bioreactor- sisted in the fragmentation of raw materials, water -volume per hour [3]. The cascade-system: hydro- dilution, dosage of the drain containing bacterial lyzer-bioreactor makes the stabilization of the bio- cultures, mixing and check up of pH. The prepared gas-stream gained from fermenter. In spite labile mixture was introduced into a hydrolyzer, from parameters of gas and the biomass in hydrolyzer where the air was removed by means of carbon the stable work of fermenter was observed. In the dioxide. For the purpose of the acceleration of the case of the corn-silage, and also in the case of the hydrolysis process, part of the resequence contain- usage of the whey, special difficulties were caused ing methanogenic bacterial cultures from the bio- by low pH of the raw material. The rise of pH was reactor was recycled to the hydrolyzer. The hydro- obtained by addition of Ca(OH)2. The addition of lyzed mixture was heated to approximately 30oC. the whey, containing hydrolyzed matters and also Hydrolyzed biomass was transported with a pump organic acids, showed their influence on the hydro- to the bioreactor. The biogas received in a fer- lysis-process and then the fermentation. Obtained menter was stored in a gasbag, and the fermented biogas without any additional treatment is fitted biomass was transformed by a siphon device to a for application as the fuel for heating and electricity container. The flow of the biogas was measured production. with a gas-meter. The temperature and the composition of the biogas were qualified in the day References cycle. The measurement of the quantity of the bio- [1]. Szewczyk K.W.: Przemysł Chemiczny, 85, 8-9 (2006), mass introduced into the hydrolyzer was done by in Polish. the balance method. The pH-value of liquid in the [2]. Jędrczak A.: Biologiczne przetwarzanie odpadów. PWN, hydrolyzer and bioreactor was measured by means Warszawa 2007 (in Polish). of pH-meter with a glass-electrode adequate to [3]. Usidus J.: Polish Patent No. 197595.

LABORATORY INVESTIGATIONS OF BIOMASS-GROWTH KINETICS IN BIOGAS PROCESS Piotr Wojciechowski, Andrzej Dobrowolski, Andrzej G. Chmielewski

Anaerobic methanated fermentation is a process, fermentor by using substrates limiting biomass in which organic matter (proteins, sugars, fats) are growth: glucose and saccharose. These parameters transformed into a mixture of methane and car- will be applied for modelling biomass growth as bon dioxide with traces of ammonia and hydrogen well as biogas production in an industrial fermen- sulfide (approximately 50 ppm) [1]. teor during radiotracer flow dynamic investigations. The purpose of this work was identification of A periodic bioreactor with the periodic mixing the biomass-growth rate kinetic parameters on the was applied to study the growth-biomass kinetics, basis of experiments carried out with a periodic in a single-stage system, i.e. the stage of hydrolysis NUCLEAR TECHNOLOGIES AND METHODS 129 and fermentation taking place in the same appa- Table. Values of kinetic parameters and the coefficient Yx/s. ratus. The mixing in bioreactor is realized by the Kinetic model closed loop circulation of fermented liquid. Substrate A scheme of the laboratory installation is present- Monod Monod-Jeruzalimski ed in Fig.1. μmax=0.5156 μmax=1.5 [1/day] [1/day]

Glucose Ks=10.331 [g/l] Ks=11.51 [g/l]

Kps=1.25 [g/l] Yx/s=0.6693 [g/g] Yx/s=0.73 [g/g]

μmax=0.3734 μmax=0.4766 [1/day] [1/day]

Saccharose Ks=15.776 [g/l] Ks=19.289 [g/l]

Kps=30.862 [g/l] Fig.1. A scheme of a laboratory installation. Yx/s=0.5869 [g/g] Yx/s=0.5956 [g/g] The method of kinetic modelling of the biomass-growth rate in the periodic-bioreactor with a mum of biomass specific growth rate [1/day], Ks – substrate (S): the glucose and the saccharose uses the substrate concentration [g/l] at μ(S)=½ μmax. the Monod and Monod-Jeruzalimski models which Kps is defined as follows [2,3]: are here presented [2]. From the biomass-growth Kps = Kp · (So – S)/P (4) point of view, most important is the dependence where: P – the concentration of products of the of the biomass specific growth rate (μ) on the con- metabolism inhibitory the biomass growth [g/l], Kp centration of substrate limiting the biomass growth. – the constant of the inhibition for products [g/l]. This dependence has the following form: Because of the difficulty in the denotation of the μ(S) = (1/X)dX/dt = μmaxf(S) (1) concentration of products (P), it is supposed that where f(S) is the standardized kinetic expression the quantity of products was proportional to the for the model of biomass growth [2,3]. utilized substrate: The Monod model does not take into account the P ~ (So – S) (5) inhibition of process by the products of bioreac- The absolute biomass-growth rate (dX/dt) and the tion. The Monod-Jeruzalimski model is taken into rate of utilized substrate (dS/dt) is descibed by a account. system of the following differential equations [2,3]: For the model of Monod: dX/dt = μmax·X·f(S) X(0) = Xo (6) f(S) = S/(Ks + S) (2) dS/dt = (-1/Yx/s)dX/dt S(0) = So (7) we have three parameters: Ks, μmax, μ. where: Yx/s – biomass efficiency coefficient (the For the model of Monod-Jeruzalimski: ratio of the increased biomass to mass of the uti- f(S) = S·Kps/((Ks + S) · (Kps + So – S)) (3) lized substrate), Xo – concentration of biomass at we have four parameters: Ks, Kps, μmax, μ, where: time t=0 [g/l]. t – the time coordinate [day], So – the initial con- The set of the above equations (6)-(7) was solved centration of the substrate at t=0 [g/l], S – the con- on the assumption of the constant value of the co- centration of the substrate at t [g/l], X – the concen- efficient Yx/s, by the integration using the Runge- tration of the biomass at t [g/l], dX/dt – the absolute -Kutta method of the fourth order in the program speed of biomass growth rate [g/(l·day)], μ(S) – Matlab 5.0. The results of solution are the two biomass specific growth rate [1/day], μmax – maxi- time series of concentration: the first one for the

Fig.2. The model of Monod – curves of the biomass growth Fig.3. The model of Monod – curves of the substratum – on saccharose: X(t) – experiment, Xm(t) – model; the coef- saccharose: S(t) – experiment, Sm(t) – model; the coeffi- ficient of correlation – 0.9946. cient of correlation – 0.9916. 130 PROCESS ENGINEERING

Fig.4. The model of Monod-Jeruzalimski – curves of the Fig.5. The model of Monod-Jeruzalimski – curves of the biomass-growth on glucose: X(t) – experiment, Xm(t) – glucose: S(t) – experiment, Xm(t) – model; the coefficient model; the coefficient of correlation – 0.9937. of correlation – 0.9963. biomass model Xm(t) and the second one for the The optimal values of model parameters are substrate model Sm(t). The kinetic parameters for given in Table and the time series of concentra- the models considered of biomass growth has been tions curves (X(t), Xm(t), S(t), Sm(t)) are presented estimated by the use of the optimization procedure in Figs.2-5. of Hook-Jeeves [4] minimizing the objective function (fc) defined as follows: References mm[1]. Szewczyk K.W.: Przemysł Chemiczny, 85, 8-9 (2006), in Polish. fc=−∑∑ X(timi ) X (t ,[p]) / X(ti ) (8) i1== i1 [2]. Kafarow W.W., Winarow A.J., Gordiejew L.S.: Modelo- wanie reaktorów biochemicznych. Wydawnictwa Nauko- where: ti=i·Δt (Δt – the step of time discretization, wo-Techniczne, Warszawa 1983 (in Polish). Δt=1 day), m – number of time steps, X(ti) – the [3]. Gavrilescu M.: Clean Techn. Environ. Policy, 3 (2002). probe of experimental time series of biomass con- [4]. Findeisen W., Szymanowski J., Wierzbicki A.: Teoria centration at time ti, Xm(ti,[p]) – the probe of i metody obliczeniowe optymalizacji. PWN, Warszawa model time series of biomass concentration of 1977 (in Polish). time ti, [p] – the vector of optimal model parameters.

NOX REMOVAL IN THE PROCESS OF ELECTRON BEAM FLUE GAS TREATMENT – CFD STUDY ON THE CONSTRUCTION OF REACTION CHAMBER Andrzej Pawelec, Andrzej Dobrowolski, Andrzej G. Chmielewski

Electron beam flue gas treatment – one of the most depends mostly on the temperature, humidity and promising multipollutant control technologies was ammonia stoichiometry, while NOx removal effi- originally developed for simultaneous nitrogen and ciency depends mainly on the dose of energy ab- sulphur oxides removal. SOx removal efficiency sorbed by the flue gas. Therefore, NOX removal

Fig.1. Scheme of the considered reactor constructions: case 1 – basic construction, case 2 – construction with sloped inlet and one guide vane, case 3 – construction with sloped inlet and two guide vanes, case 4 – construction with sloped inlet reaction chamber and two guide vanes, the first one located before the main reaction chamber and the second one – in the middle of reactor length. NUCLEAR TECHNOLOGIES AND METHODS 131 process is much more energy consuming. Energy consumption is one of the main factors affecting the operational costs of the plant [1] and it is important to find the way for reduction of energy consumption in the process. Dose distribution in a reaction chamber is not uniform and differs very narrowly with distance from the accelerator window [2]. Therefore the gas flow pattern shall be correlated with dose distribution in order to obtain the highest dose absorption. Such gas flow pattern may be obtained by a proper construction of the reaction chamber. The impact of modification of reactor construction on NOx removal efficiency was investigated by methods of computational fluid dynamics (CFD) in combination with empirical Wittig’s formula [3]. Four main types of reactor construction were con- Fig.3. Dependence of NOx removal efficiency on the dose sidered (Fig.1). for the reactor before (case 1) and after the construction modification (case 4).

chamber construction results in an increase of NOx removal efficiency (Fig.3). The research pointed that proper selection of the vane dimensions and location as well as the inlet sloping angle may reduce the energy consumption in the process up to 14% according to unmodified construction of the reactor. The results of the presented case study may be applied for improving the existing reactors and proper design of future installations. References [1]. Tymiński B., Pawelec A.: Economical evaluation of elec- Fig.2. Contours of x velocity in the axis plane for modified tron beam flue gas treatment. Technical Meeting on Ra- construction of reactor (case 4). diation Processing of Gaseous and Liquid Effluents for Contaminant Removal, Sofia, Bułgaria, 07-10.09.2004. It was noticed, that sloping of the inlet and in- IAEA, Vienna 2005, pp.25-34. IAEA-TECDOC-1473. stallation of two double-sided vanes in the middle [2]. Chmielewski A.G. et al.: Radiat. Phys. Chem., 56, of the reactor and near the inlet of the gas to the 509-518 (1999). reactor results in guiding the gas flow rate in the [3]. Wittig S. et al.: Simultane Rauchgasreingung durch upper part of the device (Fig.2). The calculations Elektronenstrahl. Karlsruhe 1988. KfK-PEF45. showed that such modification of the reaction

LABORATORY OF STABLE ISOTOPE RATIO MASS SPECTROMETRY – APPLICATION OF THE QUALITY SYSTEM AND ACCREDITATION Kazimiera Malec-Czechowska, Ryszard Wierzchnicki, Krzysztof Plewka, Piotr Wojciechowski

Since many years, the activity of the Laboratory of – determination of the stable carbon isotope Stable Isotope Ratio Mass Spectrometry has been ratio (13C/12C) of sugars from fruit juices [2], concentrated on the application of stable isotope – determination of the stable oxygen isotope mass spectrometry for environmental investiga- ratio (18O/16O) of water from fruit juices [3], tion and food authenticity control. The Laboratory – determination of the stable hydrogen isotope is dedicated to the stable isotope analysis (13C, 18O, ratio (2H/1H) of water from fruit juices [4], 15N, 34S and deuterium). Recently, the Laboratory – determination of the stable carbon isotope implemented a management system appropriate ratio (13C/12C) in the pulp of fruit juices [5]; for the scope of its activities and comply with the • wine: PN-EN ISO/IEC 17025 standard [1]. The Labora- – determination of the stable carbon isotope tory management system policies related to qual- ratio (13C/12C) in wine ethanol or ethanol ob- ity, includes a quality policy statement and is de- tained by the fermentation of musts, concen- fined in a Quality manual version 1. trated musts or rectified concentrated musts Proposal of the scope of accreditation in the [6]; first step is as follow: • honey: • fruits and vegetable juices: – determination of the stable carbon isotope 132 PROCESS ENGINEERING ratio (13C/12C) of honey and proteins from in the Laboratory. General procedures, which are honey [7]; obligatory in the course of laboratory action to • milk and milk products: realize requirements contracted in the standard – determination of the stable carbon isotope PN-EN ISO/IEC 17025, were worked out. Twenty ratio (13C/12C) of milk and milk products procedures were elaborated which regulate such (own procedure). activities as: confirming and publication of docu- Table. Results obtained in the Laboratory of Stable Isotope Ratio Mass Spectrometry in the frame of the FIT-PTS program (2008 round 2). Product sweet wine caseine collagen Sample code 08/2/A 08/2/C 08/2/Cbis δ13C [‰] -27.08 -23.33 -18.10 robust mean -27.13 -23.38 -18.08 z-scores 0.15 0.21 -0.07 δ 18O [‰] -1.52 robust mean -1.43 -- z-scores 0.58 δ 15N [‰] 6.43 6.23 robust mean - 6.35 6.17 z-scores 0.43 0.31 All investigations are realized using the method of ments, service to the customer, review of requests, isotope ratio mass spectrometry (IRMS). tenders and contracts, internal audits, management According to point 5.9 of the PN-EN ISO/IEC reviews, corrective action and preventive action, 17025 standard, the Laboratory has at disposal training of personnel, control of the equipment, quality control procedures for monitoring the valid- complaints, etc. ity of tests undertaken. The monitoring is planned In the next year we foresee to lodge an applica- and reviewed and includes the following points: tion to the Polish Centre of the Accreditation for • regular use of certified reference materials and/ the impartment of accreditation. or internal quality control using secondary reference materials; References • participation in interlaboratory comparison or [1]. PN-EN ISO/IEC 17025:2005 General requirements proficiency testing program; for the competence of testing and calibration labora- • replicate tests using the same or different tories. methods; [2]. PN-ENV 12140:2004 Fruit and vegetable juices – De- • retesting of retained items; termination of the stable carbon isotope ratio (13C/12C) • correlation of results for different characteristics of sugars from fruit juices – Method using isotope ra- of an item. tio mass spectrometry. In 2008, the Laboratory has taken part in [3]. PN-ENV 12141:2004 Fruit and vegetable juices – De- 18 16 Food Isotopic Techniques – Proficiency Testing termination of the stable oxygen isotope ratio ( O/ O) Scheme organized by EUROFINS SCIENTIFIC of water from fruit juices – Method using isotope ratio mass spectrometry. ANALYTICS, Nantes, France and Bevabs office, [4]. PN-ENV 12142:2004 Fruit and vegetable juices – De- JRC-ISPRA. Italy. Samples of sweet wine, casein termination of the stable hydrogen isotope ratio (2H/1H) and collagen were tested. The resulting statistical of water from fruit juices – Method using isotope ratio data were sent to each individual laboratory. Re- mass spectrometry. sults obtained by our Laboratory are presented in [5]. PN-ENV 13070:2004 Fruit and vegetable juices – De- Table. All results are correct; values from z-scores termination of the stable carbon isotope ratio (13C/12C) in all chances are considerably lower from 2. In- in the pulp of fruit juices – Method using isotope ratio troduced results testify about high competences of mass spectrometry. our Laboratory. The Laboratory conducts research [6]. Rozporządzenie Ministra Rolnictwa i Rozwoju Wsi z according to standardized methods and according dnia 12 maja 2003 r. w sprawie metod analiz wyrobów winiarskich do celów urzędowej kontroli pod względem to methods worked out in the laboratory which jakości handlowej. Dz. U. z 2003 r. nr 126, poz.1173, became validated. In the area of the technical ac- zał.41 (in Polish). tivity works are continued embracing the prepara- [7]. Determination of the stable carbon isotope ratio tion of technical documentation. Elaboration of (13C/12C) of honey and protein from honey – AOAC embracing necessary records are much advanced Official Method 998.12. NUCLEAR TECHNOLOGIES AND METHODS 133 SAMPLE COLLECTION AND PREPARATION

FOR CO2 ISOTOPIC ANALYSIS IN INDUSTRIAL OFF-GASES Krzysztof Plewka, Ryszard Wierzchnicki

The analysis of isotope ratios is a new method to sample from a vessel connected to a glass vacuum study of greenhouse gases origin and to investi- line and it is purified by standard cryogenic tech- gate their chemical reaction pathways [1-2]. The niques. The purification system consists of two cold main aim of the work was to elaborate a method traps. The first trap is designed for H2O condensa- for measuring isotopic composition of greenhouse tion; it is dipped in acetone chilled by liquid N2 to o gases (CO2, CH4 and N2O) emitted from chosen -73±3 C. The second trap serves to freezing CO2 o industrial processes. The first stage of realization and is dipped in LN2 at -196 C. Initially, the vessel of the project is the collection of gas samples and with the sample is connected to the vacuum line via –4 extraction of CO2 for isotopic measurements [3-5]. an o-ring joint and the line is evacuated to 10 A portable gas sampler was constructed for col- mbar. The gas accumulated in the vessel is trans- lection of gas samples at fieldwork (Fig.1). From ferred to the vacuum line and condensable com- each of the gas sampling ports, which are situated pounds are caught in cold traps. Non-condensable at the electrofilter exit, the gases are collected to gases are pumped away. The second cold trap is o three types of glass vessels. The first glass vessel is warmed to approximately 30 C to release CO2, for a vacuum purification system, the second for a while H2O remains frozen in the first trap. Liberated continuous flow purification system and the third CO2 is transferred to another glass sample vessel, one is for gas chromatography analysis. Before which is subsequently connected to the dual inlet sampling, the vessels are filled with pure helium system of the isotope ratio mass spectrometer DELTAplus (Thermo Finningan Bremen, Germany). The measurement is performed in relation to the working standard of CO2. Continuous purification system (Fig.3) has been constructed as an alternative for the vacuum puri- Fig.1. Portable gas sampler: 1 – warmed probe with two fication system for the separation of CO2 originat- ceramic filters situated coaxially, 2 – U-shape dryer filled ing from industrial processes. Carbon dioxide ex- with magnesium perchlorate anhydrous 6÷18 mesh and traction process, similarly as in the vacuum line, indicated silica gel, 3 – diaphragm pump, 4 – flow meter consists in the cryogenic separation of CO from a with maximum flow 5.0 LPM, 5 – gas vessels. 2 gas sample. The main part of the line are two heli- in the laboratory to prevent contamination from earlier samples or ambient air. The sampling set is equipped with a small diaphragm pump (12 V) (N 86 KTDCB: KNF Neuberger GmbH) with an efficiency of 360 LPH supplied with a battery (DC12V/7Ah). Combustion gases enter the sampler at a rate of 5 LPM by a warmed probe with ceramic filters situated coaxially. Since the temperature of gases is about 150oC, it is necessary to use the warmed probe to prevent condensation of water on the ceramic filters. Then, the warmed gas enters U-shape dryers filled with magnesium perchlorate anhydrous and indicated silica gel. Col- lection of one sample takes about 3 min, which is Fig.3. Continuous flow purification system: 1 – gas cylinder the time needed to flush ten times each of glass with pure helium (99.9995%), 2 – pressure controller, 3 – vessels. glass vessel with 3-way PTFE key, 4 – helicoidal cold trap For CO separation from industrial off-gas 2 for water, 5 – helicoidal cold trap for CO2 with vacuum-valves samples, a special vacuum purification system was and o-ring joint, 6 – flow meter. elaborated (Fig.2). In this method CO2 is separated from other gasses by expansion of the gas coidal glass traps which act in the same way like in previous line. The second cold trap for CO2 is equipped with vacuum-valves and an o-ring joint used for connection to spectrometer. Glass elements of the line are jointed by silicone tubes. After connection the glass vessel in the line, it is flushed ten times with pure helium at a rate of 1 LPM trough a bypass installed on the vessel. This is necessary to prevent contamination from earlier Fig.2. Vacuum purification system: 1 – glass vessel with samples or ambient air. In the second step, the –2 vacuum-valves, 2 – cold trap for water, 3 – helicoidal cold flow rate is reduced to 8·10 LPM. Helium is used trap for CO2, 4 – pressure gauge, 5 – glass vessel cold trap as a carrier gas which flows trough the vessel filled for CO2, 6 – cold trap. with the sample and then enters the cold traps. 134 PROCESS ENGINEERING The whole line is flushed ten times. Condensable References compounds are caught in the cold traps. Non-condensable gases are flushed away. In the sec- [1]. Stabe isotope measurement techniques for atmospheric greenhouse gases. IAEA, Vienna 2002. IAEA-TEC- ond helix frized CO2 and helium gas are trapped. Taking into account that working standard is pure DOC-1268. [2]. Isotope aided studies of atmospheric carbon dioxide CO2, it is necessary to pump away helium from the second trap, while CO remains frozen. After that and other greenhouse gases, Phase II. IAEA, Vienna 2 2002. IAEA-TECDOC-1269. procedure, the sample is ready for measurement [3]. Bertolini T., Rubino M., Lubritto C.: J. Mass Spectrom., in IRMS (isotope ratio mass spectrometer). 40, 1104-1108 (2005). The work was performed in the framework of [4]. Werner R., Rothe M., Brand W.: Rapid Commun. the project No. PBZ-MEiN-3/2/2006 ”Process en- Mass Spectrom., 15, 2152-2167 (2001). gineering for hazardous and greenhouse gases [5]. Iwata R., Ido T., Kovacs Z., Mahunka I.: Appl. Radiat. emission control and utilization” („Inżynieria pro- Isot., 48, 4, 483-485 (1997). cesów ograniczania emisji oraz utylizacji gazów szkodliwych i cieplarnianych”).

PREPARATION AND CHRACTERIZATION OF PVDF MEMBRANES FOR ENVIRONMENTAL APPLICATIONS Marian Harasimowicz, Mohamed Khayet1/, Grażyna Zakrzewska-Trznadel 1/ Faculty of Physics, Complutense University of Madrid, Spain

Polyvinylidene fluoride (PVDF) is an excellent membranes for membrane distillation (MD) were polymer material with high chemical resistance for prepared by the method elaborated by Khayet and acid, alkali and organic solvents. Flat-sheet porous Matsuura [1]. The concentration of PVDF in the A B

Fig.1. Membranes prepared with 12 wt% PVDF (Mw=275 000, Aldrich), 3 wt% LiCl (99%, ACS Reagent, Aldrich), N,N -dimethyl acetamide (DMAC, anhydrous 99.8%, Sigma-Aldrich): A – without silica, B – with 1 g/100 g silica (SiO2) fumed (particle size – 0.014 μm, surface area – 200±25 m2/g (Sigma-Aldrich)). NUCLEAR TECHNOLOGIES AND METHODS 135 casting solution was 12, 15 and 20 wt%. Two pore- • The scanning electron microscope (JMS-6335F) -forming additives, LiCl – 3 wt% and SiO2 – 1 wt% images showed that the structure of the top sur- were incorporated in the polymer solution. The face depended on the concentration of PVDF membranes were tested by physical methods (field and was more porous when SiO2 and LiCl were A B

Fig.2. Hollow fiber membranes prepared with 15 wt% PVDF (Mw=275 000, Aldrich), 3 wt% LiCl (99%, ACS Reagent, Aldrich), N,N-dimethyl acetamide (DMAC, anhydrous 99.8%, Sigma-Aldrich): A – without silica, B – with 1 g/100 g silica 2 (SiO2) fumed (particle size – 0.014 μm, surface area – 200±25 m /g (Sigma-Aldrich)). emission scanning microscopy, contact angle mea- added to the casting solution (Fig.1). J value was surements, X-ray diffraction) and by direct per- found to be higher and the salt retention coeffi- meation measurements. Each membrane sample cient lower when LiCl and SiO2 were added to of area 2.75x10–3 m2 was fixed between two cylin- the casting solution. drical chambers (“hot” and “cold”) filled with aque- The prepared PVDF membranes were applied ous solutions. The experimental process applied successfully in the DCMD process for desalination was a direct contact membrane distillation (DCMD). and they also can be used for the treatment of haz- The DCMD measurements were made at a mean ardous solutions, including wastes containing orga- o temperature Tm between 15 and 65 C by using 1 M nic substances (non-solvents for PVDF) at low con- NaCl solution in the “hot” chamber and pure water centrations, and for production of ultra-pure water. in the “cold” chamber. The distillate volume VD vs. Porous hollow fiber membranes (Fig.2) can be con- time t and the permeate flux J vs. mean tempera- sidered for application in membrane contactors ture Tm were obtained and the following depend- used for the treatment of various hazardous wastes, ences have been observed: as well as for radioactive waste processing [2]. • J increases with enhancing Tm when SiO was 2 References added to the PVDF polymer casting solution. • J values in DCMD experiments with NaCl were [1]. Khayet M., Matsuura T.: Eng. Chem. Res., 40, 5710-5718 lower than for the same experiments with pure (2001). [2]. Burlatsky S., Jiang D., Wysk R.: Liquid membrane water. system for removal and concentration of transuranic • Concentration of NaCl in the distillate in- elements. In: Proceedings of the Conference on In- creased with PVDF concentration and was dustry Partnerships to Deploy Environmental Tech- higher for PVDF membranes prepared with nology, Morgantown, West Virginia, USA, 21-23.10.1997. SiO2 than for those prepared without SiO2. DOE Federal Energy Center Publications, 1997. 136 PROCESS ENGINEERING APPLICATION OF RTD METHOD TO STUDY FLOW STRUCTURE AND HYDRODYNAMIC CONDITIONS IN AN APPARATUS WITH HELICAL FLOW Agnieszka Miśkiewicz, Andrzej Dobrowolski, Grażyna Zakrzewska-Trznadel

The possibility of application of fluorescein and of residence time (vard) has been evaluated. The radioactive 99mTc in the form of pertechnetate ion results obtained have shown a strong reduction of 99m – vard ( Tc O 4) as tracers for the determination of resi- with the rise of all considered process para- dence time distribution (RTD) of liquid phase, as meters. With the rise of retentate flow and trans- well as for the diagnosing hydrodynamic condi- membrane pressure the MRT decreased. The re- tions in an membrane apparatus with helical flow tentate flow structure for open-open model was was studied. By equipping a tubular membrane close to the plug flow and it was expressed by a with the movable part, namely a rotating shaft high value of Peclet number. There was no the sig- placed centrally, it was possible to create helical nificant change of Peclet number for the open-closed Taylor-Couette flow (CTF) inside the apparatus. model. For the purpose of optimal process para- Such a design may result in limited axial disper- meters estimation, the modelling of hydrodynamic sion coefficients in relation with the dispersion conditions in the membrane module using an or- coefficients in other directions, independence of thogonal central composite design (CCD) was car- mixing intensity on residence time of the media in ried out. the apparatus and good transport parameters. An As the analysis of the surface plots showed, the RTD method with application of tracers was em- effects of velocity of rotating shaft and applied ployed in the experiments. The studies were sup- pressure were significant and negative, i.e. the in- plemented by modelling. For evaluation of experi- crease of applied pressure or increase of the ve- mental data, the model of retentate flow consisting locity of rotating shaft led to the decrease of dimen- of two axial-dispersion models: open-open and sionless variance. Also, the increase of retentate open-closed connected in series, was developed. flow led to the decrease of dimensionless variance, The influence of process parameters: transmem- but the effect was less significant. More significant brane pressure (P), retentate flow (QR) and rota- was an interaction effect of QR with the other two tion frequency of the inner cylinder (Ω) on mean variables. A strong interaction effect between QR residence time (MRT) and dimensionless variance and Ω was observed. Increasing of QR was more

Ω [rpm] Ω [rpm] A)A) B)

Fig.1. Response surface plot indicating the effect of process variables upon response function: A) P=0.45 bar, B) QR=75 l/h, C) Ω=1750 rpm. NUCLEAR TECHNOLOGIES AND METHODS 137 significant at high rotation frequency of the mov- applied. The optimal parameters for the minimum able part than at the low ones, as well as increase of vard (vard=0.0087) were as follows: P=0.81 of rotation frequency was more important in a high bar, QR=105.37 l/h, Ω=2661.25 rpm. Under these QR region (Fig.1). conditions, the retentate flow structure was very As an optimization procedure, the simplex close to the plug flow. method according to Nelder-Mead algorithm was

REMOVAL OF COPPER FROM AQUEOUS SOLUTIONS BY MICELLAR-ENHANCED ULTRAFILTRATION Ioannis Xiarchos1/, Agnieszka Jaworska, Grażyna Zakrzewska-Trznadel 1/ Sector of Petroleum Engineering, Civil Engineering and Geotechnology, Delft University of Technology, the Netherlands

Membrane processes provide a viable alternative fication to study the separation of copper from for heavy metal recovery, as they can achieve high aqueous solutions. Response surface methodology permeate fluxes and high rejection coefficients with was used to study the cumulative effect of the vari- low energy costs, under mild conditions. In addition, ous parameters, namely surfactant (sodium do- membrane separation can be carried out continu- decyl sulphate – SDS, anionic) concentration, pH, ously and membrane processes can be easily com- and surfactant/metal molar ratio and to optimize bined with other separation processes (hybrid pro- process conditions for maximal removal of copper cessing). One of the available membrane processes from aqueous solutions via micellar-enhanced ulis micellar-enhanced ultrafiltration (MEUF). The trafiltration (Fig.1). For obtaining the mutual in-

Fig.1. Response surface and contour plot indicating the effect of pH and SDS/Cu2+ molar ratio upon rejection coefficient C at SDS concentration: surf=5 g/l. principle of the process is the formation of micelles teraction between the variables and optimizing by surfactant, which are spherical aggregates con- these variables, a central composite design by the taining 50-150 surfactant molecules, at concentra- use of response surface methodology was employed. tion equal or bigger than the critical micelle con- The analysis of variance (ANOVA) of the quad- centration (CMC). In MEUF, metal ions are removed ratic model demonstrated that the model was high- by binding the cations to oppositely charged mi- ly significant. The model was statistically tested celle surface, which is primarily electrostatic in and verified by experimentation. Values of pH in nature. The membrane used in the process with the range of ca. 7.5 were very successful for the pore size smaller than the diameter of the micelle, separation. The maximum rejection coefficient of rejects the micelles containing metal cations. 98.4% was obtained for the following optimal con- This work describes an experimental approach ditions: SDS/Cu2+ molar ratio *r=7.85, *pH=7.36, C to micellar-enhanced ultrafiltration and its modi- * surf =6.82 (g/l SDS).

Fig.2. Response surface and contour plot of predicted rejection as a function of pH value and SDS/Cu2+ molar ratio at constant SDS/PEG mass ratio: q=3. 138 PROCESS ENGINEERING A modification of micellar-enhanced ultrafil- a constant concentration of surfactant equal to 5 tration for the removal of copper from aqueous g/l (Fig.2). A comparison of the two systems in the solutions was studied by the implementation of region of their common factors showed that the sodium dodecyl sulphate-polyethylene glycol (PEG) addition of polyethylene glycol caused a slight in- aggregates. A full factorial design was employed crease in rejection coefficient of copper, but also for studying the effect of molar ratio of surfactant/ could function as “scavenger” for surfactant species. metal, pH and mass ratio of surfactant/polymer at NUCLEAR TECHNOLOGIES AND METHODS 139

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

INAA IN THE STUDIES OF LEAD WHITE IN THE MEDIAEVAL POLISH PAINTING OF THE POMERANIAN SCHOOL Justyna Olszewska-Świetlik1/, Ewa Pańczyk, Lech Waliś 1/ Institute for the Study, Restoration and Conservation of Cultural Heritage, Nicolaus Copernicus University in Toruń, Poland

In the second half of the XV century, Gdańsk en- Identification of materials plays an important joyed renown as one of the most significant cities role in studying works of art. Recognition of spe- of Europe. The city belonged to the Hanseatic cific features of materials allows for supplement- League and operated extensive trading activities. ing the knowledge on their nature, origins, the Its favorable economic condition promoted the region in which a given work was created as well development of the city. The rich society founded as preferred techniques. Instrumental neutron ac- both sacred and secular buildings decorated with tivation analysis (INAA) has been successfully ap- numerous works of art [1]. plied in studies of old painting. The method is used Being a significant commercial centre, Gdańsk for assaying trace elements contained in lead white. maintained wide contacts with a number of cities The pigment was a predominant type of white Europe-wide. The Gdańsk art of those times was paint used by painters from antiquity up to the particularly influenced by the Netherlands and XIX century. Northern Germany [2]. The purity of lead white is directly related to The largest and the most significant shrine in the the development of methods for production and city was the Blessed Virgin Mary’s Basilica. purification of lead. Except for the technological The Blessed Virgin Mary’s Basilica was an ex- process, distribution of trace elements depends on pression of the city’s power in its religious, social the origins of lead ore deposits. and cultural aspects. Therefore, results of assaying trace elements in Under these circumstances, wealthy families, fra- lead white by means of neutron activation analysis ternities and craft guilds were undertaking efforts are helpful in determining the time when a paint- to show their significance by funding expensive ing was created as well as any later restorations works of art for the church. In addition to a number and allow to obtain additional information on the of other works of art, numerous altar decorations origins of a painting. The neutron activation analysis in the form of triptychs or extended polyptychs is helpful both in dating a work as well as in iden- used to be exposed in the church. tifying any repainting or conservation activities. Gdańsk panel painting of the second half of the Based on currently available analytical results, XV century is a non-homogeneous combination two types of white lead have been identified: the works of art. A part of the altars might have been so-called trans-Alpine white used in paintings to imported, while another was created by foreign the North of the Alps and cis-Alpine white applied artists working in Gdańsk or by local painters. in the South, mainly in Italy. Therefore, the paintings from the Blessed Virgin All the samples were taken from paintings sub- Mary’s Basilica constitute a representative collec- jected to a routine maintenance work after reveal- tion of the Pomeranian painting [3]. ing their structure and state of preservation of the The study covered 16 paintings originating from original layers. After removal of protective coat- old altar decorations preserved in their entirety or ing with a scalpel under a microscope, a sample of part. the white was taken directly to a quartz ampoule. Additionally, West-European paintings of known The sampling spots were selected so that they had origins, such as: the Netherlandish triptych “Last not shown admixtures of other pigments as indi- Judgment” (dated 1467-1479) by Hans Memling cated by UV luminescence tests. Detailed descrip- (1435-1494) present in St. Mary’s Basilica in Gdańsk tion of the paintings is presented in Table. 1-6 since 1473, currently in the collection of the National samples from each object, with a mass from 0.1 to Museum in Gdańsk [4] and fragments of a plot 1 mg were collected. from the old altar in the St. Elisabeth Church in The analysis of lead white samples was carried Wrocław [5] (1462) illustrating “Offering of Jesus out using the INAA method without chemical in the Shrine”, by Hans Pleydenwurff (1420-1472), separation, using standards of analyzed elements. a German painter, currently in the National Museum The samples were packed together with standards in Warsaw, have been selected for comparison. of such elements as Na, K, Sc, Cr, Mn, Fe, Co, Ni, 140 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

Table. Description of the analyzed samples.

Catalogue and sample number Name of panel painting Dating Gdansk school 1P-25÷29 The Mary Retable of Priestly Gild, The Church of the Blessed Virgin Mary, Gdańsk 1473-1478 2P-17÷18 The predella with Martyrdrom of St. Adrian, The Church of the Blessed Virgin after 1468 Mary, Gdańsk 3P-12÷14 The large of Ferbers Altar, The Church of the Blessed Virgin Mary, Gdańsk 1480-1498 4P-6÷7, 9÷10 The small of Ferbers Altar, The Church of the Blessed Virgin Mary, Gdańsk 1485-1490 5P-48÷53 The Jerusalem Triptych, The Church of the Blessed Virgin Mary, Gdańsk 1490-1500 6P-30÷35 The Triptych of Crucifixion, The Church of the Blessed Virgin Mary, Gdańsk 1480-1500 7P-15÷16 The predella with life of Mary Virgin, The Church of the Blessed Virgin Mary, Gdańsk 1485-1490 8P-20÷21 The Table of Ten Commandments, The Church of the Blessed Virgin Mary, Gdańsk 1480-1490 9P-4÷5 The Saviour Christ on the doors of ciborium, The Church of the Blessed Virgin 1478-1482 Mary, Gdańsk 10P-39÷42 The Retable of St. Simon and St.Thaddeus, The Church of the Blessed Virgin 1485-1490 Mary, Gdańsk 11P-43÷47 The Retable of St. Barbara, The Church of the Blessed Virgin Mary, Gdańsk 1480-1500 12P-36 Ecce Homo, The Church of the Blessed Virgin Mary, Gdańsk 1483-1500 13P-28, 29 The Flagellation and Thorn Crown, The Church of the Blessed Virgin Mary, after 1487 Gdańsk 14P-22÷24 The predella of Mary Virgin with the Child, The Church of the Blessed Virgin after 1478 Mary, Gdańsk 15P-19 The predella of Mary Virgin Coronation, The Church of the Blessed Virgin Mary, 2nd half Gdańsk 15th century 16P-37, 38 The predella of Christ and the 12 Apostles, The Church of the Blessed Virgin Mary, about 1500 Gdańsk Malopolska school M-1 Adoration of Dead Christ, Chomranice 1438-1439 M-2 Triptych, Kamionka Mała 1456 M-3 St. Catherine of Alexandria, Biecz 1470 M-4 Mourning over Dead Christ, Czarny Potok 1449 M-5 Triptych, Nowy Sącz 1452 M-6 Triptych, Ptaszkowa 1440 Silesian School S1-7, 21 Crucifixion Triptych, Gać Śląska 1440-1450 S-2 St. Barbara’s Altarpiece, Wrocław 1447 S-3 Veraikon, Wrocław 1460 S-4 Veraikon, Legnica 1450 S-5 Crucifixion Triptych – Peter Wartenberg’s Foundation, Wrocław 1468 S-6 Werder’s Epitaph, Wrocław 1456 S-7 Triptych of St. Hedwig’s Legend, Wrocław 1440 S8-17 The Virgin and Child, Wrocław 1460 S8-23 St. James’s Life, Wrocław 1460 S-9 The Virgin in Apartment, Wrocław 1460-1465 S-10 The Polyptych from St. Elisabeth Church, Wrocław 1482 S-11 Andrzej Steinberg’s Epitaph, Świdnica 1486/87 S-12 The Retable from St. Peter and St. Paul Church, Strzegom 1486/87 S-13 Dolorous Christ from St Elisabeth Church, Wrocław 1486/87 S-14 Prince W. Zaganski’s Epitaph, Wrocław 1486/87 S-15 The Retable from The Blessed Virgin Mary Church, Wrocław na Piasku 1486/87 German and Netherlands school G-14 Hans Pleydenwurff – the Retable from St Elisabeth Church, Wrocław 1462 D – 61÷ 64 Hans Memling – The Last Judgment 1473 NUCLEAR TECHNOLOGIES AND METHODS 141 Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Zr, Mo, Ru, Out of 40 determined elements, only the ele- Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, ments identified in all tested samples were select- Tb, Dy, Ho, Er, Yb, Lu, Hf, Ta, W, Ir, Au, Hg, Th ed for further analysis. Elements such as Cd, Ga, and 238U. Also attached were the standards of gold Ho, Lu, Mo, Ni, Rb, Se, Tb, Ta and Zr, the con- and scandium evaporated onto a piece of alumin- tent of which in a majority of analyzed samples, ium foil. They played a role of the thermal neu- was below the detection threshold of the method, tron flux monitor. were disregarded. Irradiation of the samples was carried out in the The clustering analysis using STATISTICA MARIA nuclear reactor at Świerk, in a channel (StatSoft) program [6] was carried out to identify with 8*1013 n/cm2s thermal neutron flux. The irra- the similarity degree of analyzed objects. The clus- diation time was 24 h with a subsequent 8-hour tering analysis was carried out for standardized cooling. Then, the irradiated samples were un- and logarithmic variables. A cluster analysis pro- packed and washed in 1:1 hydrochloric acid solu- cedure was first applied, using all the variables for tion and rinsed in alcohol to remove surface con- all the tested 48 samples of lead white collected taminations. from the 16 paintings represented the Pomeranian Measurements of activity of the samples and school. Ultimately, 28 elements were selected for standards prepared in such a way were carried out multi-parameter statistical analysis aimed at iden- using an HP germanium detector with an active tifying the degree of similarity of analyzed paint- volume of 80 cm3 and an energy resolving power ings. The output dendrogram is shown in Fig.1. of 1.95 keV for the 1333 keV – 60Co energy. The The studies have proven that lead white used in detector cooperates with a S100 Canberra analyzer, Gdańsk paintings is similar to the trans-Alpine controlled by IBM/PS-2. The analysis of complex white used in Northern Europe. Its characteristic gamma radiation spectra was carried out using features are low contents of silver and zinc. The micro-SAMPO and Gene 2000 programes. The pigment that has been used for painting was pure, measurements were repeated 6 times within 3 which is a testimony of its very good quality. The months after irradiation. The measurement time analysis of clusters from samples of the Pomeranian varied between 300 and 10 000 s. School paintings has allowed to divide them into Forty elements were identified and determined four groups. Such a division suggests that lead ores in analyzed samples. Various methods of statisti- originating from various sources were used for the cal analysis were used to evaluate whether these production of lead white. differences are related to the use of different in- As compared to other Polish schools – that of put materials or a result from errors during the Malopolska [6] and Silesian [7,8], the Pomeranian analysis (non-representative sample collected). Ad- painting brings resemblances to the Silesian school. ditionally, only distributions of the elements that Figure 2 presents the results of this analysis. are important in lead white identification were There are distinct differences with respect to analyzed [6,7]. the Malopolska school of painting. They prove

Fig.1. Cluster analysis of 16 analyzed panel paintings Pomeranian school describes 28 features (features number = determined elements number); standardized and logarithmic variables. 142 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

Fig.2. Cluster analysis of 16 analyzed panel paintings, 22 lead white samples taking from panel paintings of Malopolska and Silesian schools and 2 samples represented German and Netherlands schools describes 28 features (features number = determined elements number); standardized variables. that sources of white lead were different. Contrary ings shows distinguishable similarities to the white to the Malopolska school, the Pomeranian school applied by Hans Memling, who worked in the represents a non-homogeneous set. Moreover, the Netherlands and the works by Pleydenwurff, the Malopolska school is distinguished by high amounts German artist, who worked for the St. Elisabeth of copper and silver that are present at sustained Church in Wrocław. That fact may prove that the level almost in all analyzed objects. methods used for the production of white lead Taking into account the results of clustering were similar and provides information on the sup- analysis, the range of concentrations (minimums ply sources of painting materials associated with and maximums) of trace elements (Ag, As, Ce, the tradition of Western and Northern Europe. Cu, Eu, La, Sb, Sm and Zn), very important in The Malopolska school is more closely related to

Fig.3. Trace element patterns in lead white from Malopolska, Gdansk and Silesian school paintings. lead white identification, was determined. Figure the tradition of Polish art. Lead ores were proba- 3 presents the distributions of these elements in bly acquired from domestic deposits from mines analyzed lead white samples from Malopolska, in the regions of Malopolska, Silesia or the Święto- Silesian and Pomeranian schools. krzyskie Mountains. The geographical location of Gdańsk, its wide contacts and trade exchange created favourable References conditions for acquiring high quality materials. [1]. Matysik S.: History of Gdańsk. In: Gdańsk, its history The white lead identified in the Pomeranian paint- and culture. Ed. F. Mamuszko. Warszawa 1969, pp.36-42. NUCLEAR TECHNOLOGIES AND METHODS 143

[2]. Gosieniecka A.: Art in Gdańsk; painting, sculpture, [6]. Pańczyk E., Ligęza M., Waliś L.: J. Radioanal. Nucl. graphics. In: Gdańsk, its history and culture. Ed. F. Ma- Chem., 244, 543 (2000). muszko. Warszawa 1969, pp.267, 274, 285. [7]. Olszewska-Świetlik J.: Techniki malarskie mistrza oł- [3]. Olszewska-Świetlik J.: Technology and technique of tarzu ze Strzegomia (1486/87) (Painting technique of Gdańsk panel painting of the second half of 15th cen- the Mater of the Strzegom altar (1486/87)). Ph.D. the- tury. UMK, Toruń 2005. sis. Toruń 2002 (in Polish). [4]. Flik J., Olszewska-Świetlik J.: The triptich “Last Judge- [8]. Pańczyk E., Olszewska-Świetlik J., Chmielewski K.: ment” by Hans Memling, National Museum in Gdańsk. Biuletyn Informacyjny Konserwatorów Dzieł Sztuki, Painting technology and technique. UMK, Toruń 2005. 15, 3-4, 35-38 (2004). [5]. Dobrzeniecki T.: Panel painting, Catalogue of the Na- tional Museum collection in Warszawa. Warszawa 1972, p.236.

INCORPORATION OF RARE EARTH ELEMENTS Ce AND La INTO 316 STEEL USING HIGH INTENSITY PULSE PLASMA BEAM TECHNIQUE Bożena Sartowska1/, Jerzy Piekoszewski1,2/, Lech Waliś1/, Marek Barlak1,2/, Zbigniew Werner2,3/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland 3/ Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa, Poland Low hardness and poor tribological properties of type (RPI) of device originally developed for nu- stainless steels impose in many cases strong limi- clear fusion studies and described in detail in [8]. tations of their use. On the other hand, there are In RPI the high intensity plasma pulses are gener- many examples in which an application requires a ated as a result of a low-pressure, high current dis- good electrolyte corrosion and high temperature charge between two concentric, cylindrical sets of corrosion resistance along with a good wear re- rod-type electrodes. The discharge is initiated by sistance. Examples of such applications include: an HV (high voltage) pulse applied with a delay sinking pumps for dirty water, liquid flow sensors, time τd after the moment of injection of working temperature, pressure and humidity sensors for gas into the inter-electrode space. For short τd, in aggressive environments, interconnectors for solid addition to the generation of plasma of the work- oxide fuel cells (SOFC) etc. In all these cases staining gas, a rapid erosion of the metallic electrodes less steels are frequently used. The beneficial ef- occurs so the beam contains ions of the working fect of active elements with high oxygen affinity, gas and ions/atoms of the electrode material. This such as yttrium, cerium, lanthanum and other rare mode is named deposition by pulse erosion (DPE earth elements (REE) on high temperature oxida- mode) and was used in the carried out experiment. tion resistance and corrosion resistance against the The electrode tips of 40 mm in length and 2 mm in aggressive media has already been studied [1,3]. diameter were machined from the chunk of misch- The incorporation of the reactive element can be metal containing Ce (64.9 wt%), La (33.7 wt%), made in the melt of bulk material or through sur- Pr, Fe and Mg. During machining, special precau- face treatment like ion implantation, sol-gel coat- tions were taken due to the high flammability of ing process etc. [1-3]. On the other hand, it is known this material. from a recent study [4,5] that the surface modifi- Conditions applied in the present experiments cation process using intense plasma pulsed leads are listed in Table. The large range of processing to improvement of the tribological properties of parameters in our present pilot experiments is unalloyed steels. dictated by a fact that it is impossible to predict Following the experience gained in modifica- the ad hoc pertinent conditions to attain the re- tion of a Ti foil by addition of Pd [6,7] in the pre- quired results. Anticipating further discussion, we sent work, in order to introduce REE into differ- Table. Parameters of the DPE mode of RPI. ent kind of steels we employed for the first time high intensity plasma pulses. The plasma pulses Parameter contain both ions/atoms of chosen elements – Ce HV [kV] 29-31.5 and La (mischmetal) and those of the working gas. The pulse energy densities with their duration Energy density [J/cm2] 5.0 in μs range were sufficient to melt the near sur- Delay time τ [μs] 150-180 face layer of the substrate and hence introduce d those elements into the surface layer of steels. Pulse duration [μs] 0.1-0.5 Here, the details of experiments and their results nitrogen are presented. Working gas The 1.4401(AISI 316) steel with the elemental Number of pulses 2, 5, 10 composition: Cr – 16.75%, Ni – 10.25%, Mo – 2.1% was used as the substrates. The main tool used for Inner and outer electrodes Ce-La tipped, (64: 250 mm length, 2 mm diameter) unalloyed steel rods their modification was the rod plasma injector 144 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS would like to mention here that even after series intense pulses, the surfaces were smoothening and of present experiments optimum conditions are the “waves” were observed. After 5 intense pulses, still not determined. The modified surfaces of the the cracked surface layers were observed. After 10 A B

C D

Fig.1. The surface morphology of 316 steel: (A) initial and modified with (B) 2, (C) 5 and (D) 10 intense plasma pulses. samples were characterized using: scanning elec- intense pulses, cracks are visible too and droplets tron microscopy technique using SEM DSM 942 are clearly seen. Observed at the modified surfaces (Zeiss, Germany) for surface morphology observa- cracks and other morphological features like drop- tions and the EDS (energy dispersion spectroscopy) lets and bubbles are characteristic of remelting elemental analysis using the Bruker (Germany) techniques based on the melting of near surface microanalysis system for efficiency of REE addi- layer of the substrate. tion process determination. Results of elemental analysis of added REE to Results of morphology observations are pre- the modified layer allow us to state that the pro- sented in Fig.1. At the surfaces of initial material, portion of Ce/La added to the surface layer is the the grains in different sizes are visible as a result same as the ratio of content of these both REE in of steel production process. Grains are distributed the initial mischmetal. The values are: 2.07, 2.03 evenly; no special direction can be distinguished. and 1.96 for 2, 5 and 10 pulses with 5 J/cm2 energy After plasma pulse modifications, the changes of density respectively and 1.92 in mischmetal. The surface morphology were observed. The initial amount of REE added to the modified steel sur- grains disappeared and different morphological faces increases with number of applied pulses details were observed. After modification with 2 (Fig.2A). Analyses of efficiency of a single pulse

Fig.2. Amount of REE addition in the DPE processes to the modified layer of 316 steel: A – REE concentration, B – efficiency of the single 5 J/cm2 pulse. NUCLEAR TECHNOLOGIES AND METHODS 145 show an interesting rule. Namely, the greater manufactured from the initial mischmetal. Effi- number of applied pulses – the lower efficiency of ciencies of DPE process for REE as determined single pulse (Fig.2B). This can be due to the fol- in the present work allows us to plan the condi- lowing fact. Each pulse causes evaporation of part tions of further experiments aimed at an improve- of the near surface material. At the beginning, an ment of corrosion and wear resistance of stainless amount of deposited REE is small and a plume of steel. evaporated atoms consists mostly of the initial substrate elements. After larger number of pulses, References the composition of the near surface layer become [1]. Abreu C.M., Cristobal M.J., Novoa X.R., Pena G., rich in REE, so probability of their removal due to Perez M.C., Rodriguez R.J.: Surf. Coat. Technol., evaporation rises and a net amount of these de- 158-159, 582-587 (2002). posited atoms decreases. Such an effect is analo- [2]. Riffard F., Buscail H., Caudron E., Cueff R., Issartel gous to that observed in ion implantation tech- C., Perrir S.: Appl. Surf. Sci., 199, 107-122 (2002). nique when with increase of the implanted dose of [3]. Alman D.E., Jablonski P.D.: Int. J. Hydrogen Energy, 32, 3743-3753 (2007). given ions results in the increase of the sputtering [4]. Sartowska B., Piekoszewski J., Waliś L., Szymczyk W., yield, so more atoms to be introduced into sub- Stanisławski J., Nowicki L., Ratajczak R., Kopcewicz strate are sputtered away. M., Kalinowska J., Barcz M., Prokert F.: Vacuum, 78, In conclusions. The irradiation of stainless steels 181-186 (2005). with intense plasma pulses with an energy density [5]. Sartowska B., Piekoszewski J., Waliś L., Senatorski J. of 5 J/cm2 containing REE ions and nitrogen as Stanisławski J., Ratajczak R., Nowicki L., Kopcewicz the working gas leads to the formation of modi- M., Prokert F., Barlak M.: Surf. Coat. Technol., 201, fied their surface layer. Observed cracks and other 8295-8298 (2007). morphological features are characteristic of re- [6]. Barson S.D., Skeldon P., Thompson G.E., Piekoszewski melting techniques of material modification. In order J.,Chmielewski A.G., Werner Z., Grotzschel R., Wieser E.: Corros. Sci., 42, 1213-1234 (2000). to improve the quality of the surface morphology by re- [7]. Bonilla F.A., Ong T.S., Skeldon P., Thompson G.E., ducing the presence of features described above we Piekoszewski J., Chmielewski A.G., Sartowska B., Sta- plan to carry out further experiments at lower energy nislawski J.: Corros. Sci., 45, 403-412 (2003). densities of pulses. The REE addition corresponds to [8]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63, the proportion of Ce/La in the tips of electrodes 701-708 (2001).

ANALYSIS OF CHANNEL SHAPES IN TRACK MEMBRANES BY THE ELECTRON MICROSCOPY METHOD Oleg L. Orelovich1/, Bożena Sartowska, Adam Presz2/, Pavel Yu. Apel1/ 1/ Joint Institute for Nuclear Research, Dubna, Russia 2/ Institute of High Pressure Physics, Polish Academy of Sciences, Warszawa, Poland

The observation and description of artificial nano- track-etched nanopores [1,2]. It has been demon- pores is motivated by the possibility of using nano- strated that the conical nanopores in polymers are meter-sized pores as single-molecule sensors for cation selective and possess diode-like voltage-cur- the detection and analysis of biopolymers. A well- rent characteristics. The ionic selectivity of the -known method for the production of uniform pores narrow track-etched pores stems from the presence in dielectrics is particle track etching. Attempts to of carboxylic groups on the surface, which has approach the geometric characteristics of the ion been mentioned for the first time for polyethylene channels have led to the development of conical terephthalate (PET) [3,4]. An essential feature of A B

Fig.1. SEM image of profiled asymmetric pores in a PET foil 12 μm in thickness etched in 6 M NaOH with the surfactant at 60oC for 5 min (A) and 6.5 min (B). 146 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

–x/t Fig.2. Part of the channel border approximated by the function: Y = A1*e + y0. The border of the membrane surface coincides with the Y axis. The concentration of NaOH was 6 M (A) and 3 M (B). The parameters of the function are: (A)

A1=-0.13071, t=0.57047, y0=0.18167; (B) A1=-0.18732, t=1.14055, y0=0.23068. the track-etched nanopores produced by the method Formation of the narrow pore tip during etch- suggested by Apel et al. [4] is geometric asymmetry. ing in the presence of a surfactant is governed by Typically, the length of the pore is of the order of the process of adsorption and diffusion of surfactant 10 μm, and the diameter changes from some hun- molecules [2-4]. As a result, the inside diameter of dreds of nm at the wide end to about 10 nm at the the channel grows at a higher etch rate than the narrow end. This makes the conical pores appli- pore entrance. cable for use in resistive-pulse technique. The The length of the self-assembled aggregate in conically shaped track-etched nano-channels have the pore entrance determines the configuration of been applied to detect single DNA and porphyrin the resulting channel. The shorter the etching time, molecules [4]. To better adjust geometric charac- the shorter is the narrow segment at the pore en- teristics of the conical nanopores to emerging ap- trance (Fig.1). This situation opens the way to con- plications, variations of etching methods have been trol of the pore shape by varying etching condi- suggested which allow enlargement of the cone tions. angle. The results of size measurements on SEM im- Polyethylene terephthalate films (Hostaphan ages allow us to obtain the modification of the pore RE, Kalle, 5 μm thick and Hostaphan RNK, Mitsu- diameter through the pore depth. Figure 2 presents bishi Polyester Films, 12 and 23 μm thick) were these results for two different NaOH concentra- irradiated with 253 MeV Kr ions in a U-400 cyclo- tions. The border of channel can be approximated tron of the Flerov Laboratory of Nuclear Reactions by exponential function 4 –x/t (Dubna, Russia). The ion fluence ranged from 10 Y = A1*e + y0 9 –2 to 3x10 cm . where: y0 – pore diameter on the membrane sur- The samples prepared in this way were etched face, x – distance from the membrane surface to with NaOH solutions to which 0.05% (w/w) of channel depth. Dowfax 2A1 (Dow Chemicals) was added to pro- The parameter t characterizes the length of nar- duce asymmetric membranes with a highly tapered rowed part of the channel that matches the thick- pore profile. The temperature during etching was ness of selective layer. kept constant at 60oC. After etching, the samples were examined using JSM-840 (JEOL, Japan) and References a LEO-1530 (Zeiss, Germany) scanning electron [1]. Apel P.Yu., Korchev Yu.E., Siwy Z., Spohr R., Yoshida microscope (SEM). Pore density and pore dia- M.: Nucl. Instrum. Meth. Phys. Res. B, 184, 337-346 meters on both surfaces of the membranes were (2001). determined. Pore profiles were determined via [2]. Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Orelovitch imaging of fractures of samples having relatively O.L., Sartowska B.: J. Membr. Sci., 282, 393-400 (2006). high pore densities (107-109 cm–2). A special tech- [3]. Harrell C.C., Choi Y., Horne L.P., Baker L.A., Siwy Z.S., Martin C.R.: Langmuir, 22, 10837-10843 (2006). nique was used to render the polymer brittle and [4]. Apel P.Yu., Blonskaya I.V., Didyk A.Yu., Dmitriev to avoid residual strain in the fractured specimens: S.N., Orelovitch O.L., Root D., Samoilova L.I., Vut- the membranes were exposed to ultraviolet (UV) sadakis V.A.: Nucl. Instrum. Meth. Phys. Res. B, 179, radiation of electromagnetic power in ranges B 55-62 (2001). (280-320 nm) and A (320-400 nm), respectively, [5]. Orelovitch O.L., Apel P.Yu., Sartowska B.: J. Microsc., on the specimen surface [5]. 224, 100-103 (2006).

INVESTIGATIONS OF A PROTON PASSING THROUGH SOLID STATE NUCLEAR TRACK DETECTORS PM-355 TYPE Bożena Sartowska, Adam Szydłowski1/, Marian Jaskóła1/, Andrzej Korman1/, Aneta Malinowska1/, Thorsten Kuehn2/ 1/ The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland 3/ Physikalisches Institut, Universität Erlangen-Nürnberg, Erlangen, Germany

Same properties of solid state nuclear track detec- ions within a wide energy range, ability of relatively tors (SSNTDs), such as their high sensitivity to high particle fluxes registration, very small sensitiv- NUCLEAR TECHNOLOGIES AND METHODS 147 ity to photons and electrons make them very use- hit at normal incidence the SSNTDs samples up ful for hot plasma experiments. At the Andrzej Soł- to 105 particles/cm2. After irradiation, the samples tan Institute for Nuclear Studies (SINS) have been were etched in 1 h steps in 6.25 N water solution of

Fig.1. The tracks fracture/shape evolution caused by 6.66 MeV protons observed after etching time. used CR-39 track detectors and recently PM-355 NaOH at a temperature of 70oC during selected derivatives of the CR-39 material (C12H18O7). The time intervals. Scanning electron microscopy (SEM) calibration studies have been performed at SINS of DSM 942 type (Zeiss, Germany) technique was for several years. As a result of these studies, we use to study the surface and fracture morphology obtained an extensive collection of data on shapes of the detectors. Both the detector surfaces – en- of tracks formed by different projectiles and their trance and exit sides – were examined for track energies [1,2]. diameter measurements. Fractures of detectors The SSNTDs of the PM-355 type (Pershore were observed for determination of the tracks Ltd, UK) with a thickness of 0.5 mm were exposed shape and depth. to protons with energies: 6.36, 6.66, 6.96, 7.25 and The widely accepted growth models of the track 7.74 MeV obtained from the University of Erlan- etch-pit involve two etch rates: the track etch rate gen-Nürnberg Tandem accelerator. Accelerated along the particle trajectory (VT) and the material 2 protons, after scattering on a 130 μg/cm gold foil bulk etch rate (VB). The latter track develops into

Fig.2. Diagrams of the track diameter evolution at the entrance and the exit sides of the PM-355 detector irradiated by (A) 6.36, (B) 6.66 and (C) 7.25 MeV protons as a function of etching time. 148 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS a conical in shape etch pit, when the track etching are the highest, i.e. the Bragg curve had its maxi- velocity VT is larger than the bulk etching velocity mum. For the protons with the energy higher than VB [1,3]. 6.66 MeV, the obtained results were not so differ- Samples of track shape of the entrance and ent. The tracks diameters at the entrance side were exit sides induced by 6.66 MeV protons in the only slightly different than those on the exit side. PM-355 detector after 3 h etching is presented in The proton range and stopping power in PM-355 Fig.1. Differences between the tracks diameter at material were calculated using the computer code the entrance and exit can be clearly seen. Developed TRIM of Zieg-ler et al. [4]. The region of the de- tracks are conical in shape at both sides of the detector in which the particle is slowed down to very tector surfaces. low energy is particularly interesting for the experi- In Figure 2, we present the diagrams of tracks mental verification of the TRIM model results. diameter evolution at the entrance and exit sides In conclusions. From our measurements it can of the PM-355 detector irradiated by protons with be noticed that the diameters and the depths of energies of 6.36, 6.66 and 7.25 MeV as a function the tracks are higher at the exit side of the detector of etching time. In the case of protons with the for 6.66 MeV proton energy (at the end of the smallest energy i.e. 6.36 MeV no tracks were de- proton range ). The observations of diameter and veloped at the exit side after 1, 2 and 3 h of etch- shape of the developed tracks at the entrance and ing. The first developed tracks at the exit side of exit side of PM-355 detector allowed us to verify the sample appeared after 4 h, i.e. when the thick- the theory of decreasing charged projectile lost ness of the detector layer removed from one side energy near the point of its range in the polymer of the detector sample was equal to about 6.6 μm material. (4 h x 1.65 μm). This means that the projectile was slowed down inside the polymer and did not pass References the whole detector across. In the case of protons [1]. Szydłowski A., Sadowski M., Czyżewski T., Jaskóła M., with higher energies the tracks at both sides were Korman A., Fijał I.: Nucl. Instrum. Meth. Phys. Res. developed and visible after the first etching hour. B, 171, 379-386 (2000). This means that the projectiles passed through the [2]. Sartowska B., Szydłowski A., Jaskóła M., Korman A.: whole plastic. Radiat. Meas., 40, 347-350 (2005). Tracks induced by 6.66 MeV protons on the [3]. Balestra S., Cozzi M., Giacomelli G., Gicomelli R., entrance surface had always (regardless of the Giorgini M., Kumar A., Mandrioli G., Manzoor S., Margiotta A.R., Madinaceli E., Patrizzi L., Popa V., etching time) smaller diameters than the adequate Quereshi I.E., Rana M.A., Sirri G., Spurio M., Togo tracks observed on the exit surface. This means V., Valieri C.: Nucl. Instrum. Meth. Phys. Res. B, 254, that the projectiles passed through the sample, but 254-258 (2007). their energy was considerably reduced. This may [4]. Ziegler F.J., Biersack J.P., Littmark U.: The stopping suggest that the coming out projectiles reached the and range of ions in solid. Pergamon Press, New York energy at which REL (rate of energy loss) values 1985.

THE ROLE OF Cr IN FORMATION OF NITROGEN EXPANDED AUSTENITE PHASE IN Fe-Cr ALLOY TREATED BY HIGH INTENSITY NITROGEN PLASMA PULSES Jerzy Piekoszewski1,2/, Ludwik Dąbrowski3/, Bożena Sartowska1/, Cezary Pochrybniak3/, Paweł Stoch3/, Wojciech Starosta1/, Lech Waliś1/, Marek Barlak1,2/, Zbigniew Werner2/ `1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland 3/ Institute of Atomic Energy, Otwock-Świerk, Poland

During the past two decades, several authors have (>15 wt%) and Ni (>5 wt%) are available in the shown that nitriding of stainless steel is possible in system. This may be the case for stationary process- such a way that a metastable phase is formed in ing but it not when transient melting process is ap- which nitrogen remains in solid solution, increas- plied. In our previous experiments [3] it was shown ing the surface hardness and wear resistance with- that γN can also be formed in carbon steels and out deterioration of the corrosion behaviour of even in pure α-iron if the substrate is treated with stainless steels. This phase is referred to as nitro- high intensity (power density106-107 W/cm2) short gen expanded austenite and is denoted as γN or S (μs range) nitrogen plasma pulses which melt the phase. Two methods have been used to procure near surface layer of the substrate. The melt dura- γN: nitrogen ion implantation at elevated tempera- tion is also in the μs range. Most effective methods o ture (400-600 C) and a high dose-rate (over 100 for detection of the presence of a γN phase are: con- μA/cm2) and nitriding by plasma immersion ion version electron Mössbauer spectroscopy (CEMS) implantation (PI3). Some of the authors e.g. [1,2] and X-ray diffraction in a grazing geometry. In claim explicitly that regardless of the method of our previous experiments we performed examina- nitriding the γN can be formed only when Fe, Cr tion of a large amount of steel samples alloyed NUCLEAR TECHNOLOGIES AND METHODS 149 with different elements. By compilation [4] of the As the next step, we plan to perform the nitro- data on the dependence of γN fraction on the con- gen pulse plasma treatment of samples, to per- centration of different alloying elements such as form CEMS measurements in two versions of Cr, C, N, we inferred the semi-quantitative regu- Doppler velocity, i.e. +/-7 mm/s and +/-2 mm/s, larity that: an amount of γN fraction is reduced and to make the “ab initio” calculations adapted with the growth of Cr content. In such a situation to modelling the real Fe-Cr-N systems, especially natural question arises – what is the role of Cr in with regard to atomic arrangement and its influ- view of the fact cited above [1,2] and from our ob- ence on the dynamics and mechanisms of the servations [3,4]. phase formation. To clarify this question we decided to limit an amount of elements of the system to Fe-Cr alloys Referenes of different compositions and to dope them with [1]. Menthe E., Rie K-T., Schultze J.W., Simon S.: Surf. N using our pulse plasma technique. Coat. Technol., 74-75, 412-416 (1995). In 2008 the following works have been done: [2]. Blawert C., Mordike B.L., Jirásková Y., Schneeweiss • preparation of 5 samples of Fe-Cr alloys with O.: Surf. Coat.Technol., 116-119, 189-198 (1999). 3.15, 6.2, 12.5, 25 and 50 wt% Cr using the arc [3]. Piekoszewski J., Sartowska B., Walis L., Werner Z., Kopcewicz M., Prokert F., Stanislawski J., Kalinowska furnace synthesis method; J., Szymczyk W.: Nukleonika, 49, 2, 57-60 (2004). • setting up the CEMS system; [4]. Piekoszewski J., Dąbrowski L., Sartowska B., Waliś L., • measurements of the virgin samples using CEMS Barlak M., Werner Z., Kopcewicz M., Kalinowska J., and XRD in grazing geometry; Nowicki L., Ratajczak R., Stanisławski J., Barcz A.: • collection of computer programs for analysis of Vacuum, 81, 1403-1407 (2007). the results.

INFLUENCE OF DISTRIBUTION OF Ti ALLOYED INTO CARBON AND CARBIDE CERAMICS BY INTENSE PLASMA PULSES ON THEIR SURFACE WETTABILITY WITH LIQUID Cu Marek Barlak1,2/, Jerzy Piekoszewski1,2/, Bożena Sartowska1/, Lech Waliś1/, Zbigniew Werner2,3/, Elżbieta Składnik-Sadowska2/, Joachim Kierzek1/, Wojciech Starosta1/, Andreas Kolitsch4/, Rainer Grötzschel4/, Katarzyna Bocheńska2/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland 3/ Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa, Poland 4/ Institute of Ion Beam Physics and Materials Research, Forschungszentrum Dresden-Rossendorf, Dresden, Germany

Nowadays it becomes obvious that the future tech- at our laboratories. We succeeded in inducing wet- nology needs lighter, stronger more corrosion-re- tability of ceramics mentioned above by liquid sistant materials capable of withstanding high copper applying a single step pretreatment proce- temperatures. Ceramics seem to be leading candi- dure. This procedure consists of using the high in- dates for meeting these requirements. The combi- tensity pulse plasma pulses in a special version of nations of various ceramic-metal (C-M) systems the so called deposition by a pulse erosion (DPE) such as C-M joints and a metal-ceramic composite technique. are crucial in this respect. Advanced ceramics in- Four kind of materials were used as substrates: clude various kinds of oxides, nitrides, silicates, car- pyrolytic graphite (Cp), glassy carbon (Cg), car- bides and glass. The current and future advanced bon-carbon composite (C/C) and silicon carbide ceramic products have been widely used in the au- (SiC). tomotive and defence industries, for aircraft, aero- The main tool used for their modification was space applications, wear-resistant parts, bioceramics, a rod plasma injector (RPI) type of device described cutting tools, superconductivity, nuclear reactors, in detail in [7,8]. etc. [1,2]. Three batches of samples were prepared: In the case when the C-M joint is to be formed, • 50 Ti mono” – 50 Ti pulses of energy density 7 the crucial problem is wettability since in the ma- Jcm–2; jority of ceramic-metal systems direct wetting is • “50 Ti multi” – 5, 10, 15 and 20 pulses of energy not observed. Over the past decades several means density of 7, 5, 3 and 1 Jcm–2, respectively; of inducing wetting have been developed [3-6]. • “200 Ti multi” – 20, 40, 60 and 80 pulses of en- Usually, the preparation of the ceramic surface ergy density of 7, 5, 3 and 1 Jcm–2, respectively. requires an adoption of the procedure consisting The samples were characterized by: scanning of several steps. The issue of wettability of carbon electron microscopy (SEM), Rutheford back scat- and carbide by liquid metals was also investigated tering (RBS) of helium ions, energy dispersive 150 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS X-ray spectroscopy (EDX), surface roughness mea- The above technique may compete with the surements and gravimetric measurements. To check existing technologies in practical applications. the wettability, the sessile drop examination was performed on all samples. After the test, the sam- References ples were examined and photographed and the [1]. Liang Y., Dutta S.P.: Technovation, 21, 61-65 (2001). wetting angle was determined using a homemade [2]. Rosso M.: J. Mater. Process. Technol., 175, 364-375 computer-supported sessile drop tester. (2006). The conclusions which can be drawn from the [3]. Suganuma K.: ISIJ International, 30, 1046-1048 (1990). results obtained can be summarized as follows. [4]. Nicholas M.G.: Material Science and Technology. For satisfactory wettability: 17B. Processing of ceramics. Part II. Weinheim, New • Area concentration of alloyed titanium should York, Basel, Cambridge, Tokyo 1996, 262 p. be sufficiently high, i.e. no less than 3e18 cm–2. [5]. Tillmann W., Lugscheider E., Xu R., Indacochea J.E.: • Top layer must contain at least 60 at.% of Ti J. Mater. Sci., 31, 445-452 (1996). [6]. Włosiński W.: The joining of advanced materials. Ofi- atoms. cyna Wydawnicza Politechniki Warszawskiej, Warsaw • Ti concentration should gradually decrease with 1999, 68 p. depth without a sharp step just beneath the sur- [7]. Piekoszewski J., Langner J.: Nucl. Instrum. Meth. Phys. face. Res. B, 53, 148-160 (1991). • The shape and size of the metallic features formed [8]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63, on the surface are not important with respect to 701-708 (2001). the wettability.

INFLUENCE OF IONIZING RADIATION ON SILVER CHLORIDE MICRORODS DEPOSITED INTO PARTICLE TRACK-ETCHED MEMBRANES Marek Buczkowski, Bożena Sartowska, Wojciech Starosta, Joachim Kierzek

In the previous year, at the Institute of Nuclear tigations concerning template deposition of AgCl Chemistry and Technology – INCT (Department of microrods into track-etched membrane (TM) have Nuclear Methods of Materials Engineering) inves- been carried out [1]. It seems that nano- and micro- A

Fig.1. SEM photographs of TMs surfaces after deposition of AgCl in pores: left part – membranes sides at AgNO3 solution, right part – membranes sides at NaCl solution; A) TM with pore size – 0.4 μm, B) TM with pore size – 0.7 μm. NUCLEAR TECHNOLOGIES AND METHODS 151 particles of AgCl or AgBr can be interesting and respectively). In the left part of this figure, is given useful materials for some applications [2,3]. a view of the sides at AgNO3 solution and in the Template deposition of AgCl microrods into right part – a view of the sides at NaCl solution. In track-etched membrane with pore diameter of 0.2 the case of Fig.2A, the time of deposition was μm made of a 10 μm thick poly(ethylene tereph- equal to 5 min. Microrods are seen with an exter- thalate) (PET) film including chemical procedure nal diameter equal to 0.4 μm. Figure 2B shows a (AgNO3+NaCl reaction in pores) has been de- sample where time of deposition was 10 min. We scribed in paper [1]. Using the same procedure, can see microrods that give the mapping of verti- template deposition in the case of TMs (from the cal and oblique tracks in the membrane sample. Joint Institute for Nuclear Research, Dubna, Samples with AgCl microrods have light-violet Russia) with pore diameters of 0.4 and 0.7 μm was colour and do not change it at visible, scattered made. The scanning electron microscope (SEM), light in contrast with the usual AgCl chemical com- DSM 942 (Zeiss, Germany) was used for sample pound (prepared in bulk) that darkens at visible surface morphology as well as membrane fracture light. In the case of UV exposition, the samples observations. with AgCl microrods darkened. Such experiments Results of SEM observations are given in Figs.1 were made at two UV radiation lengths (254 and and 2. Figure 1 shows the surfaces of membranes 366 nm) for different times of exposition. Remark- with pore size of 0.4 and 0.7 μm (A and B respec- able changes in colour of the samples were after a tively) after 5 min of deposition process. In the left few minutes of UV radiation exposition. Stronger part of this figure a view of the sides at AgNO3 solu- interaction was in the case of 366 nm UV radiation is given. One can see occasionally micrograins tion and, generally, for 0.4 μm TMs samples. The smaller than 1 μm size. In the right part of this figure above samples also darkened at direct sunlight or is given a view of the sides at NaCl solution. One electrical discharge radiation. can see micrograins of bigger size and a greater Further experiments were made with interac- number than in the previous case. At a 0.4 μm tion of gamma (60 keV) and electron beam (10 pore size sample, the size of micrograins is 1-2 μm MeV) radiation. In the case of gamma radiation, and at 0.7 μm – the size of micrograins is 2-3 μm. samples with AgCl microrods darkened relatively A

Fig.2. SEM photographs of TMs fractures with deposited AgCl microrods in pores: left part – membranes sides at AgNO3 solution, right part – membranes sides at NaCl solution; A) TM with pore size – 0.4 μm and time of deposition – 5 min, B) TM with pore size – 0.7 μm and time of deposition – 10 min. Figure 2 shows the fractures of TMs samples weakly (practically only for 0.4 μm TMs samples). with deposited AgCl microrods into pores in the Similar situation was in the case of electron beam case of pore diameters: 0.4 and 0.7 μm (A and B exposition. Such an experiment was made using 152 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS an ELEKTRONIKA 10/10 linear electron accel- References erator at the INCT (Department of Radiation Chemistry and Technology) with doses of 28 and [1]. Buczkowski M., Starosta W., Sartowska B., Kierzek J.: Template deposition of silver chloride microrods into 56 kGy. a particle track-etched membrane. In: INCT Annual It seems that TMs with deposited AgCl micro- Report 2007. Institute of Nuclear Chemistry and Tech- rods can be useful as sensors of some kinds of ion- nology, Warszawa 2008, pp.132-133. izing radiation, e.g. UV radiation. The authors [2]. Potiyaraj P., Kumlangdudsana P., Dubas S.T.: Mater. would like to continue investigations in order to Lett., 61, 11-12, 2464-2468 (2006). explain above results and to give their quantitative [3]. Sambhy V., MacBride M., Petersom B.R., Sen A.: J. description. Am. Chem. Soc., 128, 9798-9808 (2006).

SILICA BIOCIDAL MATERIALS WITH SILVER Dagmara K. Chmielewska, Andrzej Łukasiewicz

The procedures for synthesis of metal hydrosols ing radicals following hydrogen abstraction by the include: (i) reduction of aqueous ions by a variety ●OH radical (Fig.1). of reducing agents such as citric acid, sodium boro- H2O e-aq, H, OH, H2, H2O2 (1) hydride, and alkaline tetrakis (hydroxymethyl)phos- phonium chloride; (ii) radiation-induced reduction OH + RCH2OH → RC·HOH + H2O (2) nC·HOH + M(I) → (M)n + RCH OH of ions; (iii) sonochemical reduction of metal ions. 2 (3) Chemical methods apply water or organic phase (where M is a metal) transfers [1]. Since the nanoclusters are not thermo- ne-aq + M(I) → (M)n (4) dynamically stable they have a tendency to aggre- Fig.1. Reactions leading to metal cluster formation in aque- gate in bigger clusters. Therefore, different methods ous solutions. of stabilization have to be applied; one uses a cap- ping agent which covers the particle surface to This technique was followed by others and prevent further aggregation, the other is the for- single and bimetallic clusters have been synthe- mation of double layer like that formed in colloids sized applying gamma rays or electron beam. where electrostatic forces prevent aggregate growth, Silica biocides based on water glass (WG) and finally, the sorption on the solid particle surface quaternary N-alkylammonium salts (SiO2-QAC) (SiO2, TiO2) or trapping in a solid cage (zeolites) obtained by precipitation with H2SO4 from water can be used. glass and quaternary N-alkylammonium compound The radiation for the metal cluster was intro- (QAC) as well as silica materials elaborated by e.g. duced by Henglein [2] and coworkers and Belloni coating of TiO2 or other carriers ( dolomite) [3]. They described the radiolytic reduction of with salt of water glass and quaternary N-alkyl- many metal ions either single metal or in combi- ammonium compound were described previously nation with another metal to generate metallic or [4-6]. The method for synthesis of water soluble bimetallic mixtures as well as core-shell structures. silica materials (s-SiO2-QAC) containing quater- To obtain metallic particles from their parent ions nary alkylammonium salts has been also elabo- one only needs to ensure reductive conditions dur- rated previously [7]. All these materials binds Ag+ ing the irradiation. The oxidizing ●OH radicals, can from water and zero-valent silver atoms obtained conveniently be converted to reducing radicals by due to UV light irradiation. In the next step we the addition of organic scavengers (e.g. alcohols applied electron beam instead of UV radiation to and formate ions). The latter will produce reduc- silver reduction in the material matrixes. A B

Fig.2. SEM-BSE images of nano- and microclusters of silver deposited on silica biocidal materials: A – magnification 11 000x, B – magnification 30 000x. NUCLEAR TECHNOLOGIES AND METHODS 153

15 ml of 0.01 M AgNO3 solution was stirred within the matrix is brought about by hydrated elec- with 0.3 g of silica solid material in the dark and trons and hydroalkyl radicals generated during the 0.8 ml of isopropanol was added. In this way, radiolysis of the 2-propanol solution. The mean samples of silica materials obtained by the three silver clusters size increases with irradiation dose. different methods described above were prepared. References The samples were irradiated with electron beam at different doses (25, 50 and 75 kGy) to deter- [1]. Sastry M.: Curr. Sci., 85, 12, 1735-1745 (2003). [2]. Janata E., Henglein A., Ershov B.G.: J. Phys. Chem., mine the irradiation dose influence on effective- 98, 10888-10890 (1994). ness, homogeneity of silver clusters distribution in [3]. Belloni J., Mostavi M., Remita H., Marignier J.-L., the materials and size of metal clusters. Delcourt M.-O.: New J. Chem., 22, 1239-55 (1998). The ionizing radiation penetrates homogene- [4]. Łukasiewicz A., Chmielewska D., Waliś L., Rowińska ously within the solid and ensures a homogeneous L.: Pol. J. Chem. Techn., 5, 4, 20-22 (2003). initial distribution of reducing radiolytic radicals [5]. Łukasiewicz A., Krajewski K., Chmielewska D., Waliś formed by ionization and excitation of the solvent. L., Rowińska L.: Method for obtaining of new mate- The metallic particles are then produced homo- rials with biocidal activity. Polish Patent Application geneously in situ within the materials matrixes at P.357356. [6]. Łukasiewicz A., Chmielewska D., Waliś L., Krajewski room temperature (Fig.2). Furthermore, the radi- K.: Ekologia, 29, 3, 36-37 (2005), in Polish. ation-induced reduction method allows a control [7]. Łukasiewicz A., Chmielewska D.K., Waliś L.: Water of the reducing conditions, thus of the amount of soluble silica biocides containing quaternary ammonium ions simultaneously reduced to form clusters of dif- salts. In: INCT Annual Report 2006. Institute of Nuc- ferent sizes [8]. A SEM-BSE investigation allowed lear Chemistry and Technology, Warszawa 2007, p.141. to determine the size of silver clusters (tens nano- [8]. Hornebecq V., Antonietti M., Cardinal Th., Treguer- meters-one micrometer). The reduction of Ag+ -Delapierre M.: Chem. Mater., 15, 1993-1999 (2003).

CHARACTERIZATION OF Ni POROUS ELECTRODE

COVERED BY A THIN FILM OF LiMg0.05CO0.95O2 Andrzej Deptuła, Wiesława Łada, Tadeusz Olczak, Elisabetta Simonetti1/, Roberto Lo Presti1/ 1/ Italian National Agency for New Technologies, Energy and the Environment (ENEA), C.R.E. Casaccia, Rome, Italy

Molten carbonate fuel cell (MCFC) are one of the cobalt, nickel, magnesium and other elements. most promising devices for power generation be- Lithium cobaltite is a ceramic material semicon- cause of their high efficiency and low emission. ductor and is already used commercially in lith- The state of the art of the cathodic material is the ium-ion batteries. Many laboratories have studied lithiated nickel oxide, LixNi1-xO, for which the and developed cathodes in LiCoO2 [6,7]. In the oxygen reduction reaction rate (oxygen reduction ENEA laboratories, within the Agreement of reaction, ORR) is high. The main problem with Program MICA-ENEA, a process [4] for the pro- LixNi1-xO derives from the fact that its rate of dis- duction of cobaltite powders and the realization, solution in molten carbonates is very high (solu- by means of tape casting, of porous cathodes of bility 20-50 ppm). As a consequence of such phe- dimension 100 cm2 has been developed. Lithium nomenon, the cathodic nickel is dispersed and cobaltite doped with magnesium electrode has transported inside the electrolyte producing a con- been characterized outside the cell (morphology, centration gradient under the electric field of the conductivity, solubility) and with in-cell tests. The cell. Moreover, the Ni2+ ion can be reduced to comparison with nickel oxide has allowed to as- nickel in the matrix producing a short circuit of the sert that lithium cobaltite doped with magnesium cell. The dissolution rate depends on the pressure, can, from the electrochemical point of view, re- and in the case of pressurized MCFC, the estimat- place the conventional cathode. On the contrary, ed lifetime highly decreases. One way to solve such a problem is to add to the electrolyte an ion that makes it [1,2] more basic; another way is to develop an alternative cathodic material [3,4]. Different materials have been studied in these years: ferrites, cobaltites, manganites, doped metallic oxides, ilmenites, spinels and perovskites. The greater part of such materials is not stable in molten carbonates and/or they react with γ-LiAlO2 of the matrix [5]. More promising materials are LiFeO2 and LiCoO2. Both have a good wettability with the electrolyte and are more stable than LixNi1-xO in cathodic atmosphere. LiFeO2 is less expensive, but its electri- o –1 cal conductivity at 650 C is very low (0.05 S cm ) Fig.1. XRD pattern of the LiMg0.05Co0.95O2 coated nickel and sensitive to gas composition even if doped with porous electrode. 154 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS the use of lithium cobaltite is limited due to its face (Fig.2), the layer of lithium cobaltite seems to mechanical brittleness and the high cost of the be thin and uniform. raw materials but, above all, due to the process of Conductivity measurements were carried out preparation of the electrode. In order to obviate on three different electrodes. Figure 3 shows that these disadvantages it has been prepared a porous the layer prepared in the Institute of Nuclear nickel cathode covered with a thin layer of lithium Chemistry and Technology (INCT) has the resis- cobaltite doped with magnesium to maintain prop- tivity of: erties of the metallic substrate reducing nickel solu- • conventional porous nickel sheet partially oxi- bility. Lithium cobaltite thin films have been de- dized, posited by different techniques: chemical vapour • Mg-doped lithium cobaltite made in ENEA deposition, spattering and laser ablation. The elabo- laboratories, rated complex sol-gel process (CSGP) [8] was se- • porous nickel electrode coated with Mg-doped lected in order to protect the nickel cathode against lithium cobaltite (prepared in the INCT). dissolution because it is effective and less expensive. Cathodes were prepared by means of a sol-gel process [9]. The nickel cathode coated with a layer of LiCoO2 doped with magnesium was tested in a molten carbonate fuel cell with a 10x10 cm2 electrode area. The cell was assembled with a Ni-5 wt% Cr anode, a γ-LiAlO2 matrix and a Li/K carbonate electrolyte (molar ratio 62:38). The cell performance was studied at 650oC and 1 atm for more than 1000 h. The cathode kinetics was investigated by changing the partial pressure of oxygen and carbon dioxide. Fig.3. Electrical resistance at 650oC as a function of time in air of nickel oxide (1), lithium cobaltite (2), nickel covered with lithium cobaltite (3).

The nickel/lithium cobaltite cathode was tested in a 100 cm2 electrodes fuel cell with a conventional anode and tile. The cell operated in the gas –1 composition 10/10/1 Nl h of H2/N2/CO2 for about 1000 h at 650oC. The cell voltage at high current densities remained constant up to the end of the test. The cell performance gradually improved during the cell operation time, showing a voltage of 800 mV at a current density of 100 mA cm–2 after 700 h; the carbonate electrolyte, which initially filled the cathode pores, is redistributed in Fig.2. Nickel and cobalt concentration profiles obtained by EDS analysis. the first hours reducing cathode polarization. In Figure 4 are shown the SEM (scanning elec- Figure 1 shows the X-ray diffraction (XRD) pat- tron microscopy) pictures of the electrode before terns of the electrode, where after thermal treat- (A) and after (B) in-cell test (about 1000 h cell ments, the layer LiCoO2 phase was formed of lifetime). Some changes in morphology and grain lithium cobaltite on the porous nickel electrode. size occurred on the electrode surface: the large Lithium cobaltite particles homogeneously cover open porosity decreased and the electrode skele- the nickel substrate. In spite of the relatively vari- ton was composed of bigger grains and smaller able concentration of cobalt on the electrode sur- ones which had the same chemical composition.

Fig.4. SEM pictures of the electrode before (A) and after (B) in-cell test (cell lifetime – about 1000 h). NUCLEAR TECHNOLOGIES AND METHODS 155 It has been proved that the nickel electrode, [4]. Giorgi L., Carewska M., Scaccia S., Simonetti E., Zar- covered with a thin layer of lithium cobaltite doped zana F.: Denki Kagaku, 6, 482 (1966). with magnesium, fabricated in the INCT by the [5]. Giorgi L., Carewska M., Simonetti E., Scaccia S., Croce CSGP exhibits a good cell (MCFC) performance F., Pozio A.: In: Electrochemical technology of molten salts. Eds. C.A.C. Sequeira, G.S. Picard. Trans Tech that gradually improved during the cell operation Publications, Switzerland 1993, pp.285-302. time. [6]. Fukui T., Okawa H., Kodera K., Tsunooka T. : Pro- References ceedings of the 2nd International Fuel Cell Confer- ence, 05-08.02.1996, Kobe, Japan. [1]. Miyazaki Y., Yanagida M., Tanase S., Tanimoto K., [7]. Lee G.L., Selman J.R., Plomp L.: J. Electrochem. Soc., Kojima T., Ohtori N., Okuyama H., Kodama T., Mori- 140, 390 (1993). moto K., Nagashima I., Nagai C., Itoh H.: Proceedings [8]. Deptula A., Łada W., Olczak T., Lanagan M., Dorris of the 1992 Fuel Cell Seminar, 29.11-02.12.1992, Tucson, S.E., Goretta K.C., Poeppel R.B.: Method for prepar- USA. ing high-temperature superconductors. Polish Patent [2]. Miyazaki Y., Yanagida M., Tanimoto K., Kojima T., No. 172618. Ohtori N., Asai T.: Proceedings of the 1994 Fuel Cell [9]. Deptula A., Lada W.: J. New Mater. Electrochem. Syst., Seminar, 28.11-01.12.1994, San Diego, USA. 6, 33-37 (2003). [3]. Lundblad A.: Ph.D. thesis. Stockholm 1996.

DYNAMIC CORRELATIONS IN MAGNETIC COMPOSITE UNDER MAGNETIC FIELD STUDIED BY XPCS Helena Grigoriew, Lutz Wiegart1/, Anna Boczkowska2/ 1/ European Synchrotron Radiation Facility, Grenoble, France 2/ Faculty of Materials Science, Warsaw University of Technology, Poland

Composite-type material consisted of polyurethane less than 103 s, but the correlation curve slopes are gel, and carbonyl iron (CI) of 7 μm size spheres. more complicated. The gel constituents were: MDI/OAE+DCDA with molar ratio 70/30. The material was processed with 11.5 vol.% of CI under magnetic field, during 24 h at 25oC. SEM (scanning electron microscopy) images of the composite showed short chains of CI formed inside the material. XPCS (X-ray photon correlation spectroscopy) measurements were performed on the Troika beam- line (ID10A) of the European Synchrotron Radia- tion Facility (ESRF) in SAXS (small-angle X-ray scattering) configuration. The meaurements depending on time (t) and angle (q), using X-beam Fig. Correlation rates Γ(q) for different magnetic field wavelength of 1.74872 Å, and detector type CCD values. At each three curve set: bottom – perpendicular, were used. The sample was placed between electro- middle – isotropic, top – parallel to the field lines. magnet poles with magnetic lines direction perpendicular to the X-beam and parallel to the sample Correlation rates, Γ(q). The correlation rates, surface and CI chains inside it. Measurements Γ(q), were found by fitting exponential function: –Γ x were performed for: 0, 300 and 600 mT. It occurred y=a e to the subsequent g2(t) curves, in their that correlation of scattered intensity took place region of correlation behaviour [1]. Figure shows in the time range: from 5x102 to 100x102 s, with Γ(q) curves for subsequent magnetic field value, about 7 s acquisition time of a single measure- with sets of 3 curves for each directions (par, iso ment. and per). When magnetic field increases, from 0 Correlation curves, g2(t): The correlation func- through 300 to 600 mT, correlation rate also in- tion g2(t), according to the formula: creases. It occurred that the magnetic field essen- 2 g2(t)=‹I(to+t)I(to)›/‹I(to) › tially influences the correlation rate, up to 10 times was obtained from I(t,q) CCD measurements us- maximally (Fig.). Besides, within each set the high- ing masks to get them in directions: parallel (par), est curve is for direction parallel to the magnetic isotropic (iso) and perpendicular (per) to the Table. Diffusion coefficients, D [Å/s]. magnetic field lines. The curves at 0 mT, i.e. reference curves, are of Diffusion coefficients, D [Å/s] extremely slow dynamics behaviour with correla- 0 mT 300 mT 600 mT tion reached for about 104 s and of weak differentiation between the measurement directions. For par 0.0027 0.0180 0.0119 300 mT, the correlation is faster (~1.2x103 s) and iso 0.0018 0.0109 0.0096 there is also the dependence on different directions. For 600 mT the correlation is the fastest, of per 0.0011 0.0029 0.0083 156 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS field (par), the lowest one for direction perpen- magnetic field direction and are of much bigger dicular to the magnetic lines (per) and the middle values (Fig. and Table). Here dependence on the one is for isotropic (without mask) measurement. material dynamics from direction of the outer mag- The straight-line shape of all Γ(q) curves are ob- netic field is very clear, with parallel direction (par) served with no significant deviations The correla- very privileged. tion process is thus not due to structural reorgani- But for the magnetic field of 600 mT, despite zation on measured length scale. the highest correlation rate, the dependence on In the case of linear Γ(q) shape, its depend- magnetic field direction became weak, as well as ence on diffusion coefficient is: D values. (Fig. and Table). Simultaneously, on the Γ(q)=D x q Γ(q) curves the bigger fluctuation around the fit- The D [Å/s] values were found from slope of ted straight lines are observed. There probably straight lines fitted to Γ(q) (Table). mechanism of dynamics behaviour altered. For the reference curves for 0 mT, the very moderate values of the Γ(q), and D as well as no Reference differentiation from direction seem to be an evi- [1]. Lal J., Abernathy D., Auvrny L., Diat O., Gruebel G.: dence of very strong structure. Eur. Phys. J., E4, 203 (2001). For the middle value of the field (300 mT), the same parameters are strongly dependent on the NUCLEAR TECHNOLOGIES AND METHODS 157

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS

SOFTWARE MODIFICATION OF DUST POLLUTION MONITORING NETWORK Adrian Jakowiuk

When creating a software for acquisition and sented. The date and time of the measurement presentation of measuring data from a dust pollu- and dust pollution in the period in question are tion monitor AMIZ-2007, it became evident that also given. Figure 1 shows an example of wind for the users of such system some information is roses from the two measuring stations. necessary concerning the wind direction and speed. Having the results of dust pollution in differ- This results from the need to know when and ent periods of time, and the wind rose showing where the dust is introduced into air. A new ver- where from the wind is blowing, one can deduce sion of the software was developed and is now what is the source of dust pollution. It can be seen tested in the Power Station “Wybrzeże” S.A. The from Fig.1 that to control the waste storage of the dust monitoring network existing there consists of power station, the location of the monitor is cor- two dust monitors AMIZ-2004G. One of them is rect. It is supposed that the waste storage could be operating at Rewa, the other in Gdańsk in the the source of dust pollution. Preliminary results of Nowy Port district. In the frame of initiating the measurement did not confirm such expectations, function of the new system the monitors were the more so, because such storage places are gen- modernized to version AMIZ-2007 (adopted for erally quickly cultivated or forested by proper communication through the internet) and equipped services. Existing experience indicates rather on a with wind direction and wind velocity sensors. large concentration of population, particularly Thanks to such modification, it is now possible to where individual houses are heated by burning present measuring data from the monitors on coal. This can be noticed, analyzing the results of WWW page of the Power Station “Wybrzeże”. The measurement of the dust concentration monitor data are presented in the form of diagrams and at Rewa (Fig.1A), where the wind blows from the tables. In the case of wind the diagram is present- sougth, i.e. from the Rewa or Gdynia localities, ed in the form of wind rose. In order to make when the dust concentration is higher. There are identification of the dust pollution easier, the wind also other influencing factors of dust concentra- rose is shown on a map of the neighbourhood tion as, e.g. low temperature, pressure, humidity where the monitor is installed. At the wind rose, (rain), holiday or vacation periods, massive visits daily or in other periods, measured data are pre- of guests (Saturday, Sunday). Another situation A B

Fig.1. Wind roses: A – measuring station at Rewa, B – measuring station in Gdańsk in the Nowy Port district. 158 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS exists in the Nowy Port district (Fig.1B). Air qual- factors influencing the purity of air have to be ity is there measured in the middle of large living taken into account. quarters during heavy car traffic, and to the west During many years the dust monitor AMIZ is of the district where unused waste storage is lo- being consequently improved and adjusted to the cated. Here the analysis of the obtained results is newest world requirements and to the wishes of particularly important, depending on the direction our customers. In the effect, an up-to-date, fully of wind. But to be able to present final conclu- automatic, air borne dust concentration monitor sions, analysis of results of measurements has to is offered. be made at least during the whole year, and all

ALPHA IRRADIATION FACILITY AIF-08 Jan P. Pieńkos, Edward Świstowski

In the Department of Radioisotope Instruments control rotations of the radiation source and col- and Methods of the Institute of Nuclear Chemistry limator, and to control a step motor moving the and Technology (INCT) a device type AIF-08 was carriage with the sample at required distance from developed and made for irradiation of samples the radiation source. Irradiation parameters are with alpha radiation. The user (customer) of the set with keyboard of the controller. The irradiation device is the Department of Genetic Microbiology procedures are displayed at alphanumeric display and Toxicology of the Stockholm University, which with 4 lines, 20 characters in each line. Functional fixed a set of basic requirements for the construc- diagram of the AIF-08 device is shown in Fig.2. tion of the device. The device is shown in Fig.1.

Fig.1. AIF-08 device for long-term irradiation of samples.

The AIF-08 device is designed for a long-term irradiation of samples with alpha particles. Between the rotating alpha source and the sample, a rotating radiation collimator is placed, ensuring thus even irradiation of the sample. The investigated sample can be placed at a required distance from the alpha Fig.2. Functional diagram of the AIF-08 device. source. The device consists of two units: an AIF con- Controller program enables setting and stor- troller and a mechanical unit connected together age in the memory four irradiation programs in with cables in the form of a band, approximately any combinations of: 5 m long. The mechanical unit contains driving • rotation of irradiation source on/off; motors for rotating the radiation source and radi- • rotation of source collimator on/off; ation collimator and for the movement of a car- • speed setting of source and collimator rotation; riage with the sample to be irradiated. The con- • setting irradiation time, and source-sample dis- troller unit is based on a microprocessor system to tance setting.

EXAMINATIONS OF TH-2158 KLYSTRON MODULATOR FOR THE LINEAR ELECTRON ACCELERATOR LAE 10/15 Zbigniew Zimek, Zygmunt Dźwigalski, Stanisław Warchoł, Karol Roman, Sylwester Bułka

The results of measurements carried out at the based on semiconductor switch HTS 181-160 FI TH-2156 klystron modulator experimental model (current load – 1600 A, with voltage – up to 18 NUCLEAR TECHNOLOGIES AND METHODS 159 kV) is presented in this work. A set of resistors RL=8 and 16 Ω was used as a load instead of TH-2158 klystron. Usefulness of individual elements and sub-assemblies in different execution of all elements and sub-assemblies of the safety cut-out of the modulator was tested [1]. The values of RD and CD passive elements (series connection consisting of RD resistor and CD capacitor directly over the switch terminals) were optimized. TH-2158 klystron modulator design was modified according to experimental results [2,3]. A simplified scheme of the modulator and the measuring circuit are shown in Fig.1. The modulator was implemented with an additional circuit consisted of a semiconductor switch HTS 61-160 FI and a bank of resistors with joint resistance about

Fig.1. Simplified scheme of the modulator and measuring circuit. 2.5 Ω. The additional circuit was connected parallely to RL load which is marked in Fig.1 by inter- ruptible line. It was possible to start up an additional switch at each moment during the modulator Fig.2. Oscilloscope records in selected points of the modu- pulse what allowed to attach parallely to load the lator circuits. bank of resistors. The measurements of the selected pulses have been performed using 2-0.1W type of modulator load current. Main switch of the Current Transformer Stangenes, probes (P6015A modulator is switched off fastly and the modula- and P6139A) and a DPO7054 digital oscilloscope. tor load current drops to zero if the value of this Figure 2 shows the selected pulses registered current will surpass 900 A. The shapes of pulses in the different parts of the modulator. The pulses for optimized operational conditions of the modu- characterize separate phases of modulator experi- lator are presented in Fig.2B. The shapes of the ments. Oscillograms in Fig.2A illustrate setting pulses for maximum tension of the bank of capaci- the safety cut-out of the modulator. Start-up of tors (Uch=14 kV) are presented in Fig.2C. It should the additional switch causes a violent decrease be noticed that the pulse collected from the bank load resistance from 8 Ω to near 2 Ω by parallel of ceramic resistors Rs has almost identical shape attachment of 2.5 Ω resistors. This causes a change with the pulse from current transformer.

Fig.3. View of the RD and CD passive elements of the modulator. 160 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS The oscillations can be observed at the begin- observed on this bank of resistors repeats well the ning of trigger pulse of the main switch (HTS current shape on the main switch (HTS 181-160 181-160 FI). The value and considerable high speed FI) load. The pulse is served on input of the most of current rise (109 A/s) are the main reason of important sub-assembly of circuit safety cut-out those oscillations. The oscillations should be re- (input LM319 comparator). duced by implementation of double shielded input circuit located on the main switch. References Optimal values of RD and CD passive elements [1]. Dźwigalski Z., Zimek Z.: Safety cut-out and trigger have been defined experimentally. Joint resistance circuits of the TH2158 klystron modulator. In: INCT value of the bank of RD ceramic resistors type Annual Report 2007. Institute of Nuclear Chemistry AB335-56R HVR International Limited firm is and Technology, Warszawa 2008, pp.149-151. [2]. Zimek Z., Dźwigalski Z., Warchoł S., Roman K., Buł- equal to 10 Ω. Capacitor CD type 37332 General Atomics Electronic Systems (15 nH own induct- ka S.: Modernizacja Stacji Sterylizacji Radiacyjnej wy- ance) has a value equal to 40 nF. Figure 3 shows posażonej w akcelerator elektronów ELEKTRONIKA 10/10. Część I. Instytut Chemii i Techniki Jądrowej, the view of those passive elements. Warszawa 2006, 28 p. Raporty IChTJ. Seria B nr 3/2006 Experimental results have confirmed a proper (in Polish). selection of the type and values of parameters of [3]. Dźwigalski Z., Zimek Z.: Klystron modulator for “Elek- individual elements and sub-assemblies of the tronika 10/10” accelerator. In: INCT Annual Report modulator; particularly the bank of Rs ceramic re- 2004. Institute of Nuclear Chemistry and Technology, sistors was optimized. The shape of pulse voltage Warszawa 2005, pp.149-150. PUBLICATIONS IN 2008 161

PUBLICATIONS IN 2008

ARTICLES

1. Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Mamonova T.I., Orelovitch O.L., Sartowska B., Yamauchi Yu. Surfactant-controlled etching of ion track nanopores and its practical applications in membrane technology. Radiation Measurements, 43, S552-S559 (2008). 2. Atrian S., Bobrowski K., Capdevila M., Chatgialialoglu C., Ferreri C., Houée-Levin C., Salzano A.M., Scaloni A., Torreggiani A. Biomimetic chemistry on tandem protein/lipid damages under reductive radical stress. Chimia, 62, 9, 721-727 (2008). 3. Bartłomiejczyk T., Jaszczak K., Kruszewski M., Baranowski A., Parada R., Zimny J., Roso- chacki S. Micronucleus test and comet assay on mice fed over five generations a diet containing genetically modified triticale. Acta Biochimica Polonica, 55, Suppl. 3, 277 (2008). 4. Basfar A.A., Fageeha O.I., Kunnummal N., Al-Ghamdi S., Chmielewski A.G., Licki J., Pawelec A., Tymiński B., Zimek Z.

Electron beam flue gas treatment (EBFGT) technology for simultaneous removal of SO2 and NOx from combustion of liquid fuels. Fuel, 87, 1446-1452 (2008). 5. Bergès J., Varmenot N., Scemana A., Abedinzadeh Z., Bobrowski K. Energies, stability and structure properties of radicals derived from organic sulfides containing an acetyl group after the •OH attack: ab initio and DFT calculations vs experiment. Journal of Physical Chemistry A, 112, 7015-7026 (2008). 6. Bieliński D.M., Dobrowolski O., Przybytniak G. Morphological aspects of rubber fracture and wear. Journal of Applied Polymer Science, 110, 55-60 (2008). 7. Bobrowski K., Houée-Levin C., Marciniak B. Stabilization and reactions of sulfur radical cations: relevance to one-electron oxidation of methionine in peptides and proteins. Chimia, 62, 9, 728-734 (2008). 8. Brzóska K., Sochanowicz B., Kruszewski M. Oxidative stress and hyperthermia increase pirin expression in HeLa cell line. Acta Biochimica Polonica, 55, Suppl. 3, 247 (2008). 9. Buchalski P., Jadach P., Pietrzykowski A., Suwińska K., Jerzykiewicz L., Sadło J. Products of the reaction of 9-nickelafluorenyllithium complexes with water. Organometallics, 27, 3618-3621 (2008). 10. Chajduk E., Polkowska-Morenko H., Dybczyński R.S. A definitive RNAA method for determination of selenium in biological samples: uncertainty evaluation and assessment of degree of accuracy. Accreditation and Quality Assurance, 13, 443-451 (2008). 11. Chmielewska D.K., Gryczka U., Migdał W. Recent patents on creative ionizing radiation in nanotechnology. Recent Patents on Nanotechnology, 2, 201-207 (2008). 12. Chmielewski A.G., Licki J. Application of electron beam from accelerator to purification of exhaust gases from combustion of high-sulphur fossil fuels. 162 PUBLICATIONS IN 2008

Environment Protection Engineering, 34, 4, 51-59 (2008). 13. Chmielewski A.G., Pawelec A., Dobrowolski A.

Wpływ struktury przepływu spalin na stopień usuwania NOx w procesie radiacyjnego oczyszczania spalin (Influence of flue gas flow pattern on NOx removal rate in the process of electron beam flue gas treatment). Prace Naukowe Instytutu Inżynierii Chemicznej Polskiej Akademii Nauk, 11, 55-70 (2008). 14. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Dąbrowska M., Pszonicki L. GF AAS determination of cadmium, lead and copper in environmental materials and food products after separation on dithizone sorbent. Chemia Analityczna, 53, 887-894 (2008). 15. Ciesielski B., Tyszkowska M., Grudniewska A., Penkowski M., Schultka K., Peimel-Stuglik Z. The effect of dose on light-sensitivity of radicals in alanine EPR dosimeters. Spectrochimica Acta Part A, 69, 1405-1416 (2008). 16. Collins A.R., Oscoz A.A., Brunborg G., Gaivão I., Giovannelli L., Kruszewski M., Smith C.C., Štetina R. The comet assay: topic issues. Mutagenesis, 23, 3, 143-151 (2008). 17. Czub J., Banaś D., Błaszczyk A., Braziewicz J., Buraczewska I., Choiński J., Górak U., Jaskóła M., Korman A., Lankoff A., Lisowska H., Łukaszek A., Szefliński Z., Wójcik A. Biological effectiveness of 12C and 20Ne ions with very high LET. International Journal of Radiation Biology, 84, 10, 821-829 (2008). 18. Dalivelya O.V., Savina N.V., Kuzhir T.D., Buraczewska I., Wojewódzka M. Zhiznesposobnost i proliferacija kletok mlekopitajuscich pod vlijaniem antimutagena digidropiridi- novogo rjada (Viability and proliferation of mammalian cells affected by an antimutagen of dihydropyridine series). Molekuljarnaja i Prikladnaja Genetyka, 7, 49-54 (2008). 19. Danilczuk M., Coms F.D., Schlick S. Fragmentation of fluorinated model compounds: exposed to oxygen radicals: spin trapping ESR experiments and implications for the behaviour of proton exchange membranes used in fuel cells. Fuel Cells, 6, 436-452 (2008). 20. Danilczuk M., Długopolska K., Ruman T., Pogocki D. Molecular sieves in medicine. Mini-Reviews in Medicinal Chemistry, 8, 1407-1417 (2008). 21. Danko B., Dybczyński R., Samczyński Z. Accurate determination of individual lanthanides in biological materials by NAA with pre- and post-irradiation separation. Journal of Radioanalytical and Nuclear Chemistry, 278, 1, 81-88 (2008). 22. De la Fuente J.R., Kciuk G., Sobarzo-Sanchez E., Bobrowski K. Transient phenomena in the pulse radiolysis of oxoisoaporphine derivatives in acetonitrile. Journal of Physical Chemistry A, 112, 10168-10177 (2008). 23. Filarowski A., Koll A., Lipkowski P., Pawlukojć A. Inelastic neutron scattering and vibrational spectra of 2-(N-methyl-α-iminoethyl)-phenol and 2-(N-methyl- iminoethyl)-phenol: experimental and theoretical approach. Journal of Molecular Structure, 880, 97-108 (2008). 24. Fuks L., Gniazdowska E., Mieczkowski J., Sadlej-Sosnowska N. Structural features of tricarbonyl(N-methyl-2-pyridinecarboxyamide)chloro-rhenium(I)-potential precursor of radiopharmaceuticals. Polyhedron, 27, 1353-1360 (2008). 25. Gancheva V., Yordanov N.D., Callens F., Vanhaelewyn G., Raffi J., Bortolin E., Onori S., Ma- linen E., Sagstuen E., Fabisiak S., Peimel-Stuglik Z. An international intercomparison of “self-calibrated” alanine EPR dosimeters. Radiation Physics and Chemistry, 77, 357-364 (2008). 26. Głuszewski W. Opony sieciowane radiacyjnie (Radiation-induced cross-linked tyres). Postępy Techniki Jądrowej, 51, 3, 36-39 (2008). PUBLICATIONS IN 2008 163

27. Głuszewski W., Zagórski Z.P. Radiation effects in polypropylene/polystyrene blends as the model of aromatic protection effects. Nukleonika, 53, Suppl. 1, s21-s24 (2008). 28. Grądzka I., Buraczewska I., Szumiel I. Relationships between EGFR-initiated signalling, DNA double-strand break rejoining and survival in X-irradiated human glioma M059 cells. Nukleonika, 53, 2, 37-44 (2008). 29. Grądzka I., Sochanowicz B., Degen C., Jahreis G., Szumiel I. Inhibitory effect of conjugated linoleic acid on double-strand DNA break rejoining in X-irradiated HT-29 cells: possible interference with EGFR action. Acta Biochimica Polonica, 55, Suppl. 3, 68 (2008). 30. Grądzka I., Szumiel I. Sprzężone dieny kwasu linolowego (CLA) hamują naprawę DNA uszkodzonego przez promieniowanie X (Conjugated dienes of linoleic acid (CLA) inhibit DNA repair damaged by X-rays). Postępy Techniki Jądrowej, 51, 3, 24-28 (2008). 31. Grigoriew H., Chmielewska D., Gronkowski J. SAXS structural study if xerogels and aerogels formed from small-molecule organic gelators. Journal of Physics: Conference Series, 100, 052083 [4] p. DOI: 10.1088/1742-6596/100/5/052083 (2008). 32. Guzik G.P., Stachowicz W. Reliability of light-stimulated photoluminescence (PSL) in detection of irradiated food comparison with thermoluminescence method (TL). Nukleonika, 53, Suppl. 1, s25-s29 (2008). 33. Hill C., Desreux F.J., Ekberg C., Glez Espartero A., Galetta M., Modolo G., Geist A., Selucky P., Narbutt J., Madic C. Assessment of ligand extraction properties: an intercomparison campaign amongst EUROPARTners. Radiochimica Acta, 96, 259-264 (2008). 34. Hörner G., Hug G.L., Pogocki D., Filipiak P., Bauer W., Grohmann A., Lämmermann A., Pędziński T., Marciniak B. Head-to-tail interactions in tyrosine/benzophenone dyads in the ground and the excited state: NMR and laser flash photolysis studies. Chemistry. A European Journal, 14, 7913-7929 (2008). 35. Jaszczak K., Kruszewski M., Baranowski A., Parada R., Bartłomiejczyk T., Zimny J., Roso- chacki S. Micronucleus test and comet assay on mice fed over five generations a diet containing genetically modified triticale. Journal of Animal and Feed Sciences, 17, 100-109 (2008). 36. Khayet M., Cojocaru C., Zakrzewska-Trznadel G. Response surface modelling and optimization in pervaporation. Journal of Membrane Science, 321, 272-283 (2008). 37. Khayet M., Cojocaru C., Zakrzewska-Trznadel G. Studies on pervaporation separation of acetone, acetonitrile and ethanol from aqueous solutions. Separation and Purification Technology, 63, 303-310 (2008). 38. Kosior G., Samecka-Cymerman A., Chmielewski A., Wierzchnicki R., Derda M., Kemperas A.J. Native and transplanted Pleurozium schreberi (Brit.) Mitt. as a bioindicator of N deposition in a heavily industrialized area of Upper Silesia (S Poland). Atmospheric Environment, 42, 1310-1318 (2008). 39. Kruszewski M., Iwaneńko T., Bartłomiejczyk T., Woliński J., Starzyński R.R., Gralak M.A., Zabielski R., Lipiński P. Hepatic iron content corresponds with the susceptibility of lymphocytes to oxidative stress in neonatal pigs. Mutation Research – Genetic Toxicology and Environmental Mutagenesis, 657, 146-149 (2008). 40. Kruszewski M., Lewandowska H., Męczyńska S., Brzóska K., Rumianek K., Wójciuk G., Sadło J. NO for iron: genotoxicity of dinitrosyl iron complexes. Acta Biochimica Polonica, 55, Suppl. 3, 239 (2008). 164 PUBLICATIONS IN 2008

41. Kruszewski M., Sochanowicz B., Szperl M., Piotrowski W., Kolsut P., Rywik T., Kopacz M., Różański J., Korewicki J., Leszek P. The correlation among iron homeostasis in the heart and serum markers in failing human hearts. Progress in Biochemistry and Biophysics, 35, Suppl., 163-164 (2008). 42. Lankoff A., Sochacki J., Spoof L., Meriluoto J., Wójcik A., Węgierek A., Verschaeve L. Necleotite excision repair impairment by nodularin in CHO cell lines due to ERCC1/XPF inactivation. Toxicology Letters, 179, 101-107 (2008). 43. Lazurik V.T., Lazurik V.M., Popov G.F., Rogov Yu.V., Zimek Z. Integration of computation methods into radiation sterilization process. Journal of Kharkiv University, Physical Series: Nuclei, Particles, Fields, 832, 4, 77-82 (2008). 44. Leciejewicz J., Penc B., Szytuła A., Jezierski A., Zygmunt A.

Magnetic properties of the Mn5Si3 compound. Acta Physica Polonica A, 113, 4, 1193-1203 (2008). 45. Leszek P., Kruszewski M. Effects of beta-erythropoietin treatment on left ventricular remodeling, systolic function, and B-type natriuretic peptide levels in patients with cardiorenal anemia syndrome. American Heart Journal, 155, 3, e25 (2008) (DOI: 10.1016/j.ahj.2007.12.018). 46. Leszek P., Kruszewski M. Randomized, double-blind, placebo-controlled study to evaluate the effect of two dosing regiments of darbepoetin alfa in patients with heart failure and anaemia. European Heart Journal, 29, 4, 565-566 (2008). 47. Leszek P., Sochanowicz B., Szperl M., Piotrowski W., Kolsut P., Religa G., Rywik T., Różański J., Korewicki J., Kruszewski M. Niewydolność serca – ekspresja białek regulujących gospodarkę jonem żelaza w niewydolnym sercu a markery gospodarki żelazowej we krwi obwodowej (Heart failure – changes in the expression of proteins regulating the activity of iron in an insufficient heart, and the marker sof iron activity in peripheral blond). Kardiologia Polska, 66, 9, Suppl. 2, S60-S61 (2008). 48. Leszek P., Sochanowicz B., Szperl M., Piotrowski W., Kolsut P., Religa G., Rywik T., Różański J., Kruszewski M., Korewicki J. Zaawansowana niewydolność serca – zmiany w ekspresji białek regulujących gospodarkę jonem żelaza (Advanced heart failure – changes in the protein expression regulating the activity of iron ion). Kardiologia Polska, 66, 9, Suppl. 2, S229 (2008). 49. Leszek P., Sochanowicz B., Szperl M., Piotrowski W., Kolsut P., Rywik T., Kopacz M., Różański J., Korewicki J., Kruszewski M. Failing human hearts – the correlation among iron homeostasis in the hart and serum markers. European Journal of Heart Failure Supplements, 7, Suppl. 1, 135 (2008). 50. Leszek P., Sochanowicz B., Szperl M., Piotrowski W., Religa G., Rywik T., Kopacz M., Różański J., Kruszewski M., Korewicki J. Iron homeostasis in the failing human heart. European Journal of Heart Failure Supplements, 7, Suppl. 1, 137 (2008). 51. Łyczko K., Bąk J. 4 3 2 Poly[bis(μ3-acetato-κ O,O’:O:O’)bis(m2acetato-κ O,O’:O)(μ2-2,5-dimethylbenzene-1,4-diol-κ O:O’) dilead(II)]. Acta Crystallographica Section E, 64, m1341-m1342 + [8] p. 52. Majkowska A., Bilewicz A. Makrocykliczne kompleksy radionuklidów w medycynie nuklearnej (Macrocyclic complexes of radionuclides in nuclear medicine). Wiadomości Chemiczne, 62, 7-8, 610-633 (2008). 53. Męczyńska S., Lewandowska H., Sochanowicz B., Sadło J., Kruszewski M. Variable inhibitory effects on the formation of dinitrosyl iron complexes by deferoxamine and salicylal- dehyde isonicotinoyl hydrazone in K562 cells. Hemoglobin, 32, 1-2, 157-163 (2008). 54. Mioduski T., Gumiński C., Zeng D. IUPAC-NIST Solubility Data Series. 87. Rare earth metal chlorides in water and aqueous systems. Part 1. Scandium group (Sc, Y, La). PUBLICATIONS IN 2008 165

Journal of Physical and Chemical Reference Data, 37, 4, 1765-1852 (2008). 55. Morand J., Deperas-Standylo J., Urbanik W., Moss R., Hachem S., Sauerwein W., Wójcik A. Confidence limits for Neyman type A-distributed events. Radiation Protection Dosimetry, 128, 4, 437-443 (2008). 56. Morgenstern A., Lebeda O., Stursa J., Bruchertseifer F., Capote R., McGinley J., Rasmussen G., Sin M., Zielińska B., Apostolidis Ch. Production of 230U/226Th for targeted alpha therapy via proton irradiation of 231Pa. Analytical Chemistry, 80, 8763-8770 (2008). 57. Narbutt J., Krejzler J. Neutral bidentate N-heterocyclic ligands – phase transfer reagents improving the kinetics of solvent extraction of Am(III) and Eu(III) ions with tetradentate 6,6’-bis-(diethyl-1,2,4-triazin-3-yl)-2,2’-bipyridine. Radiochimica Acta, 96, 219-223 (2008). 58. Nichipor H., Yacko S., Sun Y., Chmielewski A.G., Zimek Z.

Theoretical study of dose and dose rate effect on trichloroethylene (HCl=CCl2) decomposition in dry and humid air under electron beam irradiation. Nukleonika, 53, 1, 11-16 (2008). 59. Norseev Yu.V., Bilewicz A., Pruszyński M. 211At-Rh(16-S4-diol) as a starting complex for preparing an astatine-labeled radiopharmaceutical. Radiochemistry, 50, 2, 208-212 (2008). 60. Okwieka U., Szostak M.M., Misiaszek T., Turowska-Tyrk I., Natkaniec I., Pawlukojć A. Spectroscopic, structural and theoretical studies of 2-methyl-4-nitroaniline (MNA) crystal. Electronic transitions in IR. Journal of Raman Spectroscopy, 39, 849-862 (2008). 61. Ostapczuk A., Hakoda T., Shimada A., Kojami T. Naphthalene and acenaphthalene decomposition by electron beam generated plasma application. Plasma Chemistry and Plasma Processing, 28, 483-494 (2008). 62. Ostapczuk A., Licki J., Chmielewski A.G. Polycyclic aromatic hydrocarbons in coal combustion flue gas under electron beam irradiation. Radiation Physics and Chemistry, 77, 490-496 (2008). 63. Palige J., Ptaszek S., Dobrowolski A., Chmielewski A.G. Symulacje numeryczne procesu osadzania polidyspersyjnej zawiesiny osadu czynnego w wtórnym osadniku przemysłowym (Numerical simulations of polydispersive sludge sedimentation in an industrial settler). Inżynieria i Aparatura Chemiczna, 6, 38-40 (2008). 64. Palige J., Ptaszek S., Zimnicki R., Chmielewski A.G., Wierzchnicki R. Stable isotope deuterium as a natural tracer of mixing processes in rivers. Nukleonika, 53, 2, 63-67 (2008). 65. Pawlukojć A., Prager M., Sawka-Dobrowolska W., Bator G., Sobczyk L., Ivanov A., Rols S., Grech E., Nowicka-Scheibe J., Unruh T. The structure, methyl rotation reflected in inelastic and quasielastic neutron scattering and vibrational spectra of 1,2,3,5-tetramethoxybenzene and its 2:1 complex with 1,2,4,5-tetracyanobenzene. The Journal of Chemical Physics, 129, 154506(1-12) (2008). 66. Pawlukojć A., Sobczyk L., Prager M., Bator G., Grech E., Nowicka-Scheibe J. DFT calculations of 2,6-dimethylpyrazine (26DMP) and its complex with chloranilic acid (CLA): comparison to INS, IR and Raman vibration spectra. Journal of Molecular Structure, 892, 261-267 (2008). 67. Peimel-Stuglik Z., Fabisiak S. A comparison of the performance characteristics of four film dosimeters in a 10-MeV electron beam. Applied Radiation and Isotopes, 66, 346-353 (2008). 68. Peimel-Stuglik Z., Kowalak S., Jankowska A. EPR spectra of γ-irradiated DL-α-alanine supported on molecular sieves. Spectrochimica Acta Part A, 69, 1395-1404 (2008). 69. Piątek M., El Fray M., Przybytniak G., Walo M. Wpływ budowy chemicznej oligoestrowych i oligoeterowych segmentów giętkich na właściwości termiczne i mechaniczne elastomerów termoplastycznych modyfikowanych wiązką elektronów (The in- 166 PUBLICATIONS IN 2008

fluence of the chemical composition oligoester and oligoether soft segments on thermal and mechanical properties of thermoplastic elastomers modified by eb radiation). Elastomery, 12, 3, 10-15 (2008). 70. Piątek M., El Fray M., Przybytniak G., Walo M. Wpływ wysokoenergetycznego promieniowania na właściwości biomateriałów zawierających nanonapeł- niacze (The effect of high energy radiation on nanocomposite-based biomaterials). Inżynieria Biomateriałów (Engineering of Biomaterials), 81-84, 104-107 (2008). 71. Piekara-Sady L., Jurga W., Kempiński W., Łoś Sz., Stankowski J., Piekoszewski J., Barlak M., Werner Z., Stanisławski J.

Magnetically modulated microwave absorption study of superconducting MgB2 regions. Applied Magnetic Resonance, 34, 157-162 (2008). 72. Piekoszewski J., Werner Z., Barlak M., Kolitsch A., Szymczyk W. Ion implantation followed by laser/pulsed plasma/ion beam annealing: a new approach to fabrication of superconducting MgB2 thin films. Nukleonika, 53, 1, 7-10 (2008). 73. Polkowska-Motrenko H., Chajduk E., Dudek J. Proficiency testing scheme PLANTS for the determination of selected trace elements in plant materials. Chemia Analityczna, 53, 983-992 (2008). 74. Pruszyński M., Bilewicz A., Zalutsky M.R. 211 211 Preparation of Rh[16aneS4-diol] At and Ir[16aneS4-diol] At complexes as potential precursors for astatine radiopharmaceuticals. Part I: Synthesis. Bioconjugate Chemistry, 19, 958-965 (2008). 75. Przybytniak G., Kornacka E., Mirkowski K., Walo M., Zimek Z. Functionalization of polymer surfaces by radiation-induced grafting. Nukleonika, 53, 3, 89-95 (2008). 76. Rumianek K., Wójciuk G., Brzóska K., Sadło J., Kruszewski M. The role of non-heme protein ligands in formation of dinitrosyl iron complexes in vivo. Acta Biochimica Polonica, 55, Suppl. 3, 250 (2008). 77. Sartowska B., Waliś L., Piekoszewski J., Nowicki L., Ratajczak R., Senatorski J. Modyfikacja struktury i właściwości warstw wierzchnich stali węglowych intensywnymi impulsami plazmy argonowej i azotowej (Modification of the structure and properties of the surfach layers of unalloyed steels using intense argon and nitrogen plasma pulses). Inżynieria Powierzchni, 3, 35-42 (2008). 78. Savina N.V., Dalivelya O.V., Kuzhir T.D., Grądzka I. Spravnenie dwóch sublinii kletok mlekopitajuscich po urovniju endogennych i inducirovannych radiaciej povrezhdenij genoma (The comparison of two sublines of mammalian cells by the level of endogeneous and radiation-induced genome damage). Vesti Nacyjanalnaj Akademii Navuk Belarusi, Serija Bijalagicnych Navuk (Proceedings of the National Academy of Science of Belarus, Biological Series), 3, 44-48 (2008). 79. Starosta W., Leciejewicz J. 4-Carboxypyridazin-1-ium chloride. Acta Crystallographica Section E, 64, o1553(8 p.). 80. Starosta W., Leciejewicz J. The crystal and molecular structures of hydrazine adducts with isomeric pyrazine dicarboxylic acids. The Open Crystallography Journal, 1, 31-36 (2008). 81. Starosta W., Leciejewicz J. Hydrazinediium bis(6-carboxypyridazine-3-carboxylate) dihydrate. Acta Crystallographica, Section E, 64, o461 + [7] p. (2008). 82. Starosta W., Leciejewicz J. Three-dimensional polymeric molecular pattern in the structure of a Ca(II) complex with pyrazine- 2,3,5,6-tetracarboxylate and water ligands. Journal of Coordination Chemistry, 61, 4, 490-498 (2008). 83. Szumiel I. Intrinsic radiation sensitivity: cellular signaling is the key. Radiation Research, 169, 249-258 (2008). PUBLICATIONS IN 2008 167

84. Trojanowicz M. Modern chemical analysis in archaeometry. Analytical and Bioanalytical Chemistry, 391, 915-918 (2008). 85. Walo M., Przybytniak G. Wpływ promieniowania jonizującego na termiczne właściwości segmentowych poliuretanów do celów biomedycznych (The influence of ionizing radiation on the thermal properties of segmentem polyurethanes for biomedical puprposes). Inżynieria Biomateriałów (Engineering of Biomaterials), 77-80, 117-120 (2008). 86. Wenska G., Filipiak P., Asmus K.-D., Bobrowski K., Koput J., Marciniak B. Formation of a sandwich-structure assisted, relatively long-lived sulfur-centered three-electron bonded radical anion in the reduction of a bis(1-substituted-uracilyl) disulfide in aqueous solution. Journal of Physical Chemistry B, 112, 10045-10053 (2008). 87. Wojewódzka M., Grądzka I., Buraczewska I., Brzóska K., Goncharova R.I., Szumiel I. Antimutagenic effect of 1,4-dihydropyridine derivatives in CHO-K1 cells. Acta Biochimica Polonica, 55, Suppl. 3, 256 (2008). 88. Wojewódzka M., Machaj E.K., Goździk A., Iwaneńko T., Ołdak T., Kruszewski M., Pojda Z. DNA damage in subpopulations of human lymphocytes irradiated with doses in the range of 0-1 Gy of X-radiation. Nukleonika, 53, 4, 145-149 (2008). 89. Wójcik A., Buraczewska I., Sommer S., Brzozowska K., Pręgowski J., Witkowski D., Pszona S., Bulski W. Enhanced level of micronuclei in peripheral blond lymphocytes of patients treated for restenosis with 32P endovascular brachytherapy. Cardiovascular Revascularization Medicine, 9, 149-155 (2008). 90. Xiarchos I., Jaworska A., Zakrzewska-Trznadel G. Response surface methodology for the modelling of copper removal from aqueous solutions using micellar-enhanced ultrafiltration. Journal of Membrane Science, 321, 222-231 (2008). 91. Zagórski Z.P. Ciemne strony wielkiej nauki XX wieku (Gloomy sides of great science of the twenties century). Orbital, 4, 201-203 (2008). 92. Zagórski Z.P., Głuszewski W. Radiacyjne sieciowanie kauczuku w produkcji opon samochodowych – rzeczywistość i mity (Radiation- -induced crosslinking of rubber in the production of car tyres – realisty and myths). Kauczuki Naturalne i Syntetyczne, 5, 26-29 (2008). 93. Zhydachevskii Ya., Suchocki A., Berkowski M., Sugak D., Luchechko A., Warchoł S. Technological approaches for improving thermoluminescent properties of the Czochralski-grown YAlO3:Mn crystals. Journal of Crystal Growth, 310, 3219-3223 (2008).

BOOKS

1. Advances in flow analysis. Ed. by M. Trojanowicz. Wiley-VCH Verlag, Weinheim 2008, 672 p. 2. Radiotracer residence time distribution method for industrial and environmental applications. Material for education and on-the-job training for practitioners of radiotracer technology. Chmielewski A.G. et al. (eds). Training Course Series no. 31. IAEA, Vienna 2008, 153 p.

CHAPTERS IN BOOKS

1. Berejka A.J., Kałuska I. Materials used in medical devices. 168 PUBLICATIONS IN 2008

In: Trends in radiation sterilization of health care products. IAEA, Vienna 2008, pp. 159-174. 2. Bluhm H., Han B., Chmielewski A.G., von Dobeneck D., Gohs U., Gstöttner J., Mattausch G., Morgner H., Koops H.W.P., Reichmann A., Röder O., Schultz S.W., Wenzel B., Zywitzki O. Electron beam devices for materials processing and analysis. In: Vacuum electronics. Components and devices. J.A. Eichmeier, M. Thumm (eds). Springer-Verlag, Berlin-Heidelberg 2008, pp. 155-230. 3. Chmielewski A.G., Berejka A.J. Radiation sterilization centres worldwide. In: Trends in radiation sterilization of health care products. IAEA, Vienna 2008, pp. 49-61. 4. Chmielewski A.G., Sadat T., Zimek Z. Electron accelerators for radiation sterilization. In: Trends in radiation sterilization of health care products. IAEA, Vienna 2008, pp. 27-47. 5. Cojocaru C., Zakrzewska-Trznadel G., Harasimowicz M., Jaworska A., Miśkiewicz A. Optymizacja procesu ultrafiltracji wspomaganej polimerami w aparacie helikoidalnym (Optimization of the ultrafiltration process enhanced by polymers in the helical membrane apparatus). In: Membrany i procesy membranowe w ochronie środowiska. Red. K. Konieczny, M. Bodzek. Monografie Komitetu Inżynierii Środowiskowej PAN, vol. 49. Gliwice 2008, pp. 359-363. 6. Danilczuk M., Pogocki D., Turek J., Sadło J., Michalik J. Organosilver radicals in molecular sieves. In: Zeolites and related materials: trends, targets and challenges. Proceedings of 4th International FEZA Conference. A. Gédéon, P. Massiani, F. Babonneau (eds). Elsevier 2008, pp. 933-936. 7. Dobrowolski A., Jaworska A., Zakrzewska-Trznadel G. Zastosowanie techniki planowania eksperymentów do wyznaczania optymalnych warunków pracy membrany do ultrafiltracji w procesie usuwania jonów miedzi (Application of the technique of experimental design for determination of optimal conditions of UF membrane operation in process of removing ions of copper). In: Membrany i procesy membranowe w ochronie środowiska. Red. K. Konieczny, M. Bodzek. Monografie Komitetu Inżynierii Środowiskowej PAN, vol. 49. Gliwice 2008, pp. 353-357. 8. Dziedzic-Gocławska A., Kamiński A., Uhrynowska-Tyszkiewicz I., Michalik J., Stachowicz W. Radiation sterilization of human tissue grafts. In: Trends in radiation sterilization of health care products. IAEA, Vienna 2008, pp. 231-260. 9. Houée-Levin Ch., Bobrowski K. Pulse radiolysis studies of free radical processes in peptides and proteins (Chapter 16). In: Radiation chemistry. From basics to applications in material and life sciences. M. Spotheim-Mauri- zot, M. Mostafavi, T. Douki, J. Belloni (eds). EDP Sciences, Les Ulis Cedex A 2008, pp. 233-247. 10. Meissner J., Mehta K., Chmielewski A.G. Radiation safety at irradiation facilities. In: Trends in radiation sterilization of health care products. IAEA, Vienna 2008, pp. 145-157. 11. Przybytniak G., Kornacka E., Mirkowski K., Walo M., Zimek Z. Functionalization of polymer surfaces by radiation-induced grafting for separation of heavy metal ions. In: Report of the 1st RCM on “Development of novel absorbents and membranes by radiation-induced grafting for environmental and industrial applications”, Vienna, Austria, 19-23.11.2007. IAEA, Vienna 2008, pp. 117-125. 12. Trojanowicz M. Application of moveable suspensions of solid particles in flow analysis. In: Advances in flow analysis. Ed. by M. Trojanowicz. Wiley-VCH Verlag, Weinheim 2008, pp. 79-106. 13. Wagner B., Nowak A., Bulska E., Kunicki-Goldfinger J., Schalm O., Janssens K. Analiza pierwiastkowa zabytkowych obiektów szklanych (Elemental analysis of antiqua glass objects). In: Nauka i zabytki. Nauki ścisłe w służbie archeologii, ochronie zabytków oraz historii. Państwowe Muzeum Archeologiczne, Warszawa 2008, pp. 71-81. 14. Weker W., Karbowniczek M., Pańczyk E. Badania wpływu własności fizycznych darniowej rudy żelaza na proces redukcji w piecu dymarskim (Studies of the effect of physical properties of sod iron ore on the reduction process in a primitive smelting furnace). In: Nauka i zabytki. Nauki ścisłe w służbie archeologii, ochronie zabytków oraz historii. Państwowe Muzeum Archeologiczne, Warszawa 2008, pp. 111-122. PUBLICATIONS IN 2008 169

15. Zagórski Z.P., Głuszewski W. Radiacyjna modyfikacja polipropylenu (Radiation induced modification of propylene). In: Materiały polimerowe. Praca zbior. pod red. J. Koszkula i E. Bociągi. Politechnika Częstochowska, Częstochowa 2008, pp. 247-254. 16. Zakrzewska-Trznadel G. Radioactive waste processing: advancement in pressure-driven processes and current world scenerio. In: Handbook of membrane separations: chemical, pharmaceutical, food, and biological applications. A.K. Pabby, S.S.H. Rizvi, A.M. Sastre (eds). CRC Press, Taylor & Francis Group, Boca Raton 2008, pp. 843-881. 17. Zimek Z., Kałuska I.M. Electron beam sterilization services centre in a developing country: Poland. In: Trends in radiation sterilization of health care products. IAEA, Vienna 2008, pp. 63-80.

THE INCT PUBLICATIONS

1. INCT Annual Report 2007. Institute of Nuclear Chemistry and Technology, Warszawa 2008, 219 p. 2. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Institute of Nuclear Chemistry and Technology, Warszawa 2008, 221 p. 3. Peimel-Stuglik Z. Dozymetry z wykorzystaniem cukrów. Cz.1. Dotychczasowe rozwiązania i propozycje (Sugar dosimeters. Part 1. State of the art). Instytut Chemii i Techniki Jądrowej, Warszawa 2008. Raporty IChTJ. Seria B nr 1/2008, 14 p. 4. Ostapczuk A. Obowiązujące w Polsce regulacje w zakresie emisji lotnych związków organicznych do atmosfery (Regu- lations concerning emission of volatile organic compounds into the atmosphere in Poland). Instytut Chemii i Techniki Jądrowej, Warszawa 2008. Raporty IChTJ. Seria B nr 2/2008, 16 p. 5. Chmielewski A.G., Sun Y. Emission of gaseous organic pollutants and flue gas treatment technology. Institute of Nuclear Chemistry and Technology, Warszawa 2008. Raporty IChTJ. Seria B nr 3/2008, 26 p. 6. Drzewicz P. Wielopierścieniowe węglowodory aromatyczne – występowanie i oznaczanie (Polycyclic hydrocarbons – occurence and determination). Instytut Chemii i Techniki Jądrowej, Warszawa 2008. Raporty IChTJ. Seria B nr 4/2008, 22 p. 7. Łyczko M. Porównanie wydajności reakcji otrzymywania trikarbonylkowych kompleksów technetu-99m i renu-188 na +1 stopniu utlenienia (Yields of tricarbonyl complexes of technetium-99m and rhenium-188 on +1 oxidation state – comparative study). Instytut Chemii i Techniki Jądrowej, Warszawa 2008. Raporty IChTJ. Seria B nr 5/2008, 12 p. 8. Polkowska-Motrenko H., Fuks L., Pyszynska M. Przygotowanie materiałów do badań i organizacja porównań międzylaboratoryjnych w zakresie oznaczania 137Cs i 90Sr w wodzie, mleku i glebie (Preparation of test materials and organization of interlaboratory comparison on determination of 137Cs and 90Sr radioactivity concentrations in water, milk and soil). Instytut Chemii i Techniki Jądrowej, Warszawa 2008. Raporty IChTJ. Seria B nr 6/2008, 32 p. 9. Polkowska-Motrenko H., Dudek J., Chajduk E., Czerska E. Badanie biegłości ROŚLINY 8 – oznaczanie zawartości As, Cd, Cr, Cu, Hg, Pb, Se i Zn w suszonym korzeniu marchwi (Proficiency test PLANTS 8 – determination of As, Cd, Cr, Cu, Hg, Pb, Se and Zn in dry carrot root powder). Instytut Chemii i Techniki Jądrowej, Warszawa 2008. Raporty IChTJ. Seria B nr 7/2008, 26 p. 10. Zimek Z., Dźwigalski Z., Warchoł S., Bułka S., Roman K. Modernizacja Stacji Sterylizacji Radiacyjnej: układy i instalacje liniowego akceleratora elektronów LAE-10/15. Część II (Modernization of a radiation sterilization station: arrangements and installations of the linear electron accelerator LAE-10/15. Part II). Instytut Chemii i Techniki Jądrowej, Warszawa 2008. Raporty IChTJ. Seria B nr 8/2008, 56 p. 170 PUBLICATIONS IN 2008 CONFERENCE PROCEEDINGS

1. Bobrowski K. Radiation chemistry: free radical reactions. Workshop on Radiation and Photochemistry (ISRAPS 2008), Mumbai, India, 3-5.01.2008. Lectures notes, 14 p. 2. Bobrowski K., Kciuk G., Hug G.L., Hömer G. OH-induced oxidation of dipeptides containing tyrosine and methionine: influence of amino acid sequence, conformation and pH. Proceedings of the Trombay Symposium on Radiation & Photochemistry, Pune, India, 7-11.01.2008, pp. 13-14. 3. Chmielewski A.G. Energetyka i środowisko (Power sector and the environment). Konferencja: Ekologiczna Energia i Paliwa, Chełm, Poland, 28.03.2008, [8] p. (CD ed.) 4. Chmielewski A.G., Pawelec A., Zimek Z., Licki J. Electron beam gas treatment as multipollutant control technology – present state and perspectives. 10 Annual Electric Power Conference & Exhibition, Baltimore, USA, 5-8.05.2008. Pre-conference papers, [15] p. 5. Chmielewski A.G. Przyszłość energetyczna Polski i świata (The future of power sector in Poland and in the world). Wytwarzanie energii elektrycznej i cieplnej oraz biopaliw z biomasy szansą dla regionu. Konferencja naukowo-techniczna, Zamość, Poland, 4-5.12.2008, pp. 5-12. 6. Chmielewski A.G., Polak A. Oczyszczanie i wzbogacanie biogazu (Purification and enrichment of biogas). Wytwarzanie energii elektrycznej i cieplnej oraz biopaliw z biomasy szansą dla regionu. Konferencja naukowo-techniczna, Zamość, Poland, 4-5.12.2008, pp. 22-26. 7. Dambies L., Jaworska A., Zakrzewska-Trznadel G. Chemical modification of polymers in order to improve the complexation ability of heavy metal ions. Proceedings of the XXIII International Symposium on Physico-Chemical Methods of Separation “Ars Separatoria 2008”, Toruń, Poland, 6-9.07.2008, pp. 224-227. 8. Khayet M., Harasimowicz M., Jaworska A., Zakrzewska-Trznadel G. Removal of radionuclides from water solution in ultrafiltration/complexation process with polyethersulfone (PES), polysulfone (PS) and surface-modified (SMM) membranes. Proceedings of the XXIII International Symposium on Physico-Chemical Methods of Separation “Ars Separatoria 2008”, Toruń, Poland, 6-9.07.2008, pp. 369-372. 9. Narbutt J. Effects of hydration and salvation of metal complexes on separations of metal ions by solvent extractions. In: Solvent extraction: Fundamentals to industrial applications. Proceedings of ISEC 2008 International Solvent Extraction Conference. Moyer B.A. (ed.), pp. 1035-1042. 10. Narbutt J. Hydration and salvation of metal complexes in solvent extraction systems: selectivity of metal ions separation. Proceedings of DAE-BRNS Biennial Symposium on Emerging Trends in Separation Science and Tech- nology, Delhi, India, 12-14.03.2008. Pathak P.N., Sawant R.M., Srinivasan V.S., Parmar V.S., Manchanda V.K. (eds), pp. 12-17. 11. Obryk B., Bilski P., Fuerstner M., Glaser M., Ilgner C., Olko P., Stuglik Z. Development of a method of passive measurement of radiation doses at ultra-high dose range. 2008 Nuclear Science Symposium, Medical Imaging Conference and 16th Room Temperature Semicon- ductor Detector Workshop, Dresden, Germany, 19-25.10.2008, [5] p. (CD ed.) 12. Polak A., Chmielewski A.G. Membranowy rozdział mieszanin gazowych dla potrzeb energetyki (Membrane separation of gaseous mixtures for the needs of power sector). VI Konferencja: „Dla miasta i środowiska. Problemy unieszkodliwiania odpadów”, Warszawa, Poland, 15.12.2008. Materiały konferencyjne, pp. 112-115. 13. Polkowska-Motrenko H. Preparation and use of Polish mushroom proficiency testing materials. PUBLICATIONS IN 2008 171

In: Nuclear proficiency testing. 1st International Workshop on Proficiency Testing in Applications of the Ionizing Radiation and Nuclear Analytical Techniques in Industry, Medicine, and Environment, Bucha- rest, Romania, 6-9.10.2007. Cincu E., Manea I., Woods M. (eds). AIP Conference Proceedings no. 1036. American Institute of Physics, Melville, New York 2008, pp. 123-130. 14. Zakrzewska-Trznadel G. Processing of low- and intermediate-level radioactive wastes from medical and industrial applications by membrane methods. ICOM 2008: International Congress on Membranes and Membrane Processes, Honolulu, Hawai, USA, 12-18.07.2008. Oral presentation proceedings, [2] p.

CONFERENCE ABSTRACTS

1. Barlak M., Piekoszewski J., Werner Z., Pakiela Z., Sartowska B., Składnik-Sadowska E., Waliś L., Kierzek J., Starosta W., Kolitsch A., Groetzchel R., Bocheńska K. Influence of distribution of titanium alloyed into carbon ceramics by the intense plasma pulses on their surface wettability. ION 2008: 7. International Conference - Ion Implantation and Other Applications of Ions and Elec- trons, Kazimierz Dolny, Poland, 16-19.06.2008, p. 64. 2. Bobrowski K. Intramolecular electron transfer in dipeptides containing tyrosine and methionine: relevance to radical chemistry in peptides and proteins. Free Radicals in Chemical Biology (COST CM0603). Annual Meeting for MC Members, The Sandbjerg Estate, Denmark, 26-28.06.2008, [1] p. 3. Bobrowski K., Hug G.L., Pogocki D., Hörner G., Schöneich C., Marciniak B. Conformational and geometrical influence on the type of stabilization of sulfur radical cations in peptides. 10th International Symposium on Organic Free Radicals / 3rd Pacific Symposium on Radical Chemistry, Heron Island, Australia, 3-9.08.2008, [1] p. 4. Bobrowski K., Mozziconacci O., Houeé-Levin C. Superoxide radical anions protect enkephalin from oxidation if the amine group is blocked. Pune University Workshop on Radiation & Photochemistry, Pune, India, 11-12.01.2008, [1] p. 5. Buczkowski M., Przybytniak G., Mirkowski K., Rumiński W. Influence of 10 MeV electron beam radiation on rheological properties of polypropylene. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 162. 6. Buczkowski M., Sartowska B., Starosta W. Template synthesis of silver chloride microrods using polyester track-etched membranes. 24 International Conference on Nuclear Tracks in Solids, Bologna, Italy, 1-5.09.2008. Book of abstracts, pp. 50-51. 7. Bułka S., Lazurik V.T., Lazurik V.M., Popov G., Rogov Yu., Zimek Z. Dose field formation in heterogeneous target irradiated with X-ray beam. Comparison of Monte Carlo simulation results with film dosimetry. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 140. 8. Chajduk E. Marie Curie transfer of knowledge AMERAC – importance of different analytical techniques in environmental research and monitoring. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 192. 9. Chajduk E., Polkowska-Motrenko H., Dybczyński R. RNAA definitive methods for selenium and arsenic determination in biological materials and their importance in inorganic trace analysis. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 130. 172 PUBLICATIONS IN 2008

10. Chmielewska D., Gryczka U., Migdał W., Płociński T., Starosta W., Chmielewski A.G. Nanosilver embedded hydrogels with enhanced antibacterial activity. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 170. 11. Chmielewski A.G. Electron bream technology for air pollution control. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 203. 12. Chmielewski A.G. New developments in electron beam flue gas treatment (EBFGT). 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 69. 13. Chmielewski A.G. Nuclear fuel worldwide reserves. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 24. 14. Chmielewski A.G. Radiation and chitosan. 8th International Symposium on Ionizing Radiation and Polymers (IRaP2008), Rio de Janeiro, Brazil, 12-17.10.2008, pp. 122-123. 15. Chmielewski A.G. Role of nuclear and radiation technologies in oil, gas and coal mining, distribution and power sector applications. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 21. 16. Chmielewski A.G., Chmielewska D.K. Radiation synthesis of metallic nanoclusters. 8th International Symposium on Ionizing Radiation and Polymers (IRaP2008), Rio de Janeiro, Brazil, 12-17.10.2008, p. 123. 17. Chmielewski A.G., Licki J.

Electron beam flue gas treatment process for purification of exhaust gases with high SO2 concentrations. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 69. 18. Chwastowska J., Skwara W., Dudek J., Sadowska-Bratek M., Dąbrowska M., Pszonicki L. Sorbent chelatujący z ditizonem, właściwości analityczne, możliwości zastosowania (Dithizone sorbent, analytical properties and use). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVII Poznańskiego Konserwatorium Analitycznego, Poznań, Poland, 26-27.03.2008, p. 99. 19. Çiçek E., Bardakçi B., Jaworska A. The use of zeolites to adsorb Tc-99m pertechnate, Tc-99m methylene diphosphonate and Tc-99m dimer- captosuccinic acid. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 121. 20. Çiçek E., Cojocaru C., Jaworska A., Zakrzewska-Trznadel G. Response surface methodology for the modeling of cobalt ions adsorption on Isparta Pumice. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 194. 21. Çiçek E., Cojocaru C., Zakrzewska-Trznadel G., Harasimowicz M. The characterization and modeling of cobalt ions adsorption on zeolite 4A. PUBLICATIONS IN 2008 173

International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 195. 22. Cieśla K., Nowicki A., Buczkowski M. Radiation modification of the functional properties of the edible films prepared using starch and starch- -lipid system. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 72. 23. Cojocaru C., Zakrzewska-Trznadel G., Dobrowolski A. Mathematical modeling and optimization of cross-flow ultrafiltration process. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 187. 24. Dambies L., Jaworska A., Zakrzewska-Trznadel G. Functionalisation of soluble polymers applied for removal of 60Co from radioactive wastes. 6th PIM Conference: Isotopic Processes, Cluj-Napoca, Romania, 22-24.09.2008, p. 40. 25. Danko B., Dybczyński R., Kulisa K., Samczyński Z. Different approaches to the determination of lanthanides in plant materials. Nuclear and non nuclear analytical techniques. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 133. 26. De la Fuente J., Poblete C., Aliaga C., Zapata G., Sobarzo-Sanchez E., Jullian C., Saitz C., Kciuk G., Bobrowski K. Photoreduction and photooxidation of oxoisoaporphines: laser flash photolysis study in the presence of amines and tetracyanoethylene. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 41. 27. Dybczyński R.S. Chromatografia cieczowa jako narzędzie zatężania i rozdzielania pierwiastków śladowych w połączeniu z NAA i innymi technikami instrumentalnymi (Liquid chromatography as a tool in concentration and separation of trace elements combined with NAA and other instrumental techniques). III Konferencja: Analityczne Zastosowania Chromatografii Cieczowej, Warszawa, Poland, 23-24.10.2008, p. 14. 28. Dybczyński R.S. Some examples of the use of ion exchange and extraction chromatography in inorganic trace analysis. VIII Konferencja Chromatograficzna: „Zastosowanie technik chromatograficznych w analizie środo- wiskowej i klinicznej”, Łódź, Poland, 21-23.04.2008, [1] p. 29. Dybczyński R.S. Two philosophies in designing radiochemical separations intended for neutron activation analysis. 9th International Conference on Nuclear Analytical Methods in the Life Sciences, Lisbon, Portugal, 7-12.09.2008, p. A008. 30. Dybczyński R.S. Wprowadzenie do dyskusji (Introduction to discussion). Ogólnopolska Konferencja Naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 27-28.11.2008. Streszczenia wystąpień, p. 6. 31. Fabisiak S., Virgolici M., Manea M.M., Negut C.D., Cutrubinis M., Georgescu R.M. Investigation of solid state sugar as a potential dosimetric material – physical and chemical characterization. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 142. 32. Filipiak P., Hug G.L., Bobrowski K., Marciniak B. How the time resolved techniques can support steady-state results. Based on photochemistry of thioether- -containing aromatic carboxylic acids. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 59. 174 PUBLICATIONS IN 2008

33. Filipiak P., Pietrzak M., Paczkowski J., Bobrowski K., Marciniak B. Formation of cation-radical anion pairs derived from carboxybenzophenone-tetrabutylammonium salts. Pulse radiolysis studies. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 60. 34. Fuks L., Gniazdowska E., Koźmiński P., Sadlej-Sosnowska N. 1 + 1 + fac-Tc (CO)3 and fac-Re (CO)3 complexed by pyridinecarboamide as possible radiopharmaceuticals for therapeutic applications. 4th EuCheMS Conference on Nitrogen Ligands in Coordination Chemistry, Metal-Organic Chemistry, Bio- inorganic Chemistry and Homogeneous Catalysis, Garmisch-Partenkirchen, Germany, 24-28.08.2008. Conference book, p. 112. 35. Fuks L., Gniazdowska E., Papagiannopoulou D., Koźmiński P., Papadopoulos M., Pelecanou M., Pirmettis I., Raptopoulou C., Sadlej-Sosnowska N., Tsoukalas C. I + I + fac-Tc (CO)3 and fac-Re (CO)3 complexed histidine derivatives – potential precursors of radiopharmaceuticals. EUROBIC9 – 9th European Biological Inorganic Chemistry Conference, Wrocław, Poland, 2-6.09.2008. Abstract book, [1] p. 36. Fuks L., Kothari K., Neves M. 99m + Complexes containing the [ Tc(CO)3 core for the targeted radiotherapy. EUROBIC9 – 9th European Biological Inorganic Chemistry Conference, Wrocław, Poland, 2-6.09.2008. Abstract book, [1] p. 37. Fuochi P.G., Lavalle M., Corda U., Kovacs A., Peimel-Stuglik Z., Gombia E. Stability test of gamma and electron irradiated transistors as solid state dosimeter at high dose levels. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 139. 38. Głuszewski W. Problemy ochrony radiologicznej w radiacyjnej modyfikacji materiałów (Radiation protection problems in radiation modification of materials). 11. Spotkanie Inspektorów Ochrony Radiologicznej, Dymaczewo Nowe, Poland, 27-30.05.2008. Materiały konferencyjne, pp. 26-27. 39. Głuszewski W., Zagórski Z.P. Aromatic protection effects in polypropylene radiolysis. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 168. 40. Głuszewski W., Zagórski Z.P. Badania postradiacyjnych procesów utleniania polipropylenu (Study of postirradiation processes of polymer oxidation). ChemSession’08: V Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 16.05.2008. Streszczenia, p. 41. 41. Grądzka I., Buraczewska I., Szumiel I., Brzóska K., Goncharova R., Wojewódzka M. Effect of 1,4-dihydropyridine derivatives on mutation frequency and oxidative base damage in CHO-K1 cells. The 9th International Congress on Cell Biology & The 20th Annual Conference of the Korean Society for Molecular and Cellular Biology, Seoul, Korea, 7-10.10.2008, p. 236, P2-29. 42. Grodkowski J., Kocia R., Mirkowski J. Formations and reactions of p-terphenyl related intermediates in ionic liquids. Pulse radiolysis study. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 69. 43. Grodkowski J., Kocia R., Mirkowski J. Formations of p-terphenyl excited states in ionic liquids. Pulse radiolysis study. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 62. 44. Grodkowski J., Kocia R., Mirkowski J., Szreder T. Badanie reakcji jonowo-rodnikowych w układach cieczy jonowych (Research on ionic-radical reactions in ionic liquids). PUBLICATIONS IN 2008 175

ChemSession’08: V Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 16.05.2008. Streszczenia, p. 61. 45. Gryczka U., Dondi D., Chmielewski A.G., Migdał W., Buttafava A., Faucitano A. The mechanism of chitosan degradation by gamma and e-beam irradiation. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 169. 46. Gryczka U., Gawrońska H., Migdał W., Gawroński S.W., Chmielewski A.G. Study on biological activity of chitosan after radiation processing. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 165. 47. Guzik G., Stachowicz W., Michalik J. The study on stable radicals produced by radiation in dried fruits and sugars by electron paramagnetic resonance spectrometry (EPR). International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008 p. 128. 48. Harasimowicz M., Khayet M., Zakrzewska-Trznadel G. Preparation and characterization of PVDF membranes for environmental applications. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 191. 49. Herdzik I., Narbutt J. Badanie kinetyki wymiany jonowej galu i indu w układach: wodne roztwory HCl/anionit (Dowex 1-X8) (Kinetics of ion exchange of gallium and indium ions in the system aqueous HCl/anion exchange resin (Dowex 1-X8). ChemSession’08: V Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 15.05.2008. Streszczenia, p. 48. 50. Hug G.L., Bobrowski K., Marciniak B., Pogocki D., Schöneich C., Hörner G. Free-radical reactions in cyclic dipeptides containing methionine. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 30. 51. Iller E., Polkowska-Motrenko H., Deptuła A., Wawszczak D., Łada W., Konior M., Milczarek J., Żołądek J., Zaza F. Gel metal-oxide composites as filling materials for W-188/Re-188 generator columns. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 62. 52. Iller E., Polkowska-Motrenko H., Łada W., Wawszczak D., Sypuła M., Konior M., Milczarek J., Żołądek J., Ralis J. Studies of gel metal-oxide nanocomposite samples as filling materials for W-188/Re-188 generator column. 9th International Conference on Nuclear Analytical Methods in the Life Sciences, Lisbon, Portugal, 7-12.09.2008, p. A052. 53. Jakowiuk A., Urbański P., Świstowski E., Machaj B., Pieńkos J.P., Kowalska E. Metrological features of radiometric dust concentration monitors operating with wireless communication system. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 42. 54. Kałuska I., Bułka S., Zimek Z. Risk management applied to irradiation of medical devices. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 125. 55. Kałuska I., Lazurik V.T., Lazurik V.M., Popov G., Rogov Yu., Zimek Z. Computer technology for decision of optimization tasks in radiation sterilization process. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 125. 176 PUBLICATIONS IN 2008

56. Kałuska I., Lazurik V.T., Lazurik V.M., Popov G., Rogov Yu., Zimek Z. Experimental benchmarking of software ModeStEB for simulation EB processing. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 139. 57. Kałuska I., Lazurik V.T., Lazurik V.M., Popov G., Rogov Yu., Zimek Z. Influence of boundary effects on EB dose field formation in multi-layer targets. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, pp. 124-125. 58. Kciuk G., Mirkowski J., Wiśniowski P., Bobrowski K. • • Oxidation of tyrosine and its peptides mediated by OH and N3 radicals. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 68. 59. Khayet M., Harasimowicz M., Jaworska A., Zakrzewska-Trznadel G. Removal of radionuclides from water solution with polyethersulfone (PES), polysulfone (PS) and surface-modified membranes. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 188. 60. Koźmiński P., Gniazdowska E., Fuks L., Mieczkowski J. Tricarbonyltechnetium(I)/rhenium(I) complexes with neutral bidentate ligands N, S, O donor atoms and monodentate isonitrile ligand. 4th EuCheMS Conference on Nitrogen Ligands in Coordination Chemistry, Metal-Organic Chemistry, Bio- inorganic Chemistry and Homogeneous Catalysis, Garmisch-Partenkirchen, Germany, 24-28.08.2008. Conference book, p. 139. 61. Kraś J., Nobis C., Myczkowski S. Leakage control methods for metal underground tanks and tanks placed on hardened soil with the use of radioactive tracers. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 54. 62. Krejzler J., Metwally E., Narbutt J. Temperature effect on the kinetics of solvent extraction of Am(III) and Eu(III) ions with tetradentate ligands, derivatives of bis-triazinylbipyridine. NRC7: 7th International Conference on Nuclear and Radiochemistry, Budapest, Hungary, 24-29.08.2008. Book of abstracts, p. 172. 63. Krejzler J., Zielińska B., Narbutt J. Partitioning of minor actinides from nuclear waste – contribution of INCT to the European FP7 collaborative project ACSEPT. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 182. 64. Kruszewski M., Sochanowicz B., Brzóska K., Szperl M., Piotrowski W., Kolsut P., Rywik T., Kopacz M., Rozanski J., Korewicki J., Leszek P. The correlation among iron homeostasis in the failing heart and serum markers. 1st International Conference RAHMS: Recent advantages in health and medical sciences, Paphos, Cyprus, 7-12.03.2008, p. 47. 65. Lehner K., Malec-Czechowska K., Guzik G., Stachowicz W. Detection of radiation treatment in dry plant extracts by thermoluminescence and pulsed photostimulated luminescence. Comparative study. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 104. 66. Lewandowska H., Męczyńska S., Brzóska K., Rumianek K., Wójciuk G., Sadło J., Kruszewski M. Genotoxicity of dinitrosyl iron complexes. The 9th International Congress on Cell Biology & The 20th Annual Conference of the Korean Society for Molecular and Cellular Biology, Seoul, Korea, 7-10.10.2008, p. 326, P13-29. PUBLICATIONS IN 2008 177

67. Machaj B., Urbański P., Bartak J. Simultaneous measurement of 222Rn and 220Rn in air. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 88. 68. Malinowska A., Szydłowski A., Jaskóła M., Korman A., Sartowska B. Calibration and application of modern track detectors CR-39/PM-355 in nuclear physics and high temperature plasma experiments. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 40. 69. Marciniak B., Hug G.L., Hörner G., Wójcik A., Bobrowski K. Photooxidation of sulfur-containing organic compounds. Mechanistic aspects. 10th International Symposium on Organic Free Radicals / 3rd Pacific Symposium on Radical Chemistry, Heron Island, Australia, 3-9.08.2008, [1] p. 70. Melski K., Kubera H., Głuszewski W., Zimek Z. Radiation modification PLA packaging materials. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 178. 71. Męczyńska S., Gołda S., Sadło J., Józkowicz A., Dulak J., Kruszewski M. The influence of hemin on formation of dinitrosyl complexes in vivo. ChemSession’08: V Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 16.05.2008. Streszczenia, p. 81. 72. Męczyńska S., Sadło J., Kruszewski M. Hemin increases formation of dinitrosyl iron complexes in K562 cells. SPIN 2008: 5th International Conference on Nitroxide Radicals, Ancona, Italy, 7-11.09.2008. Book of abstracts, p. P34. 73. Michalik J., Sadło J., Turek J., Sterniczuk M. Reactivity of silver paramagnetic clusters in zeolite rho. 6th Asia Pacific EPR/ESR Symposium (APES 2008), Cairns, Australia, 13-18.07.2008, [1] p. 74. Michalik J., Turek J., Danilczuk M., Sadło J. Organosilver radicals in molecular sieves. 4th International FEZA Conference, Paris, France, 2-6.09.2008. Book of abstracts and recent research reports, [1] p. 75. Michalik J., Turek J., Danilczuk M., Sterniczuk M., Sadło J. Organosilver radical in molecular sieves. 41st Annual International Meeting of the Electron Spin Resonance Group of the Royal Society of Chemistry: “Advanced techniques and applications of EPR”, London, Great Britain, 6-10.04.2008, p. 97. 76. Miljević N., Mikołajczuk A., Derda M. Nitrogen and oxygen isotope technique for fresh water analysis. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 190. 77. Misiak R., Kubica B., Lebedev V., Shishkin S., Bilewicz A.

Distribution of ruthenium and osmium tetroxide between CCl4 and aqueous phase. Model studies for chemistry of hassium. NRC7: 7th International Conference on Nuclear and Radiochemistry, Budapest, Hungary, 24-29.08.2008. Book of abstracts, p. 129. 78. Miśkiewicz A., Dobrowolski A., Zakrzewska-Trznadel G. Using tracer methods for examination of the flow structure and hydrodynamic conditions in the membrane module. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 146. 79. Miśkiewicz A., Jaworska A., Zakrzewska-Trznadel G., Gryczka U., Migdał W. Radiation-modified chitosan for removal of metals from water solutions. 178 PUBLICATIONS IN 2008

International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 172. 80. Nichipor H., Yacko S., Chmielewski A.G., Zimek Z. Kinetics and mechanism of naphthalene decomposition In flue gas under electron beam influence. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 198. 81. Nowicki A., Przybytniak G., Mirkowski K., Zimek Z. Functionalization of montmorillonite fillers with unsaturated compounds using electron beam irradiation. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 163. 82. Olszewska-Świetlik J., Pańczyk E., Waliś L. INAA in the studies of the lead-tin-yellow pigment in the mediaeval Polish painting of the Pomerania school. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 131. 83. Orelovich O.L., Sartowska B.A., Apel P.Yu. Analysis of the channel shapes in track membranes by the electron microscopy method. XIII International Conference on Electron Microscopy – EM’2008, Zakopane, Poland, 8-11.06.2008. Abstracts, p. 125. 84. Ostapczuk A., Licki J., Chmielewski A.G. EB processing of oil-combustion flue gases for PAH removal. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 204. 85. Palige J., Ptaszek S., Dobrowolski A., Chmielewski A.G. Application of radiotracer and CFD methods for investigation of internal flow structure in wastewater treatment plant apparatus. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 144. 86. Palige J., Ptaszek S., Dobrowolski A., Chmielewski A.G. Symulacje numeryczne procesu osadzania polidyspersyjnej zawiesiny osadu czynnego w wtórnym osadniku przemysłowym (Numerical simulations of polydispersive sludge sedimentation in an industrial settler). X Jubileuszowa Konferencja Rozdzielania Układów Niejednorodnych, Gdańsk, Poland, 8-10.12.2008. Streszczenia, p. 16. 87. Peimel-Stuglik Z. In search of an ecological dosimeter for high dose measurements. 7th International Topical Meeting on Industrial Radiation and Radioisotope Measurement Application, Prague, Czech Republic, 22-27.06.2008. Abstracts, p. 97. 88. Peimel-Stuglik Z. PVC films for pharmaceutical applications as sensitive routine dosimeter for electron beam irradiation and radiation indicator at ion beam experiments. 8th International Symposium on Ionizing Radiation and Polymers (IRaP2008), Rio de Janeiro, Brazil, 12-17.10.2008, p. 130. 89. Peimel-Stuglik Z. Radiation processing of fluid streams diluted aqueous solutions of sucrose as a dosimetric tool for operational qualification. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 70. 90. Peimel-Stuglik Z., Bryl-Sandelewska T., Mirkowski K., Sartowska B. Alanpol® - cheap, water resistant alanine-polymer routine dosimeter. PUBLICATIONS IN 2008 179

15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, pp. 118-119. 91. Peimel-Stuglik Z., Fabisiak S. Dosimetric properties of two PCV films produced for pharmaceutical purposes. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 138. 92. Peimel-Stuglik Z., Fabisiak S. Sucrose as double signal high dose dosimeter for ionizing radiation. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 119. 93. Pogocki D., Mirkowski J., Ruman T., Szpara K., Celuch M. Pulse radiolysis and DFT studies on the radical reaction of nicotine. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 56. 94. Polkowska-Motrenko H., Dudek J., Chajduk E. Badanie biegłości ROŚLINY 7: oznaczanie zawartości As, Cd, Cr, Cu, Hg, Pb, Se i Zn w grzybach suszonych – pieczarka szlachetna (Proficiency test PLANT 7 – determination of As, Cd, Cr, Cu, Hg, Pb, Se and Zn in dry mushroom powder (champignon)). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XVII Poznańskiego Konserwatorium Analitycznego, Poznań, 26-27.03.2008, p. 101. 95. Polkowska-Motrenko H., Dybczyński R. Certyfikowany materiał odniesienia CTA-OTL-1 (Liście tytoniu „Oriental”) – doświadczenia 18 lat stosowania (Certified Reference Material “Oriental” Tobacco Leaves (CTA-OTL-1) – eighteen years of experience). Ogólnopolska Konferencja Naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 27-28.11.2008. Streszczenia wystąpień, p. 10. 96. Połosak M., Bilewicz A. Complexes of 89Zr with macrocyclic and acyclic ligands for preparation of PET radiopharmaceuticals. NRC7: 7th International Conference on Nuclear and Radiochemistry, Budapest, Hungary, 24-29.08.2008. Book of abstracts, p. 159. 97. Pruszyński M., Bilewicz A., Zalutsky M.R. 211 + 211 + Synthesis and stability studies of Rh[16aneS4-diol] At and Ir[16aneS4-diol] At complexes – possibility new agents for labelling biomolecules with 211At. NRC7: 7th International Conference on Nuclear and Radiochemistry, Budapest, Hungary, 24-29.08.2008. Book of abstracts, p. 243. 98. Pruszyński M., Bilewicz A., Zalutsky M.R. 211 211 Synthesis of Rh[16aneS4-diol] At and Ir[16aneS4-diol] At complexes – possibly new precursors for labeling with astatine. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 60. 99. Przybytniak G., Kornacka E., Mirkowski K., Walo M., Zimek Z. Modification of PE, PP and PS by radiation-induced grafting for potential applications in metal ion adsorption. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 107. 100. Przybytniak G., Nowicki A., Walo M., Mirkowski K. Evaluation of polymers designed for radiation processing. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 71. 101. Rumianek K., Wójciuk G., Brzóska K., Sadło J., Kruszewski M. Rola wysokocząsteczkowych ligandów w powstawaniu dinitrozylowych kompleksów żelaza (The role on non-heme protein ligands in formation of dinitrosyl iron complexes). ChemSession’08: V Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 16.05.2008. Streszczenia, p. 109. 180 PUBLICATIONS IN 2008

102. Sartowska B., Piekoszewski J., Waliś L. Surface morphology of unalloyed steels remelted using intense plasma pulses. XIII International Conference on Electron Microscopy – EM’2008, Zakopane, Poland, 8-11.06.2008. Abstracts, p. 146. 103. Sartowska B., Piekoszewski J., Waliś L., Składnik-Sadowska E., Barlak M. Changes of stainless steels surface morphology as a result of interaction with intense pulsed plasma beams containing ions of rare earth elements. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 171. 104. Sommer S., Buraczewska I., Kruszewski M., Wójcik A. Biological dosimetry: perspectives and limitations. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 51. 105. Starosta W., Leciejewicz J. Catenated polymeric molecular pattern in the structure of a calcium(II) complex with pyridine-2,3-dicarboxylate (quinolinic) and water ligands. 50 Konwersatorium Krystalograficzne, Wrocław, Poland, 26-28.06.2008, p. 177. 106. Starosta W., Leciejewicz J. The crystal and molecular structures of hydrazine adducts of three isomeric pyrazine dicarboxylic acids. 50 Konwersatorium Krystalograficzne, Wrocław, Poland, 26-28.06.2008, pp. 178-179. 107. Strzelczak G., Janeba-Bartoszewicz E., Bobrowski K., Marciniak B. Electron paramagnetic resonance (EPR) study of radiation-induced radicals in 1,3,5-trithiane and its derivatives. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 78. 108. Stupińska H., Iller E., Zimek Z., Wawro D., Ciechańska D., Kopania E., Palenik J., Milczarek S., Stęplewski W., Krzyżanowska G. Environmentally friendly method to prepare microcrystalline cellulose. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 173. 109. Sun Y., Chmielewski A.G., Bułka S., Zimek Z. 4-chlorotoluene decomposition in air mixture by using electron beam technology. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 206. 110. Sun Y., Chmielewski A.G., Bułka S., Zimek Z. Toluene decomposition from gaseous phase by using electron beam irradiation. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 205. 111. Sun Y., Chmielewski A.G., Bułka S., Zimek Z., Nichipor H. Computer simulations of chloroethylenes decomposition in air under electron beam irradiation. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, pp. 141-142. 112. Sun Y., Chmielewski A.G., Licki J., Bułka S., Zimek Z. Organic compounds decomposition from simulated industrial off-gases by using electron beam irradiation. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, p. 142. 113. Szreder T., Wishart J.F., Grodkowski J., Skrzypczak A., Cook A.R. Intermediated generated in irradiated ionic liquids. Influence of anion and alkylammonium cation modification on solvated electron spectra. PULS’2008: 8th International Conference on Pulse Investigations in Chemistry, Biology and Physics, Kraków, Poland, 6-12.09.2008, p. 80. PUBLICATIONS IN 2008 181

114. Szydłowski A., Sartowska B., Jaskóła M., Korman A., Malinowska A. An extended study of the etching characteristics of CR-39 detectors. 24 International Conference on Nuclear Tracks in Solids, Bologna, Italy, 1-5.09.2008. Book of abstracts, p. 150. 115. Urbański P., Machaj B., Jakowiuk A., Świstowski E., Bartak J., Pieńkos J.P., Kowalska E., Fuks L. Simple radiation gauges for routine laboratory measurements. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 147. 116. Velizarov S., Miśkiewicz A., Crespo J. Electrochemical mineralization of water-soluble organic compounds using boron-doped diamond anode connected with membrane process. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 193. 117. Waliś L., Pańczyk E., Kunicki-Goldfinger J., Kierzek J., Chmielewska D. The role of physical techniques in cultural heritage studies. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 132. 118. Walo M., Przybytniak G., Mirkowski K. Wpływ promieniowania jonizującego na segmentowe poliuretany (Influence of ionizing radiation on segmental polyurethane resins). V Szkoła Analizy Termicznej SAT’08, Zakopane, Poland, 6-9.04.2008. Streszczenia, [1] p. 119. Werner Z., Pisarek M., Ratajczak R., Piekoszewski J., Barlak M. Chemical effects in Zr and Co implanted sapphire. ION 2008: 7. International Conference – Ion Implantation and Other Applications of Ions and Elec- trons, Kazimierz Dolny, Poland, 16-19.06.2008, p. 49. 120. Wierzchnicki R. Study of isotopic composition of milk and dairy products. Workshop on Marie Curie Host Fellowships for the Transfer of Knowledge – Advanced Methods for Envi- ronment Research and Control (AMERAC) contract no. MTKD-CT-2004-509226: “Separation processes and analytical methods for environmental studies and applications”, Warszawa, Poland, 6.08.2008, [2] p. 121. Wierzchnicki R., Derda M. Sulfur isotopic composition of milk and dairy products. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 196. 122. Wierzchnicki R., Plewka K.

Sample collection and preparation for CO2 isotopic analysis in industrial off-gasses. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 92. 123. Wójcik A., Deperas-Standyło J., Deperas-Kamińska M., Sommer S., Urbanik W. Statistical models for partial-body dose assessment: gaps and approaches. Partial-Body Radiation Diagnostic Biomarkers and Medical Management of Radiation Injury Work- shop, Bethesda, USA, 5-6.05.2008, [1] p. 124. Xiarchos I., Jaworska A., Zakrzewska-Trznadel G. Response surface methodology for the modelling of copper removal from aqueous systems via micellar enhanced ultrafiltration. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 189. 125. Zagórski Z.P. Software and hardware in the origins of life chemistry. Chembiogenesis 2008: Kickoff Meeting of COST Action CM0703 “Systems Chemistry”, Maratea, Italy, 8-10.10.2008. Abstracts, p. 20. 182 PUBLICATIONS IN 2008

126. Zagórski Z.P. Software and hardware in the origins of life chemistry. ESF-COST High-Level Research Conference “Systems Chemistry”, Maratea, Italy, 3-7.10.2008. Abstracts, p. 54. 127. Zagórski Z.P., Głuszewski W. Unit processes and unit operations in radiation processing. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 67. 128. Zagórski Z.P., Głuszewski W., Rajkiewicz M., Mikołajska A. Modification of elastomers by ionizing radiation. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 167. 129. Zakrzewska-Trznadel G. Liquid low and intermediate-level radioactive wastes treatment – the challenge for membrane methods. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 28. 130. Zakrzewska-Trznadel G., Cuna S., Wierzchnicki R., Derda M. The study of isotopic fractionation in the process of analysis of isotopic ratios 15N/14N and 18O/16O in nitrate from water. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 186. 131. Zakrzewska-Trznadel G., Jaworska A., Miśkiewicz A., Harasimowicz M., Dobrowolski A. Application of ultrafiltration enhanced by sorption on natural sorbents for removal of ions of radioactive metals from water solutions. 6th PIM Conference: Isotopic Processes, Cluj-Napoca, Romania, 22-24.09.2008, p. 39. 132. Zimek Z., Dźwigalski Z., Warchoł S., Bułka S., Roman K. Electron accelerator for radiation sterilization and R&D study. 15th International Meeting on Radiation Processing (IMRP), London, Great Britain, 21-25.09.2008. Conference handbook, pp. 143-144. 133. Zimek Z., Dźwigalski Z., Warchoł S., Roman K., Bułka S. Wybrane wyniki badań urządzeń i podzespołów nowego akceleratora elektronów 10 MeV, 10-15 kW (Selected results of examination of appliances and sub-systems of the linear electron accelerator LAE 10/15 type). IV Kongres Polskiego Towarzystwa Próżniowego oraz VIII Krajowa Konferencja Techniki Próżni, Janów Lubelski, Poland, 21-24.09.2008. Program i streszczenia prac, [1] p. 134. Zimek Z., Kałuska I., Bułka S. Risk management applied to irradiation of medical devices. International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008. Conference abstracts. Warszawa, Institute of Nuclear Chemistry and Technology 2008, p. 176.

SUPPLEMENT LIST OF THE PUBLICATIONS IN 2007

1. Chmielewski A.G. Inżynieria chemiczna i procesowa w Instytucie Chemii i Techniki Jądrowej w Warszawie (Chemical and processing engineering in the Institute of Nuclear Chemistry and Technology). In: Inżynieria chemiczna i procesowa w Polsce. Pod red. Cz. Strumiłło. PAN Oddział w Łodzi, Łódź 2007, pp. 443-453. 2. Chmielewski A., Gradoń L. Prof. dr hab. Anatol Selecki i Jego rola we współtworzeniu Wydziału Inżynierii Chemicznej i Procesowej [na Politechnice Warszawskiej] (Professor Anatol Selecki and his role in the co-operating of the Depart- ment of Chemical and Process Engineering [on the Warsaw Technical University]). PUBLICATIONS IN 2008 183

In: Inżynieria chemiczna i procesowa w Polsce. Pod red. Cz. Strumiłło. PAN Oddział w Łodzi, Łódź 2007, pp. 43-49. 3. Danko B., Trochimczuk W., Samczyńki Z., Hamerska-Dudra A., Dybczyński R.S. An attempt to differentiate the affinity of individual lanthanides to the resin using temperature driven swelling of the thermosensitive copolymer of N-isopropylacrylamide and 2-(methacryloyloxy)ethyl phosphate – thermodynamic studies. Reactive & Functional Polymers, 67, 1651-1659 (2007). 4. Licki J., Chmielewski A.G., Bigos A. Control systems of electron beam flue gas treatment technology. Raport IAE-130/A. Instytut Energii Atomowej, Otwock-Świerk 2007, 8 p. 5. Licki J., Chmielewski A.G., Bigos A., Jedynak A. Monitoring system and analytical methods for electron beam flue gas treatment technology. Raport IAE-131/A. Instytut Energii Atomowej, Otwock-Świerk 2007, 12 p. 6. Lipiński P., Gralak M.A., Starzyński R.R., Usińska A., Kruszewski M. Metabolizm żelaza u nowo narodzonych ssaków (Iron metabolizm in newly born mammals). In: Sterowanie rozwojem układu pokarmowego u nowo narodzonych ssaków. Praca zbior. pod red. R. Za- bielskiego. Państwowe Wydawnictwo Rolnicze i Leśne, Warszawa 2007, pp. 243-269. 7. Melski K., Kubera H., Głuszewski W., Zimek Z. Changes of mechanical properties of EKO FPO wrap packaging materials after treatment by ionizing radiation. In: Current trends in commodity science. Vol. 1. R. Zieliński (ed.) Poznań University of Economics Publish- ing House, Poznań 2007, pp. 524-529. 8. Prager M., Pawlukojć A., Wischnewski A., Wuttke J. Inelastic neutron scattering study of methyl groups rotation in some methylxanthines. The Journal of Chemical Physics, 127, 214509(1-10) (2007). 9. Tudek B., Kruszewski M. Mechanizmy naprawy DNA w tkankach o szybkim rozwoju i nowotworowych (Mechanisms of DNA repair in quickly developing and cancerous tissues). In: Sterowanie rozwojem układu pokarmowego u nowo narodzonych ssaków. Praca zbior. pod red. R. Za- bielskiego. Państwowe Wydawnictwo Rolnicze i Leśne, Warszawa 2007, pp. 292-310. 184 NUKLEONIKA

NUKLEONIKA THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH

EDITORIAL BOARD Andrzej G. Chmielewski (Editor-in-Chief, Poland), Krzysztof Andrzejewski (Poland), Janusz Z. Beer (USA), Jacqueline Belloni (France), Grażyna Bystrzejewska-Piotrowska (Poland), Gregory R. Choppin (USA), Władysław Dąbrowski (Poland), Hilmar Förstel (Germany), Andrei Gagarinsky (Russia), Andrzej Gałkowski (Poland), Evgeni A. Krasavin (Russia), Stanisław Latek (Poland), Robert L. Long (USA), Sueo Machi (Japan), Dan Meisel (USA), Jacek Michalik (Poland), Heino Nitsche (USA), Robert H. Schuler (USA), Christian Streffer (Germany), Irena Szumiel (Poland), Piotr Urbański (Poland), Alexander Van Hook (USA)

CONTENTS OF No. 1/2008

1. Assessment of a new scintillation crystal (LaBr3) in PET scanners using Monte Carlo method A.R. Karimian, C.J. Thompson 2. Ion implantation followed by laser/pulsed plasma/ion beam annealing: a new approach to fabrication of superconducting MgB2 thin films J. Piekoszewski, Z. Werner, M. Barlak, A. Kolitsch, W. Szymczyk

3. Theoretical study of dose and dose rate effect on trichloroethylene (HClC=CCl2) decomposition in dry and humid air under electron beam irradiation H. Nichipor, S. Yacko, Y. Sun, A.G. Chmielewski, Z. Zimek 4. Plutonium and gamma emitters in the northeastern part of Bory Tucholskie (Poland) J.W. Mietelski, S. Mirocha, J. Bogacz 5. Activity ratios of thorium isotopes in living species compared with other environmental samples R. Kierepko, J.W. Mietelski, P. Gaca, E. Tomankiewicz 6. Dose assessment and radioactivity of the mineral water resources of Dimeh springs in the Chaharmahal and Bakhtiari Province, Iran D. Shahbazi-Gahrouei, M. Saeb

CONTENTS OF No. 2/2008 1. Relationships between EGFR-initiated signalling, DNA double-strand break rejoining and survival in X-irradiated human glioma M059 cells I. Grądzka, I. Buraczewska, I. Szumiel 2. Determination of the geometry function for a brachytherapy seed, comparing MCNP results with TG-43U1 analytical approximations G. Raisali, M.G. Ghonchehnazi, P. Shokrani, M. Sadeghi 3. Light yield non-proportionality and intrinsic energy resolution of doped CsI scintillators W. Chewpraditkul, L. Swiderski, M. Moszynski 4. 10 MeV electron beam cross-linking of plasticized PVC in presence of EHPTM and TAC additives A. Behjat, Dj. Gheysari 5. Stable isotope deuterium as a natural tracer of mixing processes in rivers J. Palige, S. Ptaszek, R. Zimnicki, A.G. Chmielewski, R. Wierzchnicki 6. Peculiarities of 137Cs translocation in higher plants under environmental and laboratory conditions D. Marčiulionienė, B. Lukšienė, D. Kiponas 7. Damage distributions in GaAs single crystal irradiated with 84Kr (394 MeV), 209Bi (710 MeV) and 238U (1300 MeV) swift ions NUKLEONIKA 185

A.Yu. Didyk, F.F. Komarov, L.A. Vlasukova, E.A. Gracheva, A. Hofman, V.N. Yuvchenko, R. Wiśniewski, T. Wilczyńska

CONTENTS OF No. 3/2008 1. Comparison of dichromate and ethanol-chlorobenzene dosimeters in high dose radiation processing B. Šećerov, G. Bačić 2. Functionalization of polymer surfaces by radiation-induced grafting G. Przybytniak, E.M. Kornacka, K. Mirkowski, M. Walo, Z. Zimek 3. New microwave assisted radiolabelling method and rat brain biodistribution study of two new 99mTc-tricarbonyl complexes as potential brain imaging agents M. Trabelsi, A. Mekni, C. Solanki, P. Maltby, M. Saidi 4. Dense plasma source development and jet injection in Globus-M A.V. Voronin, V.K. Gusev, Yu.V. Petrov, E.E. Mukhin, S.Yu. Tolstyakov, G.S. Kurskiev, M.M. Kochergin, K.G. Hellblom 5. Damage and modification of materials produced by pulsed ion and plasma streams in Dense Plasma Focus device V.N. Pimenov, E.V. Demina, S.A. Maslyaev, L.I. Ivanov, V.A. Gribkov, A.V. Dubrovsky, Ü. Ugaste, T. Laas, M. Scholz, R. Miklaszewski, B. Kolman, A. Tartari 6. Transient induced molecular negative ions formed in cold electron collisions with polarized molecules E.I. Toader, W.G. Graham 7. Coloured-noise-induced transitions in nonlinear structures R. Mankin, T. Laas, E. Soika, A. Sauga, A. Rekker, A. Ainsaar, Ü. Ugaste

CONTENTS OF No. 4/2008 1. Reduction of transgenerational radiation induced genetic damages observed as numerical chromosomal abnormalities in preimplantation embryos by vitamin E M. Salimi, H. Mozdarani 2. DNA damage in subpopulations of human lymphocytes irradiated with doses in the range of 0-1 Gy of X-radiation M. Wojewódzka, E.K. Machaj, A. Goździk, T. Iwaneńko, T. Ołdak, M. Kruszewski, Z. Pojda 3. Biological evaluation of [18F]-nifedipine as a novel PET tracer for L-type calcium channel imaging H. Sadeghpour, A.R. Jalilian, M. Akhlaghi, A. Shafiee, M. Mirzaii, R. Miri, F. Saddadi 4. Thick zinc electrodeposition on copper substrate for cyclotron production of 64Cu M. Sadeghi, M. Amiri, P. Rowshanfarzad, Z. Gholamzadeh, M. Ensaf 5. Genotoxic effects of 60Co γ-rays on Chinese hamster ovary (CHO) cells T. Dicu, I. Brie, P. Virag, E. Fischer, M. Perde, V. Foris, V. Cernea, C. Cosma 6. Evaluation of set-up verification with the analysis of systematic and random errors in radiotherpy – a study of the Great Poland Cancer Centre Ł. Szczurek, A. Skrobała, T. Piotrowska, A. Jodda 7. Computations of fuel management in MARIA reactor with highly poisoned beryllium matrix K.J. Andrzejewski, T.A. Kulikowska, Z.E. Marcinkowska 8. A comparison of the basic photon and electron dosimetry data for Neptun 10PC linear accelerators P. Shokrani, S. Monadi

SUPPLEMENT No. 1/2008 Proceedings of the 14th National Scientific Meeting of the Polish Radiation Research Society, 24-26 September 2007, Kielce, Poland 1. Foreword A. Lankoff 2. Medium-mediated bystander response of X-ray-irradiated normal human lymphocytes in vitro M. Konopacka 186 NUKLEONIKA

3. Modulation of the growth of pulmonary tumor colonies in mice after single or fractionated low-level irradiations with X-rays E.M. Nowosielska, A. Cheda, J. Wrembel-Wargocka, M.K. Janiak 4. The influence of low frequency magnetic field upon cultivable plant physiology M. Rochalska 5. Radiation effects in polypropylene/polystyrene blends as the model of aromatic protection effects W. Głuszewski, Z.P. Zagórski 6. Reliability of light-stimulated photoluminescence (PSL) in detection of irradiated food comparison with thermoluminescence method (TL) G.P. Guzik, W. Stachowicz 7. Computation of the effect of pH on spur chemistry in water radiolysis at elevated temperatures D. Swiatla-Wojcik 8. Methods and measurements in radiation synovectomy with 90Y of knee joint dosimetry M. Kempińska 9. Applications of recombination chambers in the dosimetry of high energy radiation fields M. Zielczyński, N. Golnik, M.A. Gryziński

SUPPLEMENT No. 2/2008 Proceedings of the International Conference on Recent Developments and Applications of Nuclear Technologies, 15-17 September 2008, Białowieża, Poland 1. Foreword P. Urbański 2. Nuclear and radiation safety and security J. Niewodniczański 3. Nuclear fissile fuels worldwide reserves A.G. Chmielewski 4. Calibration and applications of modern track detectors CR-39/PM-355 in nuclear physics and high temperature plasma experiments A. Malinowska, A. Szydłowski, M. Jaskóła, A. Korman, B. Sartowska, M. J. Sadowski, J. Badziak, J. Że- browski 5. Measurement of radon concentration in the air by PicoRad detectors N.D. Chau 6. Modern micropattern gas detectors M. Bochenek, S. Koperny, T.Z. Kowalski 7. Factors affecting the precision of measurements with the usage of proportional counters M. Bochenek, S. Koperny, T.Z. Kowalski 8. Determination of initial recombination of ions created in quasi-pulsed radiation fields M. Zielczyński, N. Golnik, M.A. Gryziński 9. Metrological features of a beta absorption particulate air monitor operating with wireless communication system A. Jakowiuk, P. Urbański, E. Świstowski, B. Machaj, J. Pieńkos, E. Kowalska 10. Changes of stainless steels surface morphology as a result of interaction with intense pulsed plasma beams containing ions of rare earth elements B. Sartowska, J. Piekoszewski, L. Waliś, E. Składnik-Sadowska, M. Barlak 11. The use of definitive methods based on radiochemical neutron activation analysis for the determination of selenium and arsenic in materials used in proficiency testing E. Chajduk, H. Polkowska-Motrenko, R.S. Dybczyński 12. Role of nuclear and radiation technologies in oil, gas and coal mining, distribution and power sector applications A.G. Chmielewski

13. Electron beam flue gas treatment process for purification of exhaust gases with high SO2 concentrations A.G. Chmielewski, J. Licki NUKLEONIKA 187

14. Evaluation of polymers designed for radiation processing G. Przybytniak, A. Nowicki, K. Mirkowski 15. Study on biological activity of chitosan after radiation processing U. Gryczka, H. Gawrońska, W. Migdał, S.W. Gawroński, A. G. Chmielewski 16. Recent studies of irradiated mangoes in Brazil: a trend towards commercial approach S.F. Sabato, J.M. Silva, J.N. Cruz, P.O. Broisler, P.R. Rela, S. Salmieri, M. Lacroix 17. Vitamin E content and sensory qualities of γ-irradiated sunflower whole grain cookies M.S. Taipina, L.C.A. Lamardo, M.A.B. Rodas, N.L. del Mastro 18. Study of some physicochemical and rheological properties of irradiated honey A. Bera, L.B. Almeida-Muradian, S.F. Sabato 19. Study on stable radicals produced by ionizing radiation in dried fruits and related sugars by electron paramagnetic resonance spectrometry and photostimulated luminescence method – I. D-fructose G.P. Guzik, W. Stachowicz, J. Michalik 20. Principles of safety use of radioiodine in the treatment of well-differentiated thyroid carcinoma (DTC) A. Kowalczyk, G. Krajewska, Z. Podgajny, G. Kamiński 21. Development and production of radioactive sources used for cancer treatment in Brazil M.E.C.M. Rostelato, P.R. Rela, C.A. Zeituni, A. Feher, J.E. Manzoli, J.A. Moura, E.S. Moura, C.P.G. Silva 22. Sedimentation rates and dating of bottom sediments in the Southern Baltic Sea region M.M. Suplińska, Z. Pietrzak-Flis 23. Dynamic neutron radiography studies of water migration in beds of natural zeolite J. Żołądek, J.J. Milczarek, I. Fijał-Kirejczyk 24. Response surface methodology for cobalt removal from aqueous solutions using Isparta pumice and zeolite 4A adsorbents E. Çiçek, C. Cojocaru, G. Zakrzewska-Trznadel, A. Jaworska, M. Harasimowicz 25. Distribution of stable isotopes in the River Sava in Serbia N.R. Miljević, D.D. Golobočanin, M.L. Nadeždić, N. Ogrinc 26. Leakage control methods for metal underground tanks and tanks placed on hardened soil with the use of radioactive tracers J. Kraś, C. Nobis, S. Myczkowski 27. Mechanical and thermal properties of commercial multilayer flexible plastic packaging materials irradiated with electron beam V.M. Oliveira, B.R. Nogueira, A.V. Ortiz, E.A.B. Moura

Information INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY NUKLEONIKA Dorodna 16, 03-195 Warszawa, Poland phone: (+4822) 504-11-32; fax: (+4822) 811-15-32; e-mail: [email protected] Abstracts and full texts are available on-line at http://www.nukleonika.pl 188 THE INCT PATENTS AND PATENT APPLICATIONS IN 2008

THE INCT PATENTS AND PATENT APPLICATIONS IN 2008

PATENTS

1. Sposób otrzymywania nowych materiałów aktywnych biocydowo (Method for obtaining new materials of biocide activity) A. Łukasiewicz, K. Krajewski, L. Waliś, D. Chmielewska, L. Rowińska Polish Patent No. 197165 2. Sposób otrzymywania dwutlenku tytanu oraz tytanianów litu i baru z czterochlorku tytanu (Method for obtaining titanium dioxide and titanates of lithium and barium from titanium tetrachloride) A. Deptuła, W. Łada, T. Olczak, A.G. Chmielewski, S. Casadio, C. Alvani, F. Croce Polish Patent No. 198039 3. Sposób otrzymywania radionuklidów aktynu-225 i aktynu-228 (Method for obtaining 225Ac and 228Ac radionuclides) B. Bartoś, A. Bilewicz, B. Włodzimirska Polish Patent No.198366 4. Sposób modyfikowania pigmentów mineralnych (Method for modification of mineral pigments) A. Łukasiewicz, D. Chmielewska, L. Waliś, J. Michalik Polish Patent No. 198371 5. Sposób otrzymywania termotopliwej wkładki grzejnej (Method for obtaining thermomeltable heater insert) L. Legocka, A. Woźniak, K. Mirkowski, Z. Zimek, A. Nowicki Polish Patent No. 198586 6. Sposób otrzymywania katod Ni/NiO (Method for obtaining Ni/NiO cathodes) W. Łada, A. Deptuła, T. Olczak, A.G. Chmielewski, A. Moreno Polish Patent No. 199551 7. Urządzenie do równomiernego rozdziału strumienia gazu na wlocie do aparatu (A device for uniform distribution of gas stream at the inlet to an apparatus) A.G. Chmielewski, A. Pawelec, B. Tymiński Polish Patent No. 200288 8. Sposób rozdzielenia izotopów siarki 34S i 32S (Method for separation of sulphur isotopes 34S and 32S) A.G. Chmielewski, A. Mikołajczuk, N. Miljević Polish Patent No. 200364 9. Sposób topienia termoplastycznych tworzyw sztucznych i urządzenie do realizacji tego sposobu (Method and a device for melting thermoplastic plastics) A.G. Chmielewski, B. Tymiński, K. Zwoliński Polish Patent No. 200385

PATENT APPLICATIONS

1. Method for the preparation of hydrogel wound dressings D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik Ukraine, application No. 200810581 (with Przedsiębiorstwo Produkcyjno-Handlowe KIK) 2. Method for the preparation of hydrogel wound dressings D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik Russia, application No. 2008134320 (with Przedsiębiorstwo Produkcyjno-Handlowe KIK) 3. Method for the preparation of hydrogel wound dressings D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka. P. Kik Belarus, application No. 20081103 (with Przedsiębiorstwo Produkcyjno-Handlowe KIK) THE INCT PATENTS AND PATENT APPLICATIONS IN 2008 189

4. Method and equipment for simultaneous removal of acidic inorganic pollutants and volatile organic compounds from the stream of flue gas A.G. Chmielewski, J. Licki, A. Pawelec, B. Tymiński, Ahmed Ali Basfar Saudi Arabia, application No. 08290209

5. Sposób przygotowania przemysłowych gazów odlotowych do oczyszczania z SO2 i NOx metodą radiacyjną (Method for the preparation of industrial flue gases to the purification from SO2 and NOx) A. Pawelec, B. Tymiński, P.D. Dymitrova, D.Z. Naydenov, L.T. Radkov P 385911 6. Urządzenie do radiacyjnego oczyszczania przemysłowych gazów odlotowych (A device for preparing industrial flue gases to be purified by radiation technique) A.G. Chmielewski, A. Pawelec, A. Dobrowolski, N.N. Dutskinov, K.L. Nikolov, L.K. Stamatov, Y.G. Pelovski P 386160 (with TPS SVILOZA JSCo, Sofia, Bulgaria) 7. Dozymetr promieniowania gamma (A dosimeter for gamma radiation) Z. Stuglik P 386927 8. Sposób automatycznej regulacji wzmocnienia fotopowielacza, gdy mierzone promieniowanie jonizujące występuje okresowo (Method for automatic control of amplification of a photomultiplier when ionization radiation occurs periodically) B. Machaj, J. Bartak, A. Jakowiuk P 386616 9. Sposób otrzymywania nowych krzemionkowych sorbentów metali i biocydów (Method for obtaining new silica sorbents for metals and biocides) A. Łukasiewicz, D. Chmielewska, L. Waliś P 386617 190 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

1. DZIEŃ INFORMACYJNY 7. PROGRAMU RAMOWEGO EURATOM (INFORMATION DAY ON THE 7TH EURATOM FRAME PROGRAMME, 15 FEBRUARY 2008, WAR- SZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, National Contact Point regarding Euratom • Otwarcie (Opening) A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Prezentacja 7PR i 7PR Euratom (Introduction to the 7th Frame Programme and 7th Euratom Frame Programme) A. Buczkowska-Garbarczyk (National Contact Point regarding Euratom, Warszawa, Poland) • Wyniki pierwszego konkursu w Euratomie (Results of the first competition in Euratom) • Nowości – wsparcie Ministerstwa Nauki i Szkolnictwa Wyższego – „Granty na granty” dla polskich koor- dynatorów projektów (Novelties – support of the Ministry of Scientific Research and Information Tech- nology – “Grants on grants” for the Polish coordinators of projects) • 7. Program Ramowy: zasady uczestnictwa, programy szczegółowe, przygotowanie wniosku (The 7th Frame Programme: principles of participation, detailed programmes, preparation of application) • 7. Program Ramowy Euratom – tematyka otwartego konkursu (The 7th Euratom Frame Programme – topics of open competition) • Przykłady projektów realizowanych w obszarach: radiobiologii, radioekologii, rozdziału i transmutacji (Examples of topics accomplished in the fields: radiobiology, radioecology, separation and transmutation) • Pytania i odpowiedzi (Questions and answers) • Konsultacje (Consultations)

2. SEMINARIUM DLA PRACOWNIKÓW URZĘDU ORAZ RADNYCH DZIELNICY WAR- SZAWA-WŁOCHY (SEMINAR FOR THE STAFF AND ALDERMAN OF THE DISTRICT WARSZAWA-WŁOCHY), 13 MAY 2008, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology

LECTURES • Prezentacja głównych kierunków działalności naukowej Instytutu oraz możliwości wykorzystania technik radiacyjnych w rolnictwie, ochronie środowiska, przemyśle i medycynie (Introduction to the main fields of scientific activities of the Institute and the possibilities of using radiation techniques in agriculture, environmental protection, industry and medicine) W. Migdał (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Promieniowanie jonizujące (Ionizing radiation) U. Gryczka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Akceleratory elektronów (Electron accelerators) S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Napromieniowanie żywności (Food irradiation) W. Migdał (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

3. THE FINAL WORKSHOP IN THE FRAME OF THE MARIE CURIE HOST FELLOW- SHIPS FOR TRANSFER OF KNOWLEDGE: CHEMICAL STUDIES FOR DESIGN AND PRODUCTION OF NEW RADIOPHARMACEUTICALS (POL-RAD-PHARM), 17 MAY 2008, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 191

Organizing Committee: Prof. J. Narbutt, Ph.D., D.Sc., Prof. A. Bilewicz, Ph.D., D.Sc., E. Gniazdowska, Ph.D., L. Fuks, Ph.D.

LECTURES • Chemical studies for design and production of new pharmaceuticals (POL-RAD-PHARM) – the research training project, action Marie Curie Host Fellowships for Transfer of Knowledge, 6th Framework Pro- gramme. Attempt to summarize J. Narbutt (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Towards Tc(III)- or Re(III)-labelled peptides with tunable lipophilicity E. Gniazdowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Koźmiński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) + + • Tc(CO)3 and Re(CO)3 complexes with imidazol-substituted propanoic acid L. Fuks (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Tricarbonyl technetium(I) and rhenium(I) complexes with neutral bidentate ligands M. Łyczko (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Macrocyclic complexes of Sc-47 and Sc-44 as precursors for therapeutic and PET radiopharmaceuticals A. Majkowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • New methods for astatination of biomolecules by metal cation bridge M. Pruszyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Practical training in ICP-MS analytical technique gained at the CNRS Analytical Chemistry Laboratory, Pau, France Z. Samczyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Applications of ICP-MS and other hyphenated techniques to the determination of total Se content and selenium speciation in biological materials E. Chajduk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Production and application of V-48 at the Institute of Nuclear Physics in Cracow B. Petelenz (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland) • Nuclear targeting with intercalators R. Alberto (Institute of Inorganic Chemistry, University of Zürich, Switzerland), K. Zelenka (Institute of Inorganic Chemistry, University of Zürich, Switzerland) • 99mTc-labelled biomolecules using “4+1” complexes J.-U. Künstler (Institute of Radiopharmacy, Forschunszentrum Dresden-Rossendorf, Germany), H.-J. Pietzsch (Institute of Radiopharmacy, Forschunszentrum Dresden-Rossendorf, Germany) • Biophosphonic acid radiopharmaceuticals M. Neves (Nuclear and Technological Institute (ITN), Sacavém, Portugal) • Development of radiopharmaceuticals – my experience K. Kothari (Bhabha Atomic Research Centre, Trombay, Mumbai, India)

ROUND TABLE DISCUSSION – moderator: J. Narbutt (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

4. WORKSHOP ON “SEPARATION PROCESSES AND ANALYTICAL METHODS FOR ENVIRONMENTAL STUDIES AND APPLICATIONS” IN THE FRAME OF THE MARIE CURIE HOST FELLOWSHIPS FOR THE TRANSFER OF KNOWLEDGE PROJECT “ADVANCED METHODS FOR ENVIRONMENT RESEARCH AND CONTROL (AMERAC)”, 6 AUGUST 2008, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Assoc. Prof. G. Zakrzewska-Trznadel, Ph.D., D.Sc., A. Jaworska, M.Sc., M. Buta

OPENING J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 192 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

LECTURES • Reuse of indigo dyeing textile wastewaters using membrane technology N. Uzal (Kocaeli University, Turkey) • Experimental study on particle deposition on a microsieve membrane J. Lin (Institute of Fluid Mechanics of Toulouse, France) • The use of molecular sieves to adsorb some radiopharmaceuticals E. Çiçek (Mehmet Akif Ersoy University, Burdur, Turkey) • An IR study of trimethyl phosphate adsorbed on NaY zeolite E. Çiçek (Mehmet Akif Ersoy University, Burdur, Turkey) • Application of low-cost materials for oil-spill sorption and for removal of heavy metal ions from wastewaters C. Cojocaru (”Gh. Asachi” Technical University, Iaşi, Romania) • Investigation of clogging in PDMS micro-separators J. Lin (Institute of Fluid Mechanics of Toulouse, France) • Analysis of sulphur isotopes in dairy samples – the report from scientific visit to Institute of Agricultural Climate Research, Braunschweig, Germany R. Wierzchnicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

CLOSING REMARKS

5. 8th INTERNATIONAL CONFERENCE ON PULSE INVESTIGATIONS IN CHEMISTRY, BIOLOGY AND PHYSICS PULS’2008, 6-12 SEPTEMBER 2008, KRAKÓW, POLAND Organized by the Institute of Nuclear Chemistry and Technology, Technical University of Łódź Organizing Committee: J.L. Gębicki, Ph.D., D.Sc., Prof. K. Bobrowski, Ph.D., D.Sc., L. Gębicka, Ph.D., D.Sc., P.B. Wiśniowski, Ph.D., M. Szadkowska-Nicze, Ph.D., D.Sc., T. Szreder, Ph.D.

LECTURES Session I Chair: K.-D. Asmus (Adam Mickiewicz University, Poznań, Poland) • Novel carbon nanostructures – time resolved radiolytic and photolytic investigations D.M. Guldi (Friedrich-Alexander University of Erlangen-Nuremberg, Germany) Session II Chair: S. Pimblott (The University of Manchester, United Kingdom) • Chemical dynamics using laser photolysis – laser induced fluorescence S.K. Sarkar (Bhabha Atomic Research Centre, Mumbai, India), P.D. Naik (Bhabha Atomic Research Centre, Mumbai, India) • Novel time-resolved techniques for studying hydrogen-bonded systems J. Waluk (Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa, Poland) Session III Chair: Y.A. Berlin (Northwestern University, Evanston, USA) • Photo-oxidation of methionine and its derivatives studied by time-resolved CINDP O.B. Morozova (International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia), A.V. Yurkovskaya (International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia) • Opportunities in real-time chemistry in solution using picosecond X-ray diffraction J. Davidsson (Uppsala University, Sweden) • Photoreduction and photooxidation of oxoisoaporphines: Laser flash photolysis study in the presence of amines and tetracyanoethylene J. De la Fuente (Universidad de Chile, Santiago, Chile), C. Poblete (Universidad de Chile, Santiago, Chile), Ch. Aliaga (Universidad de Chile, Santiago, Chile), G. Zapata (Universidad de Chile, Santiago, Chile), E. Sobarzo-Sanchez (Universidad de Santiago de Compostela, Chile), C. Jullian (Universidad de Chile, Santiago, Chile), C. Saitz (Universidad de Chile, Santiago, Chile), G. Kciuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Bobrowski (Institute of Nuclear Chemistry and Technology, War- szawa, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 193

Session IV Chair: M. Jonsson (Royal Institute of Technology (KTH), School of Chemical Science and Engineering, Stockholm, Sweden) • Solvation structure and dynamics of water and ionic liquids studied by time-resolved X-ray and optical spectroscopy R.A. Crowell (Brookhaven National Laboratory, Upton, USA), J.F. Wishart (Brookhaven National Labo- ratory, Upton, USA), M. Newton (Brookhaven National Laboratory, Upton, USA), C.G. Elles (Argonne National Laboratory, USA), I.A. Shkrob (Argonne National Laboratory, USA), D. Arms (Argonne National Laboratory, USA), E. Lundahl (DePaul University, Chicago, USA) • Ultrafast studies of electron scavenging in ionic liquids J.F. Wishart (Brookhaven National Laboratory, Upton, USA), A. Cook (Brookhaven National Laboratory, Upton, USA) Session V Chair: V. Feldman (Lomonosov Moscow State University, Russia) – • • Scavenging of eHYD and OH in concentrated HCl and NaCl aqueous solutions. Picosecond pulse radiolysis study E. Atinault (Université Paris-Sud, Orsay, France; Université de Nantes, France), V. de Waele (Université Paris-Sud, Orsay, France), U. Schmidhammer (Université Paris-Sud, Orsay, France), M. Fattahi-Vanani (Université de Nantes, France), M. Mostafavi (Université Paris-Sud, Orsay, France) • Recent developments of the picosecond pulsed electron accelerator and using ultrashort THz pulses to study excition and charge carrier dynamics W. Knulst (Delft University of Technology, The Netherlands), M.J.W. Vermeulen (Delft University of Tech- nology, The Netherlands), J.M. Schins (Delft University of Technology, The Netherlands), L.D.A. Siebbeles (Delft University of Technology, The Netherlands) Session VI Chair: J. Bergès (Université Pierre et Marie Curie, Paris, France) • Solvation dynamics of electron in liquid polyols M. Mostafavi (Université Paris-Sud, Orsay, France), I. Lampre (Université Paris-Sud, Orsay, France), P. Per- not (Université Paris-Sud, Orsay, France) • Bimolecular vs. monomolecular reactions of the radiolytically generated cation radicals in inert matrix S. Naumov (Leibniz Institute of Surface Modification, Leipzig, Germany), W. Knolle (Leibniz Institute of Surface Modification, Leipzig, Germany), I. Janovský (Leibniz Institute of Surface Modification, Leipzig, Germany) • Bifunctional radical cations: fine tuning of charge localization and reactivity through conformational control V. Feldman (Lomonosov Moscow State University, Russia), K. Nuzhdin (Lomonosov Moscow State Uni- versity, Russia), A. Egorov (Lomonosov Moscow State University, Russia), A. Kobzarenko (Lomonosov Moscow State University, Russia) Session VII Chair: J. De la Fuente (Universidad de Chile, Santiago, Chile) • Ultrafast charge carrier multiplication and nature of excited states in PbSe quantum dots M.T. Trinh (Delft University of Technology, The Netherlands), A.J. Houtepan (Delft University of Tech- nology, The Netherlands), J.M. Schins (Delft University of Technology, The Netherlands), J. Piris (Delft University of Technology, The Netherlands), W. Knulst (Delft University of Technology, The Netherlands), L.D.A. Siebbeles (Delft University of Technology, The Netherlands) • Charge dynamics in organic crystals, supermolecules, and dendrimers A. Saeki (Osaka University, Japan), S. Seki (Osaka University, Japan), S. Tagawa (Osaka University, Japan) Session VIII Chair: J. Pączkowski (University of Technology and Life Sciences, Bydgoszcz, Poland) • Chemical bond cleavage studied by laser flash photolysis and pulse radiolysis M. Yamaji (Gunma University, Maebashi City, Japan) • Kinetic and energetic analysis of the free electron transfer A. Baidak (Leibniz Institute of Surface Modification, Leipzig, Germany), S. Naumov (Leibniz Institute of Surface Modification, Leipzig, Germany), O. Brede (University of Leipzig, Germany) Session IX Chair: O. Brede (University of Leipzig, Germany) • Mechanistic studies on the C-C bond cleavage reactions of arylcarbinyloxyl radicals 194 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

M. Bietti (Università degli Studi di Roma “Tor Vergata”, Italy), M. Salamone (Università degli Studi di Roma “Tor Vergata”, Italy) • Reactive fates of halogenated alkoxyl radicals and hydroperoxide in aqueous solutions R. Flyunt (Leibniz Institute of Surface Modification, Leipzig, Germany), O. Makogon (Institute of Physico- -Chemistry, National Academy of Sciences of the Ukraine, L’viv, Ukraine), T. Tobien (LEAP Technologies, Carrboro, USA), S. Naumov (Leibniz Institute of Surface Modification, Leipzig, Germany), K.-D. Asmus (Adam Mickiewicz University, Poznań, Poland) Session X Chair: T. Sarna (Jagiellonian University, Kraków, Poland) • Radiation damage in proteins: theoretical (and experimental) aspects I. Carmichael (University of Notre Dame, USA), E.F. Garman (University of Oxford, United Kingdom) • The catalytic role of thiyl radicals in peptide and protein damage Ch. Schöneich (University of Kansas, Lawrence, USA), O. Mozziconacci (University of Kansas, Lawrence, USA), T. Nauser (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland) Session XI Chair: B. Marciniak (Adam Mickiewicz University, Poznań, Poland) • Free-radical reactions in cyclic dipeptides containing methionine G.L. Hug (University of Notre Dame, USA; Adam Mickiewicz University, Poznań, Poland), K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Marciniak (Adam Mickiewicz University, Poznań, Poland), D. Pogocki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Rzeszów University of Technology, Poland), Ch. Schöneich (University of Kansas, Lawrence, USA), G. Hör- ner (Adam Mickiewicz University, Poznań, Poland) • Novel aggregation pathway of proteins mediated by cysteinyl radicals and its significance for biotechnology O. Mozziconacci (University of Kansas, Lawrence, USA), V. Sharov (University of Kansas, Lawrence, USA), T.D. Williams (University of Kansas, Lawrence, USA), B.A. Kerwin (Amgen Inc., Seattle, USA), Ch. Schöneich (University of Kansas, Lawrence, USA) Session XII Chair: C. Ferreri (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy) • Redox reactions of the 21st amino acid, selenocysteine T. Nauser (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland), D. Steinmann (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland) • Kinetics oxidation of glutathione and ascorbate by amino acid and protein radicals J.M. Gebicki (Macquarie University, Sydney, Australia), A. Domazou (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland), T. Nauser (Swiss Federal Institute of Technology (ETH) Zürich, Switzer- land), W.H. Koppenol (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland) • Limiting factors of intramolecular hydrogen-atom transfer reactions. Steric and kinetic solvent effects G. Hörner (Adam Mickiewicz University, Poznań, Poland), G.L. Hug (University of Notre Dame, USA), B. Marciniak (Adam Mickiewicz University, Poznań, Poland) Session XIII Chair: Ch. Houeé-Levin (Université Paris-Sud, Orsay, France) • One-electron reduction of 8-bromopurine nucleosides and excess electron transfer through DNA Ch. Chatgilialoglu (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy) • Experimental studies of electron transfer within DNA M. Wolszczak (Technical University of Łódź, Poland) Session XIV Chair: J.M. Gebicki (Macquarie University, Sydney, Australia) • Pulse radiolysis studies of the chemistry of probes for “reactive oxygen species” and of the enhancement of radiation-induced cell killing by nitric oxide L.K. Folkes (University of Oxford, United Kingdom), E. Madej (University of Oxford, United Kingdom), K.B. Patel (University of Oxford, United Kingdom), P. Wardman (University of Oxford, United Kingdom), M. Wrona (University of Oxford, United Kingdom) • Pulse radiolysis studies on the free radical chemistry of ubiquinone and ubiquinol in biological contexts R.F. Anderson (University of Auckland, New Zealand), A. Maroz (University of Auckland, New Zealand), S.S. Shinde (University of Auckland, New Zealand), R.A.J. Smith (University of Otago, Dunedin, New Zealand), M.P. Murphy (Medical Research Council, Dunn Human Nutrition Unit, Cambridge, United CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 195

Kingdom), R. Hille (University of California, Riverside, USA), G. Cecchini (University of California, San Francisco, USA) Session XV Chair: R. Bisby (University of Salford, United Kingdom) • Time-resolved studies on drug-biomolecule interactions M.A. Miranda (Universidad Politécnica de Valencia, Spain) • Tetrathiomolybdate – a potent drug and a radical scavenger I. Zilbermann (Nuclear Research Center Negev, Beer-Sheva, Israel; Ben-Gurion University of the Negev, Beer-Sheva, Israel), I. Popivker (Nuclear Research Center Negev, Beer-Sheva, Israel; Ben-Gurion Uni- versity of the Negev, Beer-Sheva, Israel), E. Maimon (Nuclear Research Center Negev, Beer-Sheva, Israel; Ben-Gurion University of the Negev, Beer-Sheva, Israel), H. Cohen (Ben-Gurion University of the Negev, Beer-Sheva, Israel; Ariel University Center of Samaria, Israel), N. Meyerstein (Ben-Gurion University of the Negev, Beer-Sheva, Israel), D. Meyerstein (Ariel University Center of Samaria, Israel; Ben-Gurion University of the Negev, Beer-Sheva, Israel) • Generation of reactive oxygen species by a water soluble Pd-bacteriochlorophyll derivative; EPR, laser flash photolysis and time-resolved singlet oxygen phosphorescence study G. Szewczyk (Jagiellonian University, Kraków, Poland), I. Ashur (Weizmann Institute of Science, Rehovot, Israel), R. Goldschmidt (Weizmann Institute of Science, Rehovot, Israel), I. Pinkas (Weizmann Institute of Science, Rehovot, Israel), Y. Salomon (Weizmann Institute of Science, Rehovot, Israel), T. Sarna (Jagiellon- ian University, Kraków, Poland), A. Scherz (Weizmann Institute of Science, Rehovot, Israel) Session XVI Chair: J. Kroh (Technical University of Łódź, Poland) • Inelastic interactions of electrons with biomolecules: from gas phase to complexes and clusters S. Denifl (Freie Universität Berlin, Germany), S. Ptasinska (Freie Universität Berlin, Germany), P. Sulzer (Freie Universität Berlin, Germany), F. Zappa (Freie Universität Berlin, Germany), F. Ferreira da Silva (Freie Universität Berlin, Germany), M. Probst (Freie Universität Berlin, Germany), A. Mauracher (Freie Universität Berlin, Germany), E. Illenberger (Freie Universität Berlin, Germany), D.K. Bohme (York University, Toronto, Canada), T.D. Märk (Comenius University in Bratislava, Slovakia), P. Scheier (Uni- versity of Innsbruck, Austria)

POSTER PRESENTATIONS • Pulse radiolysis studies on formation of Ag clusters in aqueous solutions of acrylamide A. Balcerzyk (Technical University of Łódź, Poland), M. Szadkowska-Nicze (Technical University of Łódź, Poland) • Electron and proton transfer to the active site of thioredoxin. A QM/MM study J. Bergés (Université Pierre et Marie Curie, Paris, France), G. Rickard (University of Calgary, Canada), A. Rauk (University of Calgary, Canada), Ch. Houée-Levin (Université Paris-Sud, Orsay, France) • Pulse radiolysis and laser flash photolysis studies of antimalarial drugs R.H. Bisby (University of Salford, United Kingdom), F.M.D. Ismail (Liverpool John Moores University, United Kingdom), S. Navaratnam (University of Salford, United Kingdom; Science and Technology Facilities Council, Daresbury Laboratory, Warrington, United Kingdom) • Pulse radiolysis and DFT studies on the radical reaction of nicotine D. Pogocki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Rzeszów University of Technology, Poland), J. Mirkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Ruman (Rzeszów University of Technology, Poland), K. Szpara (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Rzeszów University of Technology, Poland), M. Celuch (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Oxidation of FeII-cytochrome c to FeIII-cytochrome c by nitrogen dioxide A.S. Domazou (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland), W.H. Koppenol (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland) • The role of hydroperoxide as a precursor of radiation induced graft polymerization I. Enomoto (Tokyo Metropolitan Industrial Technology Research Institute, Japan; University of Tokyo, Japan), Y. Katsumura (University of Tokyo, Japan; Japan Atomic Energy Agency, Takasaki, Japan), H. Kudo (University of Tokyo, Japan), S. Soeda (Tokyo Metropolitan Industrial Technology Research Insti- tute, Japan) • How the time resolved techniques can support steady-state results. Based on photochemistry of thioether- -containing aromatic carobxylic acids P. Filipiak (Adam Mickiewicz University, Poznań, Poland), G.L. Hug (University of Notre Dame, USA), K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Marciniak (Adam Mickiewicz University, Poznań, Poland) 196 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

• Formation of cation – radical anion pairs derived from carboxybenzophenone – tetrabutylammonium salts. Pulse radiolysis studies P. Filipiak (Adam Mickiewicz University, Poznań, Poland), M. Pietrzak (University of Technology and Life Science, Bydgoszcz, Poland), J. Paczkowski (University of Technology and Life Sciences, Bydgoszcz, Poland), K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Marciniak (Adam Mickiewicz University, Poznań, Poland) • Reactions of heme proteins with carbonate radical anion L. Gębicka (Technical University of Łódź, Poland), J. Didik (Technical University of Łódź, Poland), J.L. Gębicki (Technical University of Łódź, Poland) • Formations of p-terphenyl excited states in ionic liquids. Pulse radiolysis study J. Grodkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Kocia (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Mirkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • A computer simulation of electron transfer reaction assisted by the excitation energy migration via diffusion mechanism M. Gutman (Technical University of Łódź, Poland), M. Hilczer (Technical University of Łódź, Poland), M. Tachiya (National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan) • Distribution of the rate constant of quenching of individual excited probes M. Hilczer (Technical University of Łódź, Poland), M. Tachiya (National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan) • The influence of the quantity and the location of reaction centers on the effective radius of diffusion-controlled reactionn I.S. Ivanishko (Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia), V.I. Borovkov (Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia; Novosibirsk State University, Russia) • Computer simulation of electron-ion recombination in radiation track in liquid argon M. Jaskolski (Technical University of Łódź, Poland), M. Wójcik (Technical University of Łódź, Poland) • Radiolysis of selected perfluoropolyethers S. Karolczak (Technical University of Łódź, Poland) • • • Oxidation of tyrosine and its peptides mediated by OH and N3 radicals G. Kciuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Mirkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Wiśniowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Formations and reactions of p-terphenyl related intermediates in ionic liquids. Pulse radiolysis study J. Grodkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Kocia (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Mirkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Physicochemical properties of berberine and palmatine upon binding to DNA and HSA M. Marszałek (Technical University of Łódź, Poland), M. Wolszczak (Technical University of Łódź, Poland) • Investigation of oxidative coupling of thiophene and its disubstituted derivatives in low temperature organic matrices by means of pulse radiolysis technique R. Michalski (Technical University of Łódź, Poland), A. Sikora (Technical University of Łódź, Poland), M. Brzeziński (Technical University of Łódź, Poland), J. Admaus (Technical University of Łódź, Poland), A. Marcinek (Technical University of Łódź, Poland) • The ultra-fast pulse radiolysis system applied to high temperature radiolysis Y. Muroya (University of Tokyo, Japan), M. Lin (Japan Atomic Energy Agency, Takasaki, Japan), Z. Han (University of Tokyo, Japan), A. Sakumi (University of Tokyo, Japan), T. Ueda (University of Tokyo, Japan), Y. Katsumura (Japan Atomic Energy Agency, Takasaki, Japan; University of Tokyo, Japan) • Photosensitized ocidation of methionine derivatives. Laser flash photolysis studies T. Pędziński (Adam Mickiewicz University, Poznań, Poland), A. Markiewicz (Adam Mickiewicz University, Poznań, Poland), G.L. Hug (University of Notre Dame, USA), B. Marciniak (Adam Mickiewicz Univer- sity, Poznań, Poland) • Photoinduced electron transfer reactions in the 10-methylacridinium cation – benzyltrimethylsilane system. Steady-state and flash photolysis studies A. Bednarek (Adam Mickiewicz University, Poznań, Poland), T. Pędziński (Adam Mickiewicz University, Poznań, Poland), A. Wójcik (Adam Mickiewicz University, Poznań, Poland), B. Marciniak (Adam Mickie- wicz University, Poznań, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 197

• Hydrogen atom yields in the radiolysis of water M. Huerta Parajon (University of Notre Dame, USA; The University of Manchester, United Kingdom), J.A. LaVerne (University of Notre Dame, USA), S.M. Pimblott (University of Notre Dame, USA; The University of Manchester, United Kingdom) • Characterisation of transient products of one-electron oxidation of apocynin and related compounds Ł. Piotrowski (Technical University of Łódź, Poland), A. Sikora (Technical University of Łódź, Poland), J. Adamus (Technical University of Łódź, Poland), A. Marcinek (Technical University of Łódź, Poland), J. Zielonka (Medical College of Winsconsin, Milwaukee, USA), B. Kalyanaraman (Medical College of Win- sconsin, Milwaukee, USA) • Ionic strength effects on electron transfer in aqueous solution M. Steblecka (Technical University of Łódź, Poland), M. Wolszczak (Technical University of Łódź, Poland), M. Hilczer (Technical University of Łódź, Poland) • Electron paramagnetic resonance (EPR) study of radiation-induced radicals in 1,3,5-trithiane and its derivatives G. Strzelczak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Janeba-Bartosze- wicz (Adam Mickiewicz University, Poznań, Poland), K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Marciniak (Adam Mickiewicz University, Poznań, Poland) • Computation of pH effect on track processes in water at high temperatures D. Światla-Wojcik (Technical University of Łódź, Poland) • Intermediates generated in irradiated ionic liquids. Influence of anion and alkylammonium cation modification on solvated electron spectra T. Szreder (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Technical University of Łódź, Poland), J.F. Wishart (Brookhaven National Laboratory, Upton, USA), J. Grodkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Skrzypczak (Poznań University of Technology, Poland), A.R. Cook (Brookhaven National Laboratory, Upton, USA) • Ascorbyl radicals in homogeneous and microheterogeneous systems M. Szymańska (Technical University of Łódź, Poland), J.L. Gębicki (Technical University of Łódź, Poland) • Nucleation steps of metal aggregates hosted in zeolite colloidal suspensions Z. Tahri (Université Paris-Sud, Orsay, France), F. Luchez (Université des Sciences et Technologies de Lille, France), I. Yordanov (Université de Hute Alsace, Mulhouse, France), O. Poizar (Université des Sciences et Technologies de Lille, France), A. Moissette (Université des Sciences et Technologies de Lille, France), S. Mintova (Université de Hute Alsace, Mulhouse, France), V. de Waele (Université Paris-Sud, Orsay, France) • Geminate charge recombination in monocrystalline polymer solids M. Wójcik (Technical University of Łódź, Poland), M. Tachiya (National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan) • Modelling fast DNA repair by electron transfer between guanosine radical and amino acids: a microsecond time-resolved CIDNP study O. Morozova (International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia), A. Yurkovskaya (International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia) • On the reaction of metal-triphosphate complexes with radicals in aqueous solutions G. Yardeni (Nuclear Research Center Negev, Beer-Sheva, Israel; Ben-Gurion University of the Negev, Beer-Sheva, Israel), I. Zilberamnn (Nuclear Research Center Negev, Beer-Sheva, Israel), E. Maimon (Nuclear Research Center Negev, Beer-Sheva, Israel), H. Cohen (Ben-Gurion University of the Negev, Beer-Sheva, Israel; Ariel University Center of Samaria, Israel), D. Meyerstein (Ben-Gurion University of the Negev, Beer-Sheva, Israel; Ariel University Center of Samaria, Israel) • Effect of water chemistry and noble metal particles on radiation induced dissolution of spent nuclear fuel O. Roth (Royal Institute of Technology (KTH), School of Chemical Science and Engineering, Stockholm, Sweden), M. Trummer (Royal Institute of Technology (KTH), School of Chemical Science and Engineer- ing, Stockholm, Sweden), M. Jonsson (Royal Institute of Technology (KTH), School of Chemical Science and Engineering, Stockholm, Sweden)

6. JOINT WORKING GROUPS MEETING: FREE RADICALS IN CHEMICAL BIOLOGY – COST CHEMISTRY CM0603, 10-11 SEPTEMBER 2008, KRAKÓW, POLAND Organized by the Institute of Nuclear Chemistry and Technology, Technical University of Łódź Organizing Committee: Prof. K. Bobrowski, Ph.D., D.Sc., P. Wiśniowski, Ph.D., Ch. Chatgilialoglu, Ph.D., J.L. Gębicki, Ph.D., D.Sc., J. Caldentey, Ph.D. 198 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

LECTURES • Presentation of the COST Action CM0603 “Free radicals in chemical biology” Ch. Chatgilialoglu (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy) • Redox reactions of the 21st amino acid selenocysteine T. Nauser (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland), D. Steinmann (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland) • Kinetics of oxidation of glutathione and ascorbate by amino acid and protein radicals J.M. Gebicki (Macquarie University, Sidney, Australia), A. Domazou (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland), T. Nauser (Swiss Federal Institute of Technology (ETH) Zürich, Switzer- land), W.H. Koppenol (Swiss Federal Institute of Technology (ETH) Zürich, Switzerland) • Limiting factors of intramolecular hydrogen-atom transfer reactions. Steric and kinetic solvent effects G. Hörner (Adam Mickiewicz University, Poznań, Poland), G.L. Hug (University of Notre Dame, USA), B. Marciniak (Adam Mickiewicz University, Poznań, Poland) • One-electron reduction of 8-bromopurine nucleosides and excess electron transfer through DNA Ch. Chatgilialoglu (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy) • Experimental studies on electron transfer within DNA M. Wolszczak (Technical University of Łódź, Poland) • Do oxygen free radicals exert a retro-control on the production of superoxide ions by NADPH oxidase? A radiolysis study M. Gelinotte (Université Paris-Sud, Orsay, France), T. Bizouarn (Université Paris-Sud, Orsay, France), L. Baciou (Université Paris-Sud, Orsay, France), Ch. Houée-Levin (Université Paris-Sud, Orsay, France) • Theoretical calculations and experimental data on spectral, kinetic and thermodynamic properties of Se∴N and S∴N three-electron-bonded, structurally stabilized σ2σ* radicals in aqueous environment S. Naumov (Leibniz Institute of Surface Modification, Leipzig, Germany), M. Bonifačić (Ruđer Bošković Institute, Zagreb, Croatia), R.S. Glass (The University of Arizona, Tucson, USA), K.-D. Asmus (Adam Mickiewicz University, Poznań, Poland) • Membrane and radiations: formation of trans fatty acids C. Ferreri (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy) • Low energy electron induced chemistry in dry DNA S. Ptasińska (The Open University, Milton Keynes, United Kingdom), L. Sanche (Université de Sher- brooke, Canada), N.J. Mason (The Open University, Milton Keynes, United Kingdom) • Pulse radiolysis studies of the chemistry of probes for “reactive oxygen species” and of the enhancement of radiation-induced cell killing by nitric oxide L.K. Folkes (University of Oxford, United Kingdom), E. Madej (University of Oxford, United Kingdom), K.B. Patel (University of Oxford, United Kingdom), P. Wardman (University of Oxford, United Kingdom), M. Wrona (University of Oxford, United Kingdom) • Pulse radiolysis studies on the free radical chemistry of ubiquinone and ubiquinol in biological contexts R.F. Anderson (University of Auckland, New Zealand), A. Maroz (University of Auckland, New Zealand), S.S. Shinde (University of Auckland, New Zealand), R.A.J. Smith (University of Otago, Dunedin, New Zealand), M.P. Murphy (Medical Research Council, Dunn Human Nutrition Unit, Cambridge, United Kingdom), R. Hille (University of California, Riverside, USA), G. Cecchini (University of California, San Francisco, USA) • Time-resolved studies on drug-biomolecule interactions M.A. Miranda (Universidad Politecnica de Valencia, Spain) • Tetrathiomolybdate – a potent drug and a radical scavenger I. Zilbermann (Nuclear Research Center Negev, Beer-Sheva, Israel; Ben-Gurion University of the Negev, Beer-Sheva, Israel), I. Popivker (Nuclear Research Center Negev, Beer-Sheva, Israel; Ben-Gurion Uni- versity of the Negev, Beer-Sheva, Israel), E. Maimon (Nuclear Research Center Negev, Beer-Sheva, Israel; Ben-Gurion University of the Negev, Beer-Sheva, Israel), H. Cohen (Ben-Gurion University of the Negev, Beer-Sheva, Israel; Ariel University Center of Samaria, Israel), N. Meyerstein (Ben-Gurion University of the Negev, Beer-Sheva, Israel), D. Meyerstein (Ben-Gurion University of the Negev, Beer-Sheva, Israel; Ariel University Center of Samaria, Israel) • Generation of reactive oxygen species by a water soluble Pd-bacteriochlorophyll derivative: EPR, laser flash photolysis and time-resolved singlet oxygen phosphorescence study G. Szewczyk (Jagiellonian University, Kraków, Poland), I. Ashur (Weizmann Institute of Sciences, Rehovot, Israel), R. Goldschmidt (Weizmann Institute of Sciences, Rehovot, Israel), I. Pinkas (Weizmann Institute CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 199

of Sciences, Rehovot, Israel), Y. Salomon (Weizmann Institute of Sciences, Rehovot, Israel), T. Sarna (Jagiellonian University, Kraków, Poland), A. Scherz (Weizmann Institute of Sciences, Rehovot, Israel)

7. INTERNATIONAL CONFERENCE ON RECENT DEVELOPMENTS AND APPLICA- TIONS OF NUCLEAR TECHNOLOGIES, 15-17 SEPTEMBER 2008, BIAŁOWIEŻA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, AGH University of Science and Technology, PGE Polska Grupa Energetyczna S.A., Polish Nuclear Society, International Atomic Energy Agency, National Atomic Energy Agency, Council for Atomic Energy, Polish Nuclear Tech- nology Platform, POLON-ALFA Organizing Committee: Assoc. Prof. G. Zakrzewska-Trznadel, Ph.D., D.Sc., W. Głuszewski, M.Sc., S. Ptaszek, M.Sc., A. Jaworska, M.Sc., A. Jakowiuk, M.Sc., B. Sartowska, Ph.D., Z. Stęgowski, Ph.D., Assoc. Prof. G. Przybytniak, Ph.D., D. Sc., H. Trojanowska, M.Sc.

LECTURES Plenary session I: Nuclear energy for Poland • Nuclear and radiation safety and security J. Niewodniczański (National Atomic Energy Agency, Warszawa, Poland) • It’s high time to accelerate nuclear power development in Poland H. Trojanowska (PGE Polska Grupa Energetyczna S.A., Warszawa, Poland) • Basics in the nuclear power development: important questions in course of the public debate O. Skoniczny (PGE Polska Grupa Energetyczna S.A., Warszawa, Poland) • Development of sustainable nuclear energy in Europe B. Mysłek-Laurikainen (Institute of Atomic Energy, Otwock-Świerk, Poland) Plenary session II: Application of nuclear and ionizing radiation • IAEA activities in support of capacity development and application of radioisotope products and radiation technology M. Haji-Saedi (International Atomic Energy Agency, Vienna, Austria), A. Safrany (International Atomic Energy Agency, Vienna, Austria), M.H. Sampa (International Atomic Energy Agency, Vienna, Austria), Joon-Ha Jin (International Atomic Energy Agency, Vienna, Austria), M.R.A. Pillai (International Atomic Energy Agency, Vienna, Austria), N. Ramamoorthy (International Atomic Energy Agency, Vienna, Austria) • The Pavia’s IUSS Master in nuclear and ionizing radiations technologies A. Faucitano (University of Pavia, Italy) • Role of nuclear and radiation technologies in oil, gas and coal mining, distribution and power sector applications A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Session I: Nuclear energy and waste treatment • Nuclear fuel worldwide reserves A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Which nuclear power technologies may serve Poland the best J. Cetnar (AGH University of Science and Technology, Kraków, Poland), S. Taczanowski (AGH Univer- sity of Science and Technology, Kraków, Poland) • Nitride – 15N nuclear fuels for advanced Nuclear Power Reactors and Accelerator Driven Systems D. Axente (National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj-Napoca, Romania) • Nuclear safety research at the Forschungszentrum Juelich, Germany M. Rossbach (Forschungszentrum Jülich, Germany), M. Florjan (Forschungszentrum Jülich, Germany) • Liquid low and intermediate-level radioactive wastes treatment – the challenge for membrane methods G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Neutron fields produced in heavy spallation targets by 200 MeV electron beams A. Polański (The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland; Joint Institute for Nuclear Research, Dubna, Russia), B. Słowiński (Warsaw University of Technology, Poland; Institute of Atomic Energy, Otwock-Świerk, Poland) Session II: Food irradiation • A study on optimization the sample preparation for gas chromatographic methods used in routine irradiated foodstuffs detection 200 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

M. Virgolici (Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest, Romania), A.V. Medvedovici (University of Bucharest, Romania), M.M. Manea (Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest, Romania), M. Cutrubinis (Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest, Romania), I.V. Moise (Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest, Romania), R.M. Georgescu (Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest, Romania) • Vitamin E content and sensory qualities of γ-irradiated sunflower whole grain cookies M.S. Taipina (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), L.C.A. Lamardo (Instituto Adolfo Lutz, São Paulo, Brazil), M.A.B. Rodas (Instituto Adolfo Lutz, São Paulo, Brazil), N.L. del Mastro (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Evaluation of γ-radiation on volatiles in green tea G.B. Fanaro (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), D.C. Salum (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), T.C.F. Nunes (University of São Paulo, Brazil), E. Purgatto (University of São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Comet assay to verify the quality of irradiated frozen chicken giblets R.C. Duarte (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.M. Araújo (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), G.B. Fanaro (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), V.Y.G.T. Panelli (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) Session III: Nuclear techniques for industry and environment I • Optimization of industrial radiography technique for defect detection of oil and gas pipeline in weld regions by image processing methods A. Karimian (University of Isfahan, Iran), M. Torabian (Azad University, Isfahan, Iran), M. Yazdchi (Uni- versity of Isfahan, Iran) • Corrosion detection improvement of oil and gas pipelines with industrial radiography method by using image processing A. Karimian (University of Isfahan, Iran), M. Yazdani (Azad University, Isfahan, Iran), A. Movafeghi (INRA, Teheran, Iran) • Metrological features of radiometric dust concentration monitors operating with wireless communication system A. Jakowiuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Urbański (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Świstowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Machaj (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J.P. Pieńkos (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Kowalska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Measurement of thin layer thickness deposited on a substrate by HPIXE method P. Brisset (CEA/DRT/LIST/DETECS/SSTM C.E., Saclay, France), D. Chambellan CEA/DRT/LIST/ DETECS/SSTM C.E., Saclay, France), J. de Sanoit CEA/DRT/LIST/DETECS/SSTM C.E., Saclay, France) Session IV: Environment and radiation protection • Distribution of stable isotopes in the Sava River in Serbia N. Miljević (Vinča Institute of Nuclear Sciences, Belgrade, Serbia), D. Golobočanin (Vinča Institute of Nuclear Sciences, Belgrade, Serbia), M. Nadeždić (Republic Hydrometeorological Service of Serbia, Bel- grade, Serbia), N. Ogrinc (Jožef Stefan Institute, Ljubljana, Slovenia) • Preliminary studies on origin of variations in concentration of radium isotopes in ground waters N.D. Chau (AGH University of Science and Technology, Kraków, Poland), M. Kopeć (AGH University of Science and Technology, Kraków, Poland) • Natural radioactive elements and chemical composition of Carpathian mineral waters N.D. Chau (AGH University of Science and Technology, Kraków, Poland), L. Rajchel (AGH University of Science and Technology, Kraków, Poland), E. Chruściel (AGH University of Science and Technology, Kraków, Poland), J. Motyka (AGH University of Science and Technology, Kraków, Poland) • Investigation of particle size-dependent neutron shielding efficiency J. Kim (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), Y.R. Uhm (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), B.C. Lee (Korea Atomic Energy Research Insti- tute, Daejeon, Republic of Korea), M. Lee (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), C.K. Rhee (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 201

• Biological dosimetry: perspectives and limitations S. Sommer (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), I. Buraczewska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Kruszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Wójcik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Stockholm University, Sweden) Session V: Nuclear techniques for industry and environment II • Leakage control methods for metal underground tanks and tanks placed on hardened soil with the use of radioactive tracers J. Kraś (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), C. Nobis (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Myczkowski (Institute of Nuclear Chemistry and Tech- nology, Warszawa, Poland) • Scintillating setup for high accessibility detection of low activity ionizing radiations B. Hautefeuille (AXINT, Lyon, France), P. Anfré (AXINT, Lyon, France), O. Tillement (Laboratoire de Physico-Chimie des Matériaux Luminescents, CNRS, Villeurbanne, France) • Calibration and application of modern track detectors CR-39/PM-355 in nuclear physics and high temperature plasma experiments A. Malinowska (The Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), A. Szydłowski (The Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), M. Jaskóła (The Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), A. Korman (The Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), B. Sartowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Session VI: Radiopharmaceuticals and radioisotope production 211 211 • Synthesis of Rh[16aneS4-diol] At and Ir[16aneS4-diol] At complexes – possibly new precursors for labelling with astatine M. Pruszyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Bilewicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M.R. Zalutsky (Duke University Medical Center, Durham, USA) • Concept of boron neutron capture therapy facility at reactor Maria in Świerk K. Pytel (Institute of Atomic Energy, Otwock-Świerk, Poland), K. Andrzejewski (Institute of Atomic Energy, Otwock-Świerk, Poland), I. Owsianko (Institute of Atomic Energy, Otwock-Świerk, Poland), N. Golnik (Institute of Atomic Energy, Otwock-Świerk, Poland) • Gel metal-oxide composites as filling materials for W-188/Re-188 generator columns E. Iller (Institute of Atomic Energy, Otwock-Świerk, Poland), H. Polkowska-Motrenko (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Deptuła (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), D. Wawszczak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), W. Łada (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Konior (Institute of Atomic Energy, Otwock-Świerk, Poland), J. Milczarek (Institute of Atomic Energy, Otwock-Świerk, Poland), J. Żołądek (Institute of Atomic Energy, Otwock-Świerk, Poland), F. Zaza (Italian National Agency for New Technologies, Energy and the Environment (ENEA), Cassacia Research Center, Italy) • Development and production of radioactive sources for cancer treatment in Brazil M.E.C.M. Rostelato (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Com- mission (CNEN), São Paulo, Brazil), P.R. Rela (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C.A. Zeituni (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A. Feher (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), J.E. Manzoli (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Com- mission (CNEN), São Paulo, Brazil), J.A. Moura (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), E.S. Moura (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C.P.G. Silva (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) Session VII: Industrial application of radiation • Mobile electron accelerator for environmental researches B. Han (EB Tech Co., Ltd., Daejeon, Republic of Korea), S. Kim (EB Tech Co., Ltd., Daejeon, Republic of Korea), W. Kang (EB Tech Co., Ltd., Daejeon, Republic of Korea), M. Lee (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), I. Jung (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), R.A. Salimov (Budker Institute of Nuclear Physics, Novosibirsk, Russia), N.K. Kuksanov (Budker Institute of Nuclear Physics, Novosibirsk, Russia) • Unit processes and unit operations in radiation processing Z.P. Zagórski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), W. Głuszewski (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland) 202 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

• Electron beam flue gas treatment process for purification of exhaust gases with high SO2 concentrations A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Licki (Institute of Atomic Energy, Otwock-Świerk, Poland) • Radiation processing of fluid streams diluted aqueous solutions of sucrose as a dosimetric tool for operational qualification Z. Peimel-Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Evaluation of polymers designed for radiation processing G. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Nowicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Walo (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Mirkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiation modification of the functional properties of the edible films prepared using starch and starch-lipid system K. Cieśla (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Nowicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Buczkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Development of an irradiation system for a small size continuous run multipurpose gamma irradiator W.A.P. Calvo (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), P.R. Rela (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C.M. Napolitano (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), Y. Kodama (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), N.M. Omi (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Com- mission (CNEN), São Paulo, Brazil), F.E. da Costa (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), L.G. de Andrade e Silva (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) Session VIII: Nuclear medicine and therapy • PET-CT imaging in clinical hematology M. Dziuk (Mazovian PET-CT Centre, Warszawa, Poland) • Supported software for SPECT images analysis and myocardial perfusion diagnosis Z. Stęgowski (AGH University of Science and Technology, Kraków, Poland), J. Dudała (AGH University of Science and Technology, Kraków, Poland), K. Matusiak (AGH University of Science and Technology, Kraków, Poland), A. Różańska (AGH University of Science and Technology, Kraków, Poland), A. Stępień (Military Hospital in Kraków, Poland) • Radioisotope somatostatin analogues in diagnosis and treatment tumours with overexpression of somatostatin receptors N. Szaluś (Military Institute of Health Services, Warszawa, Poland), G. Kamiński (Military Institute of Health Services, Warszawa, Poland), K. Obuchowski (Military Institute of Health Services, Warszawa, Poland), Z. Podgajny (Military Institute of Health Services, Warszawa, Poland), E. Dziuk (Military Insti- tute of Health Services, Warszawa, Poland) • Neurodegenerative disorders recognition using X-ray fluorescence microscopy and artificial neural networks methods Z. Stęgowski (AGH University of Science and Technology, Kraków, Poland), J. Chwiej (AGH University of Science and Technology, Kraków, Poland), M. Lankosz (AGH University of Science and Technology, Kraków, Poland), M. Szczerbowska-Boruchowska (AGH University of Science and Technology, Kraków, Poland), D. Adamek (Jagiellonian University, Kraków, Poland) • New challenges on tumor nuclear imaging targeting integrin αvβ3 M. Bilski (Military Institute of Hygiene and Epidemiology, Warszawa, Poland), I.P. Grudziński (Military Institute of Hygiene and Epidemiology, Warszawa, Poland), U. Karczmarczyk (National Medicines Insti- tute, Warszawa, Poland), M. Maurin (National Medicines Institute, Warszawa, Poland), R. Zdanowski (Military Institute of Hygiene and Epidemiology, Warszawa, Poland), J. Pietrzykowski (Institute of Atomic Energy, Otwock-Świerk, Poland), R. Mikołajczak (Institute of Atomic Energy, Otwock-Świerk, Poland), E. Dziuk (Military Institute of Health Services, Warszawa, Poland), M.P. Dąbrowski (Military Institute of Hygiene and Epidemiology, Warszawa, Poland), M.K. Janiak (Military Institute of Hygiene and Epide- miology, Warszawa, Poland) • Electronics X-ray sources for brachytherapy M. Słapa (The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), M. Traczyk (The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), M. Talejko (The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland) • Mechanical properties of human bone-tendon-bone grafts and human pins and screws grafts preserved by different methods and radiation-sterilised used for ligamet reconstruction CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 203

A. Kamiński (Medical University of Warsaw, Poland; National Centre of Tissue and Cell Banking, War- szawa, Poland), G. Gut (Medical University of Warsaw, Poland; National Centre of Tissue and Cell Bank- ing, Warszawa, Poland), I. Uhrynowska-Tyszkiewicz (Medical University of Warsaw, Poland; National Centre of Tissue and Cell Banking, Warszawa, Poland) Poster session: Environment and radiation protection • Temporal variability of radon-222 in near-ground atmosphere P. Wach (AGH University of Science and Technology, Kraków, Poland), M. Zimnoch (AGH University of Science and Technology, Kraków, Poland), K. Różański (AGH University of Science and Technology, Kraków, Poland), K. Kozak (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland) • Study of the elemental concentration of air particulate matter by EDXRF method collected in Poland L. Samek (AGH University of Science and Technology, Kraków, Poland), M. Lankosz (AGH University of Science and Technology, Kraków, Poland) • Measurement of radon concentration in the air by PicoRad detectors N.D. Chau (AGH University of Science and Technology, Kraków, Poland) • Quality control for irradiated culture media used in a microbiological laboratory L. Trandafir (Horia Hulubei Institute of Physics and Nuclear Engineering, Bucharest, Romania), M. Con- stantin (Horia Hulubei Institute of Physics and Nuclear Engineering, Bucharest, Romania), M. Alexandru (Horia Hulubei Institute of Physics and Nuclear Engineering, Bucharest, Romania), M. Ene (Horia Hu- lubei Institute of Physics and Nuclear Engineering, Bucharest, Romania) • Simultaneous measurement of 222Rn and 220Rn in air B. Machaj (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Urbański (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Bartak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Uranium activity in coal and coal mining wastes in the Lublin Coal Basin L. Gazda (Lublin University of Technology, Poland), B. Polednik (Lublin University of Technology, Poland), J. Zawiślak (Lublin University of Technology, Poland) • The Gamma-Ray Spectrometry Laboratory for high-precision measurements of gamma radionuclide concentrations in environmental samples P. Jodłowski (AGH University of Science and Technology, Kraków, Poland), S.J. Kalita (AGH University of Science and Technology, Kraków, Poland) • Measurement of radionuclides in soil, vegetation and water samples from Kohistan (Pakistan) using gamma spectrometry M. Ismail (University of Peshawar, Pakistan), H.M. Khan (University of Peshawar, Pakistan), P. Akhter (Pakistan Institute of Nuclear Science and Technology, Islamabad, Pakistan), K. Khan (Pakistan Institute of Nuclear Science and Technology, Islamabad, Pakistan)

• Sample collection and preparation for CO2 isotopic analysis in industrial off-gases R. Wierzchnicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Plewka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Sedimentation rates and dating of bottom sediments in the southern Baltic Sea region M. Suplińska (Central Laboratory for Radiological Protection, Warszawa, Poland), Z. Pietrzak-Flis (Central Laboratory for Radiological Protection, Warszawa, Poland) • 137Cs distribution in soil and plants in the Opole vicinity, 20 years after Chernobyl power plant accident S. Wołkowicz (Polish Geological Institute, Warszawa, Poland), M. Matul (The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), B. Mysłek-Laurikanen (Institute of Atomic Energy, Otwock- -Świerk, Poland) • The use of 137Cs for dating and sedimentation rate determination of Wilanów Lake deposit mud S. Wołkowicz (Polish Geological Institute, Warszawa, Poland), H. Tomassi-Morawiec (Polish Geological Institute, Warszawa, Poland), B. Mysłek-Laurikanen (Institute of Atomic Energy, Otwock-Świerk, Poland) Poster session: Food irradiation • Evaluation of gamma rays effect on aflatoxins degradation in laboratorial agar residues V.D. Rogovschi (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), S. Aquino (Instituto Adolfo Lutz, São Paulo, Brazil), T.C.F. Nunes (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), P. Zorzete (University of São Paulo, Brazil), E. Gonçalez (Instituto Biológico, São Paulo, Brazil), B. Corrêa (University of São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Insti- tute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) 204 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

• Effects of radiation processing in Turkey meat ready to eat R.G. Debiazzi (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), E.O. Telles (University of São Paulo, Brazil), S.C. Balian (University of São Paulo, Brazil), R.C. Duarte (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Insti- tute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Radiation effects on broccoli, cabbage and cauliflower (Brassica spp) minimally processed T.C.F. Nunes (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), V.D. Rogovschi (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), G.B. Fanaro (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), S.M. Alencar (Uni- versity of São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Comparison between e-beams and 60Co treatment in soybean G.B. Fanaro (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), R.C. Duarte (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), V.D. Rogovschi (Nuclear and Energetic Re- search Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C. Furgeri (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Sensorial analysis of “chimarrão” beverage processed by ionizing radiation C. Furgeri (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), P.V. Silva (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.M. Araújo (Nuclear and Energetic Research Insti- tute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), D.H.M. Bastos (Univer- sity of São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Institute (IPEN), Nu- clear Energy National Commission (CNEN), São Paulo, Brazil) • Sensorial analysis of pistachio radiated by electron beams P.V. Silva (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C. Furgeri (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), R.G. Debiazzi (Nuclear and Energetic Research Insti- tute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), V.Y.G.T. Panelli (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A.L.C.H. Villavicencio (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Detection of radiation treatment in dry plant extracts by thermoluminescence and pulsed photostimulated luminescence. Comparative study K. Lehner (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Malec-Czechowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Guzik (Institute of Nuclear Chem- istry and Technology, Warszawa, Poland), W. Stachowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Recent studies of irradiated mangoes in Brazil: a trend to commercial approach S.F. Sabato (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), J.M. Silva (Nuclear and Energetic Research Institute (IPEN), Centro Re- gional de Ciências Nucleares do Nordeste, Recife, Brazil), J.N. Cruz (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), P.O. Broisler (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), P.R. Rela (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), S. Salmieri (INRS – Institut Armand-Frappier, Canadian Irradiation Center, Laval, Canada), M. Lacroix (INRS – Institut Armand-Frappier, Canadian Irradiation Center, Laval, Canada) • Effect of electron radiation on sugar content of inverted liquid sugar P. Podadera (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), S.F. Sabato (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Study of some physicochemical and rheological properties of irradiated honey A. Bera (University of São Paulo, Brazil), L.B. Almeida-Muradian (University of São Paulo, Brazil), S.F. Sabato (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) Poster session: Nuclear medicine and therapy • Sentinel lymph node biopsy in breast cancer (dual method) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 205

A. Giżewska (Military Institute of Health Services, Warszawa, Poland), Z. Stembrowicz-Nowakowska (Military Institute of Health Services, Warszawa, Poland), Z. Zaremba (Military Institute of Health Services, Warszawa, Poland), E. Dziuk (Military Institute of Health Services, Warszawa, Poland) • Application of image analysis system to study radiosensitivity of prostate cancer patients lymphocytes to the induction of chromosome aberrations A. Cebulska-Wasilewska (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland; Jagiellonian University, Kraków, Poland), M. Wikłacz (The Henryk Niewod- niczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland), Z. Rudek (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland), J. Miszczyk (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland), M. Krzysiek (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland) • Application of SCGE (comet) assay to studies on response to the challenging dose of X-rays in lymphocytes of prostate cancer patients and benign prostate hyperplasia A. Cebulska-Wasilewska (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland; Jagiellonian University, Kraków, Poland), M. Krzysiek (The Henryk Niewod- niczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland), A. Panek (The Hen- ryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland), W. Lipczyński (Jagiellonian University, Kraków, Poland), M. Dobrowolska (Jagiellonian University, Kraków, Poland), Z. Dobrowolski (Jagiellonian University, Kraków, Poland) • New scintigraphic technique of bone imaging by using hybrid camera combining SPECT and spiral CT Z. Stembrowicz-Nowakowska (Military Institute of Health Services, Warszawa, Poland), A. Giżewska (Military Institute of Health Services, Warszawa, Poland), E. Dziuk (Military Institute of Health Services, Warszawa, Poland) • Principles of safety use of radioiodine in the treatment of well differentiated thyroid carcinoma (DTC) A. Kowalczyk (Military Institute of Health Services, Warszawa, Poland), Z. Podgajny (Military Institute of Health Services, Warszawa, Poland), G. Kamiński (Military Institute of Health Services, Warszawa, Poland) • Separation of 48V from the titanium target and preparation of the V(VI)-EDTMP complex B. Petelenz (The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland) Poster session: Radiopharmaceuticals and radioisotope production • Quality control of organic impurities in substrate for synthesis of 99mTc-mebrofenine radiotracer R. Lipka (Institute of Atomic Energy, Otwock-Świerk, Poland), J. Pijarowska (Institute of Atomic Energy, Otwock-Świerk, Poland), A. Jaroń (Institute of Atomic Energy, Otwock-Świerk, Poland), K. Bielak (Insti- tute of Atomic Energy, Otwock-Świerk, Poland) • Separation of Mo-99 from uranium solution using α-benzoinooxime precipitation W. Wojdowska (Institute of Atomic Energy, Otwock-Świerk, Poland), J. Parus (Institute of Atomic Energy, Otwock-Świerk, Poland), D. Pawlak (Institute of Atomic Energy, Otwock-Świerk, Poland) • The development of method for preparation of human albumin microspheres as potential radionuclide carriers for diagnostic and therapeutic use A. Jaroń (Institute of Atomic Energy, Otwock-Świerk, Poland), J. Pijarowska (Institute of Atomic Energy, Otwock-Świerk, Poland), E. Byszewska (Institute of Atomic Energy, Otwock-Świerk, Poland), E. Iller (Institute of Atomic Energy, Otwock-Świerk, Poland), E. Jakubowska (Institute of Atomic Energy, Otwock-Świerk, Poland) • The use of zeolites to adsorb Tc-99m pertechnetate, Tc-99m methylene diphosphonate and Tc-99m dimer- captosuccinic acid E. Çiçek (Mehmet Akif Ersoy University, Burdur, Turkey), B. Bardakçi (Mehmet Akif Ersoy University, Burdur, Turkey), A. Jaworska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Usefulness of somatostatin receptor scintigraphy with 99mTc-HYNIC-TATE in visualization of medullary thyroid carcinoma Z. Podgajny (Military Institute of Health Services, Warszawa, Poland), N. Szaluś (Military Institute of Health Services, Warszawa, Poland), G. Kamiński (Military Institute of Health Services, Warszawa, Poland), A. Kowalczyk (Military Institute of Health Services, Warszawa, Poland) • Somatostatin receptor scintigraphy with 99mTc-HYNIC-TATE in visualization of non-radioiodine-avid differentiated thyroid carcinoma Z. Podgajny (Military Institute of Health Services, Warszawa, Poland), N. Szaluś (Military Institute of Health Services, Warszawa, Poland), G. Kamiński (Military Institute of Health Services, Warszawa, Poland), A. Kowalczyk (Military Institute of Health Services, Warszawa, Poland), A. Giżewska (Military Institute of Health Services, Warszawa, Poland), 206 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

• Thermoluminescent and simulation dosimetry of the 125I brachytherapy seed C.A. Zeituni (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil; Universidade Presbiteriana Mackenzie, São Paulo, Brazil), J.E. Manzoli (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil; Universidade São Judas Tadeu, São Paulo, Brazil), E.S. Moura (Nuclear and Energetic Re- search Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil; Faculdades Oswaldo Cruz, São Paulo, Brazil), L.A.A. Terremoto (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.E.C.M. Rostelato (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), J.A. Moura (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A. Feher (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Application of recombination chambers filled with nitrogen for microdosimetry and dosimetry of epithermal neutron beams P. Tulik (Institute of Atomic Energy, Otwock-Świerk, Poland), N. Golnik (Institute of Atomic Energy, Otwock-Świerk, Poland) • Immunological properties of 60Co gamma rays irradiated bothropstoxin-I J.A. Baptista (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), D.P. Vieira (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil; Institute of Tropical Medicine, São Paulo, Brazil), A.J. Galisteo Júnior (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Com- mission (CNEN), São Paulo, Brazil; Institute of Tropical Medicine, São Paulo, Brazil), P. Caproni (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M. Casare (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Com- mission (CNEN), São Paulo, Brazil), H.F. de Andrade Júnior (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil; Institute of Tropical Medicine, São Paulo, Brazil), P.J. Spencer (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), N. Nascimento (Nuclear and Energetic Research In- stitute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) Poster session: Analytical nuclear methods • The study on stable radicals produced by radiation in dried fruits and sugars by electron paramagnetic resonance spectrometry (EPR) G.P. Guzik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), W. Stachowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • The preparation of 57Co radioactive cores of sources applied in Mössbauer spectroscopy I. Cieszykowska (Institute of Atomic Energy, Otwock-Świerk, Poland), M. Żółtowska (Institute of Atomic Energy, Otwock-Świerk, Poland), M. Mielcarski (Institute of Atomic Energy, Otwock-Świerk, Poland) • RNAA definitive methods for selenium and arsenic determination in biological materials and their importance in inorganic trace analysis E. Chajduk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), H. Polkowska-Motrenko (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Dybczyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • INAA in the studies of the lead-tin-yellow pigment in the mediaeval Polish painting of the Pomerania School J. Olszewska-Świetlik (Nicolaus Copernicus University, Toruń, Poland), E. Pańczyk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), L. Waliś (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • The role of physical techniques in cultural heritage studies L. Waliś (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Pańczyk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Kunicki-Goldfinger (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Kierzek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), D. Chmielewska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Different approaches to the determination of lanthanides in plant materials. Nuclear and non nuclear analytical techniques B. Danko (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Dybczyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Kulisa (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Samczyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Poster session: Dosimetry in radiation applications • Dosimetric properties of two different types of commercial window glasses gamma- and electron-irradiated CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 207

P.G. Fuochi (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy), U. Corda (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy), M. Lavalle (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy), A. Kovàcs (Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary), M. Baranyai (Institute of Isotopes, Hungarian Academy of Sciences, Budapest, Hungary), A. Mejri (Centre National des Sciences et Technologies Nucléaires (CNSTN), Tunis, Tunisia), K. Farah (Centre National des Sciences et Technologies Nucléaires (CNSTN), Tunis, Tunisia) • Determination of initial recombination of ions created in quasi-pulsed radiation fields M. Zielczyński (Institute of Atomic Energy, Otwock-Świerk, Poland), N. Golnik (Institute of Atomic Energy, Otwock-Świerk, Poland), M.A. Gryziński (Institute of Atomic Energy, Otwock-Świerk, Poland) • Dosimetric properties of two PCV films produced for pharmaceutical purposes Z. Peimel-Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Fabisiak (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland) • Experimental benchmarking of software ModeStEB for simulation EB processing I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), V.T. Lazurik (Kharkiv National University, Ukraine), V.M. Lazurik (Kharkiv National University, Ukraine), G. Popov (Kharkiv National University, Ukraine), Yu. Rogov (Kharkiv National University, Ukraine), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Dose field formation in heterogeneous target irradiated with X-ray beam. Comparison of Monte Carlo simulation results with film dosimetry S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), V.T. Lazurik (Kharkiv National University, Ukraine), V.M. Lazurik (Kharkiv National University, Ukraine), G. Popov (Kharkiv National University, Ukraine), Yu. Rogov (Kharkiv National University, Ukraine), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Development of crystals based on cesium iodide for measurements of gamma radiation and alpha particles M. da Conceição Costa Pereira (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), T.M. Filho (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.M. Hamada (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Investigation of solid state sugar as a potential dosimetric material – physical and chemical characterization S. Fabisiak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Virgolici (Horia Hu- lubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania), M.M. Manea (Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania), C.D. Negut (Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania), M. Cutrubinis (Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania), R.M. Georgescu (Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania) Poster session: Nuclear techniques for industry and environment • Application of radiotracer and CFD methods for investigation of internal flow structure in wastewater treatment plant apparatus J. Palige (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Ptaszek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Dobrowolski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Changes in time of neutron emission of isotope neutron sources 241Am-Be, 239Pu-Be and 252Cf E.T. Józefowicz (Institute of Atomic Energy, Otwock-Świerk, Poland), K. Józefowicz (Institute of Atomic Energy, Otwock-Świerk, Poland) • Using tracer methods for examination of the flow structure and hydrodynamic conditions in the membrane module A. Miśkiewicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Dobrowolski (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Simple radiation gauges for routine laboratory measurements P. Urbański (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Machaj (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Jakowiuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Świstowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Bartak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J.P. Pieńkos (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Kowalska (Institute of Nuclear Chem- istry and Technology, Warszawa, Poland), L. Fuks (Institute of Nuclear Chemistry and Technology, War- szawa, Poland) 208 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

• Factors affecting the precision of measurements with the usage of proportional chamber M. Bochenek (AGH University of Science and Technology, Kraków, Poland), S. Koperny (AGH Univer- sity of Science and Technology, Kraków, Poland), T.Z. Kowalski (AGH University of Science and Tech- nology, Kraków, Poland) • Modern micropatern gas detectors M. Bochenek (AGH University of Science and Technology, Kraków, Poland), S. Koperny (AGH Univer- sity of Science and Technology, Kraków, Poland), T.Z. Kowalski (AGH University of Science and Tech- nology, Kraków, Poland) • Mechanical control design of a gamma ray computed tomography for multiphase flow systems analyses in gas absorption column W.A.P. Calvo (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.M. Hamada (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), F.E. Sprenger (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), P.A.S. Vasquez (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission CNEN, São Paulo, Brazil), P.R. Rela (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), J.F.T. Martins (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), J.C.S.M. Pereira (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C.H. de Mesquita (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Water migration in beds of natural zeolite J. Żołądek (Institute of Atomic Energy, Otwock-Świerk, Poland), J.J. Milczarek (Institute of Atomic Energy, Otwock-Świerk, Poland), I. Fijał-Kirejczyk (Institute of Atomic Energy, Otwock-Świerk, Poland) • Dynamical neutron radiography studies of drying of kaolin clay cylinders I. Fijał-Kirejczyk (Institute of Atomic Energy, Otwock-Świerk, Poland), J.J. Milczarek (Institute of Atomic Energy, Otwock-Świerk, Poland), J. Banaszak (Poznań University of Technology, Poland) • Radiometric method for clarification and densification efficiency estimation of aggregated suspensions B. Polednik (Lublin University of Technology, Poland), L. Gazda (Lublin University of Technology, Poland), J. Zawiślak (Lublin University of Technology, Poland) Poster seassion: Industrial application of radiation • Radiation curing of silica and silica-rubber composites D. Dondi (University of Pavia, Italy), A. Buttafava (University of Pavia, Italy), A. Faucitano (University of Pavia, Italy) • Radiation processing of detergents and possible environmental benefits S.I. Borrely (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), N. Hamada (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.F. Romanelli (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.C. Pereira (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), G.P. da Silva (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Com- mission (CNEN), São Paulo, Brazil), L.C.A. Mesquita (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.C.F. de Moraes (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Remediation of pesticide contaminated soil by ionizing radiation J.S. Santos (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), H. Oikawa (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), M.N. Mori (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), W.A.P. Calvo (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C.L. Duarte (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Toxicity study on radiation treated non-biodegradable chemicals M.J. Lee (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), S.H. You (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), T.H. Kim (Korea Atomic Energy Research Insti- tute, Daejeon, Republic of Korea), S.D. Kim (Kwangju Institute of Science and Technology, Daejeon, Republic of Korea) • Properties of epoxy-PES systems as polymer matrices for carbon fibre composites produced by e-beam curing S. Alessi (University of Palermo, Italy), D.Gh. Conduruta (University of Palermo, Italy), G. Pitarresi (Uni- versity of Palermo, Italy), M. Lavalle (Institute for the Organic Synthesis and Photoreactivity (ISOF), CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 209

National Research Council, Bologna, Italy), P.G. Fuochi (Institute for the Organic Synthesis and Photo- reactivity (ISOF), National Research Council, Bologna, Italy), U. Corda (Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy), C. Dispenza (University of Palermo, Italy), G. Spadaro (University of Palermo, Italy) • Mechanical and thermal properties of commercial multilayer flexible plastics packaging materials irradiated with electron beam E.A.B. Moura (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A.V. Ortiz (Unipac Embalagens Ltda, São Paulo, Brazil), V.M. Oliveira (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Influence of 10 MeV electron beam radiation on rheological properties of polypropylene M. Buczkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Przybytniak (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Mirkowski (Institute of Nuclear Chem- istry and Technology, Warszawa, Poland), W. Rumiński (“Microspun Products” Sp. z o.o., Warszawa, Poland) • Functionalization of montmorillonite fillers with unsaturated compounds using electron beam irradiation A. Nowicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Mirkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Electron beam irradiation effects on morphologic properties of the PET/PP/PE/EVA polymeric blend E.L. Rossini (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), L.G. de Andrade e Silva (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil) • Study on biological activity of chitosan after radiation processing U. Gryczka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), H. Gawrońska (Warsaw University of Life Sciences (SGGW), Poland), W. Migdał (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S.W. Gawroński (Warsaw University of Life Sciences (SGGW), Poland), A.G. Chmie- lewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Electron beam processing of materials for industrial utilization – developments in India K.S.S. Sarma (Bhabha Atomic Research Centre, Mumbai, India; Board of Radiation and Isotope Tech- nology, Navi Mumbai, India), S. Sabharwal (Bhabha Atomic Research Centre, Mumbai, India) • Modification of elastomers by ionizing radiation Z.P. Zagórski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), W. Głuszewski (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Rajkiewicz (Rubber Research Institute “STOMIL”, Piastów, Poland), A. Mikołajska (Rubber Research Institute “STOMIL”, Piastów, Poland) • Aromatic protection effects in polypropylene radiolysis W. Głuszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z.P. Zagórski (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland) • Improved image reconstruction of a gamma-ray CT based on the EM algorithm N.Y. Lee (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), S.H. Jung (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), J.B. Kim (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea), T.Y. Kwon (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea) • Nanosilver embedded hydrogels with enhanced antibacterial activity D. Chmielewska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), U. Gryczka (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland), W. Migdał (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), T. Płociński (Warsaw University of Technology, Poland), W. Starosta (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Changes of stainless steels surface morphology as a result of interaction with intense pulsed plasma beams containing ions of rare earth elements B. Sartowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Piekoszewski (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland; The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), L. Waliś (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Składnik-Sadowska (The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland), M. Barlak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; The Andrzej Sołtan Insti- tute for Nuclear Studies, Otwock-Świerk, Poland) • Radiation-modified chitosan for removal of metals from water solutions A. Miśkiewicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Jaworska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Zakrzewska-Trznadel (Institute of Nuclear 210 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

Chemistry and Technology, Warszawa, Poland), U. Gryczka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), W. Migdał (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Environmentally friendly method to prepare microcrystalline cellulose H. Stupińska (Institute of Biopolymers and Chemical Fibres, Łódź, Poland), E. Iller (Institute of Atomic Energy, Otwock-Świerk, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), D. Wawro (Institute of Biopolymers and Chemical Fibres, Łódź, Poland), D. Ciechańska (Insti- tute of Biopolymers and Chemical Fibres, Łódź, Poland), E. Kopania (Institute of Biopolymers and Chemical Fibres, Łódź, Poland), J. Palenik (Institute of Biopolymers and Chemical Fibres, Łódź, Poland), S. Milczarek (Institute of Biopolymers and Chemical Fibres, Łódź, Poland), W. Stępniewski (Institute of Biopolymers and Chemical Fibres, Łódź, Poland), G. Krzyżanowska (Institute of Biopolymers and Chem- ical Fibres, Łódź, Poland) • Economics of industrial-scale electron beam wastewater treatment plant B. Han (EB Tech Co., Daejeon, Republic of Korea), J.K. Kim (EB Tech Co., Daejeon, Republic of Korea), Y. Kim (EB Tech Co., Daejeon, Korea), J.S. Choi (Korea Dyeing Technology Center, Republic of Korea), M.J. Lee (Korea Atomic Energy Research Institute, Daejeon, Republic of Korea) • Investigation of irradiated biodegradable blends by FTIR and WAXD Y. Kodama (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), L.D.B. Machado (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), C. Giovedi (Centro Tecnológico da Marinha em São Paulo, Brazil), N.B. de Lima (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), A.T. de Lacerda (Nuclear and Energetic Research Institute (IPEN), Nuclear Energy National Commission (CNEN), São Paulo, Brazil), K. Nakayama (National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan) • Risk management applied to irradiation of medical devices Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Bułka (Institute of Nuclear Chemistry and Tech- nology, Warszawa, Poland) • Archives decontamination by gamma irradiation E. Bratu (Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania), I.V. Moise (Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania) • Radiation modification PLA packaging materials K. Melski (Poznań University of Economics, Poland), H. Kubera (Poznań University of Economics, Poland), W. Głuszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Experiences in using natural gamma radiation for measurement of ash content in coal T. Sikora (Research and Development Centre for Electrical Engineering and Automation in Mining EMAG, Katowice, Poland), J. Dziubiński (Research and Development Centre for Electrical Engineering and Automation in Mining EMAG, Katowice, Poland) Poster session: Nuclear energy and radioactive waste • Partitioning of minor actinides from nuclear waste – contribution of INCT to the European FP7 collaborative project ACSEPT J. Krejzler (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Zielińska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Narbutt (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Proposed for Polish power system nuclear reactors and settlement the NPP J. Adamski (Warsaw University of Technology, Poland), N. Uzunow (Warsaw University of Technology, Poland) • Evaluation of circuit activation and radiotoxicity in the LBE-cooled XADS using Monte Carlo method MCB J. Cetnar (AGH University of Science and Technology, Kraków, Poland), G. Domańska (AGH University of Science and Technology, Kraków, Poland) Marie Curie Transfer of Knowledge: Advanced Methods for Environment Research and Control (AMERAC) • The study of isotopic fractionation in the process of analysis of isotopic ratios 15N/14N and 18O/16O in nitrate from water G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Cuna (National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj-Napoca, Romania), R. Wierzchnicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Der- da (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 211

• Mathematical modeling and optimization of cross-flow ultrafiltration process C. Cojocaru (“Gh. Asachi” Technical University, Iaşi, Romania), G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Dobrowolski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Removal of radionuclides from water solution with polyethersulfone (PES), polysulfone (PS) and surface- -modified membranes M. Khayet (University Complutense of Madrid, Spain), M. Harasimowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Jaworska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Response surface methodology for modelling removal of copper from aqueous systems via micellar enhanced ultrafiltration I. Xiarchos (visiting researcher to the INCT, Greece), A. Jaworska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Nitrogen and oxygen isotope technique for fresh water analyses N. Miljević (Vinča Institute of Nuclear Sciences, Belgrade, Serbia), A. Mikołajczuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Derda (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Preparation and characterization of PVDF membranes for environmental applications M. Harasimowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Khayet (Uni- versity Complutense of Madrid, Spain), G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Marie Curie Transfer of Knowledge AMERAC – importance of different analytical techniques in environmental research and monitoring E. Chajduk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Electrochemical mineralization of water-soluble organic compounds using boron-doped diamond anode connected with membrane process S. Velizarov (Universidade Nova de Lisboa, Caparica, Portugal), A. Miśkiewicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Crespo (Universidade Nova de Lisboa, Caparica, Portugal) • Response surface methodology for the modeling of cobalt ions adsorption on Isparta pumice E. Çiçek (Mehmet Akif Ersoy University, Budur, Turkey), C. Cojocaru (“Gh. Ashi” Technical University, Iaşi, Romania), A. Jaworska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Za- krzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • The characterization and modeling of cobalt ions adsorption on zeolite 4A E. Çiçek (Mehmet Akif Ersoy University, Budur, Turkey), C. Cojocaru (“Gh. Ashi” Technical University, Iaşi, Romania), G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Harasimowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), • Sulfur isotopic composition of milk and dairy products R. Wierzchnicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Derda (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

8. THIRD RESEARCH COORDINATION MEETING ON ELECTRON BEAM TREATMENT OF ORGANIC POLLUTANTS CONTAINED IN GASEOUS STREAMS, 15-19 SEPTEM- BER 2008, BIAŁOWIEŻA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency Organizing Committee: A. Ostapczyk, Ph.D., M.H. Sampa, Ph.D.

LECTURES • Kinetics and mechanism of naphthalene decomposition in flue gas under electron beam influence H. Nichipor (Joint Institute for Power and Nuclear Research – “Sosny”, National Academy of Sciences of Belarus, Minsk, Belarus), S. Yacko (Joint Institute for Power and Nuclear Research – “Sosny”, National Academy of Sciences of Belarus, Minsk, Belarus), A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • EB technology for combustion flue gases cleaning M. Stefanova (Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria), S.P. Marinov (Institute of Organic Chemistry with Centre of Phytochemistry, 212 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

Bulgarian Academy of Sciences, Sofia, Bulgaria), M.S. Callen (Instituto de Carboquimica, Spanish National Research Council (CSIC), Zaragoza, Spain), A.M. Mastral (Instituto de Carboquimica, Spanish National Research Council (CSIC), Zaragoza, Spain) • Development of removal technology for volatile organic compounds (VOCS) using electron beams T. Hakoda (Japan Atomic Energy Agency, Takasaki, Japan), A. Shimada (Japan Atomic Energy Agency, Takasaki, Japan), K. Hirota (Japan Atomic Energy Agency, Takasaki, Japan) • VOC removal characteristics for e-beam-catalyst coupling with respect to catalysts and humidity Yeong-Sik Son (Konkuk University, Seoul, Republic of Korea), J. Kim (Konkuk University, Seoul, Republic of Korea), K. Kim (National Institute of Environmental Research, Incheon, Republic of Korea), Young-Suk Son (Konkuk University, Seoul, Republic of Korea) • Treatment of odorous compound (dimethyl sulfide and trimethylamine) using electron beam irradiation technique M.N. Othman (Malaysian Nuclear Agency, Kajang, Malaysia), M.N.M. Yunus (Malaysian Nuclear Agency, Kajang, Malaysia), K.Z.M. Dahlan (Malaysian Nuclear Agency, Kajang, Malaysia), K.H.K. Hamid (Tech- nical University of MARA, Shah Alam, Malaysia), T. Hakoda (Japan Atomic Energy Agency, Takasaki, Japan) • Electron beam technology for air pollution control A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • EB processing of oil-combustion flue gases for PAH removal A. Ostapczuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Licki (Institute of Atomic Energy, Otwock-Świerk, Poland), A.G. Chmielewski (Institute of Nuclear Chemistry and Tech- nology, Warszawa, Poland) • Organic pollutants treatment by using electron beam technology Y. Sun (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • VOCS removal by combined electron beam and microwave treatment D. Ighigeanu (National Institute for Laser, Plasma and Radiation Physics, Bucharest, Romania), I. Cali- nescu (University Politehnica of Bucharest, Romania), O. Martin (National Institute for Laser, Plasma and Radiation Physics, Bucharest, Romania), C. Matei (National Institute for Laser, Plasma and Radia- tion Physics, Bucharest, Romania) • Electron-beam induced PAHs transformation in flue gases G. Gerasimov (Lomonosov Moscow State University, Russia) • Electron-beam treatment influence on PAH content in flue gases streams from energy generation A.M. Mastral (Instituto de Carboquimica, Spanish National Research Council (CSIC), Zaragoza, Spain), M.S. Callen (Instituto de Carboquimica, Spanish National Research Council (CSIC), Zaragoza, Spain), J.M. López (Instituto de Carboquimica, Spanish National Research Council (CSIC), Zaragoza, Spain), M.T. de la Cruz (Instituto de Carboquimica, Spanish National Research Council (CSIC), Zaragoza, Spain)

9. ROCZNE SEMINARIUM PROJEKTU BADAWCZO-ROZWOJOWEGO “INTELIGENT- NY SYSTEM POMIARÓW STĘŻENIA ZANIECZYSZCZEŃ POWIETRZA JAKO NA- RZĘDZIE WSPOMAGANIA ZARZĄDZANIA OCHRONĄ POWIETRZA ATMOSFE- RYCZNEGO” (ANNUAL SEMINAR ON THE RESEARCH AND DEVELOPMENT PROJECT “INTELLIGENT SYSTEM FOR THE MEASUREMENTS OF AIR POLLU- TION AS A TOOL FOR THE AID OF AMBIENT AIR PROTECTION MANAGEMENTS”), 12 DECEMBER 2008, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology OPENING A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

LECTURES • Opracowanie i wykonanie modelu systemu do ciągłych pomiarów (automatycznych) pyłu zawieszonego w powietrzu wraz z bezprzewodową transmisją danych. Wykonanie dwóch egzemplarzy systemu, przepro- wadzenie instalacji w wybranych miejscach pomiarowych, testowanie aparatury i oprogramowania (Design and development of a model of the system for on-line, automatic measurements of the dust in air with wireless transmission of the results. Manufacturing of two specimens of the system, software development, providing installation and testing) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 213

A. Jakowiuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J.P. Pieńkos (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Urbański (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Analiza pierwiastkowa różnych frakcji pyłu zawieszonego (PM10/PM2,5) z zastosowaniem rentgenowskiej analizy fluorescencyjnej (w tym określenie i optymalizacja warunków pobierania próbek pyłu zawieszonego oraz opracowanie wyników pomiarów i ich ocena statystyczna) (Elemental XRF analysis of the suspended dust collected with PM10 and PM2.5 samplers. Optimization of the sampling conditions and processing of the obtained results using advanced statistical procedures) M. Lankosz (AGH University of Science and Technology, Kraków, Poland), L. Samek (AGH University of Science and Technology, Kraków, Poland)

• Analiza danych archiwalnych i bieżących o zanieczyszczeniach powietrza: SO2/NOx/pył/aerozole oraz danych meteorologicznych (T/P/M/Wv/Wk/Wp/opad/) zarejestrowanych w IGF PAN (określenie trendów). Badania i analiza rozkładów wielkości aerozolu submikronowego oraz własności elektrycznych atmosfery (Analysis of the archive and current data concerning ambient air pollutants: SO2/NOx/dust/aerosols and meteorological parameters collected by the Institute of Geophysics of Polish Academy of Sciences. Inves- tigation and analysis of the submicron aerosols size distribution, and electric features of the atmosphere) M. Kubicki (Institute of Geophysics, Polish Academy of Sciences, Warszawa, Poland) • Inwentaryzacja źródeł pyłu zawieszonego w wybranych miejscach powiatu otwockiego i miasta Otwock na podstawie zezwoleń, rejestracji i badań własnych z uwzględnieniem specyficznych warunków lokalnych oraz rozpoznanie możliwości wykorzystania modeli emisyjnych. Analiza możliwości ograniczenia stężenia pyłu zawieszonego i/lub aerozolu z uwzględnieniem czynników ekonomicznych i uwarunkowań lokalnych (Recognising sources of the suspended dust emitters in chosen places of the Otwock district and the city of Otwock. The data are to be collected basing on the administrative permission and licensing documentation, as well as on some own examinations. Feasibility study of applicability of some theoretical emission models will be prepared) M. Sowiński (The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland) • Badanie rozkładów pyłu zawieszonego i/lub aerozoli (3 nanometrów-10 mikrometrów) z uwzględnieniem korelacji różnych frakcji pyłu i/lub aerozoli z parametrami meteorologicznymi (Investigation of the grain size distribution of the suspended dust and/or aerosols (3 nm-10 μm), considering correlations of the various dust and/or aerosol fractions with meteorological parameters) M. Kowalski (The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland), M. Sowiński (The An- drzej Sołtan Institute for Nuclear Studies, Świerk, Poland) • Zastosowanie matematyczno-statystycznej analizy sygnału do predykcji stężeń zanieczyszczeń powietrza, badania korelacji pomiędzy nimi oraz parametrami meteorologicznymi. Opracowanie, zainstalowanie, testowanie predyktora zanieczyszczeń powietrza w oparciu o dane imisji, sieci neuronowe i prognozowane parametry meteorologiczne (Application of statistical analysis of the measurement results for prediction of air pollution. Investigation of correlations between them and meteorological parameters. Develop- ment, installation and testing of the air pollution predictor employing imision data, neural networks and forecasted meteo parameters) K. Siwek (Warsaw University of Technology, Poland), J. Szlachciak (Warsaw University of Technology, Poland)

CLOSING REMARKS A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

10. VI KONFERENCJA „PROBLEMY UNIESZKODLIWIANIA ODPADÓW” (VI CONFER- ENCE ON PROBLEMS OF WASTE DISPOSAL), 15 DECEMBER 2008, WARSZAWA, POLAND Organized by the Warsaw University of Technology, Solid Communal Waste Utilization Plant (Warszawa), Institute of Nuclear Chemistry and Technology, Gdańsk University of Technology Organizing Committee: M. Obrębska, Ph.D., A. Polak, M.Sc., M. Kalita, M.Sc.

LECTURES Session A/I. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY) Chairman: A. Biń (Warsaw University of Technology, Poland) • Recykling i odzysk odpadów poli(chlorku winylu) (Recycling and recovery of polyvinylchloride) M. Obłój-Muzaj (Industrial Chemistry Research Institute, Warszawa, Poland) • Technologia unieszkodliwiania i wykorzystania popiołów ze spalania węgla oraz utylizacji i ceramizacji osadów ściekowych, odpadów komunalnych i innych (Technology for waste neutralization and the use of ashes from coal combustion, utilization and making ceramic from liquid sludge, municipal wastes and others) 214 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

J. Sokołowski (Warsaw University of Technology, Poland), K. Łuczaj (Warsaw University of Technology, Poland), A. Szudarska (Warsaw University of Technology, Poland) • Utylizacja przepracowanych płynów chłodniczych z wykorzystaniem membranowych procesów rozdziału (Utilization of used antifreezes with the use of membrane separation processes) T. Porębski (Industrial Chemistry Research Institute, Warszawa, Poland), W. Ratajczak (Industrial Chem- istry Research Institute, Warszawa, Poland), S. Tomzik (Industrial Chemistry Research Institute, Warszawa, Poland) Session B/I. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL-ECONOMIC-LAWFUL) Chairman: M. Obrębska (Warsaw University of Technology, Poland) • Projekt Pilotażowy. Koncepcja rozwoju selektywnej zbiórki odpadów na terenie dzielnicy Białołęka (Con- ception of selective collection of wastes in the Białołęka Commune – pilot project) J. Kaznowski (Major of Białołęka Commune, Warszawa, Poland) • Projekty budowy instalacji termicznego przekształcania odpadów komunalnych w Polsce – bariery i szanse (Projects of construction of thermal installations for transformation of municipal wastes in Poland – barriers and chances) T. Pająk (AGH University of Science and Technology, Kraków, Poland) • Gospodarka odpadami medycznymi jako element miejskiego systemu gospodarki odpadami na przykładzie Warszawy. Problemy i proponowane kierunki działań (Medical waste disposal as an element of a municipal system of waste disposal; Warszawa as an example. Problems nad proposed trends of activity) A. Rolewicz-Kalińska (Warsaw University of Technology, Poland) Session A/II. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY) Chairman: A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Sekwestracja CO2 poprzez karbonatyzację minerałową (Sequestration of CO2 by mineral carbonatization) J. Bałdyga (Warsaw University of Technology, Poland), M. Henczka (Warsaw University of Technology, Poland), K. Sokolnicka (Warsaw University of Technology, Poland), M. Materek (Warsaw University of Technology, Poland) • Technologia przerobu odpadowych tworzyw sztucznych na paliwa ciekłe (Technology for processing plastic wastes to obtain liquid fuels) R. Rozwałka (NOR-ECO Sp. z o.o., Warszawa, Poland), W. Naguszewski (NOR-ECO Sp. z o.o., Warszawa, Poland), A. Jaszczyk (NOR-ECO Sp. z o.o., Warszawa, Poland), A. Darkowski (NOR-ECO Sp. z o.o., Warszawa, Poland), Ł. Nowak (NOR-ECO Sp. z o.o., Warszawa, Poland) • Krajowe instalacje odzysku odpadów tworzyw sztucznych w świetle danych wojewódzkich planów gospodarki odpadami (National installations for recovery of plastic wastes in the light of provincional data on the plans for waste disposal) R. Wasielewski (Institute for Chemical Processing of Coal, Zabrze, Poland), A. Sobolewski (Institute for Chemical Processing of Coal, Zabrze, Poland) Session B/II. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL ECONOMIC-LAWFUL) Chairman: T. Pająk (AGH University of Science and Technology, Kraków, Poland) • Analiza problemu oddziaływania zapachowego na podstawie skarg ludności oraz inwentaryzacji źródeł odorantów w gospodarce ściekowej w Polsce oraz na terenie województwa mazowieckiego (Analysis of odour impact based on complains of population and listing of the sources of odorous substances in sewage disposal in Poland and particularly in the Mazowsze province) A. Malanowska (Warsaw University of Technology, Poland), A. Kulig (Warsaw University of Technology, Poland) • Zastosowanie detektora PID w przenośnych analizatorach LZO oraz przenośnym chromatografie gazowym Voyager do oceny skażenia środowiska naturalnego oraz wykrywania wybranych odorów i merkaptanów (Application of a PID detector in portable analyzers LZO and in a portable chromatograph, type Voyager, to evaluate pollution of the natural environment and to detect selected odorous substances and mercaptone) K. Pawłowski (Atut Sp. z o.o., Lublin, Poland) Session A/III. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY) Chairman: A. Kulig (Warsaw University of Technology, Poland) • Zanieczyszczenie związkami chlorowcoorganicznymi – problem zaopatrzenia miast w dobrej jakości wodę (Pollution with chloroorganic compounds – problem of good quality water supply of towns) Z. Malinowska (WAT Military University of Technology, Warszawa, Poland), A. Świątkowski (WAT Mili- tary University of Technology, Warszawa, Poland) • Wpływ stopnia segregacji stałych odpadów komunalnych na ich wartość opałową na przykładzie ZUSOK w Warszawie (Effect of segregation of solid municipal wastes on their combustible value, taking ZUSOK in Warszawa as an example) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008 215

M. Kobus (Warsaw University of Technology, Poland), M. Obrębska (Warsaw University of Technology, Poland) • Nieuchronność zakazu stosowania żywic formaldehydowych i problem unieszkodliwiania ich odpadów (In- evitable prohibition of the use of formaldehyde resins and the problem of disposal of their wastes) Z.K. Brzozowski (Central Institute for Labour Protection – National Research Institute, Warszawa, Poland; Warsaw University of Technology, Poland) Session B/III. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL ECONOMIC-LAWFUL) Chairman: P. Grzybowski (Warsaw University of Technology, Poland) • Eliminacja zagrożeń wynikających z niekontrolowanego rozwoju grzybów mikroskopowych (Elimination of hazards resulting from the uncontrolled growth of microscopic fungi) P. Grzybowski (Warsaw University of Technology, Poland) • Ekologiczne spalanie mączki mięsno-kostnej (Ecological combustion of the meat-and-bone meal) H. Karcz (ZBUS-TKW Combustion Sp. z o.o., Głowno, Poland), K. Wierzbicki (Institute for Buildings Mechanization and Electrification of Agriculture, Warszawa, Poland), M. Kantorek (ZBUS-TKW Com- bustion Sp. z o.o., Głowno, Poland), A. Kozakiewicz (ZBUS-TKW Combustion Sp. z o.o., Głowno, Poland)

POSTERS • Emulsje wielokrotne w procesie usuwania polifenoli (Multiple emissions in the removal process of poliphe- nols) E. Dłuska (Warsaw University of Technology, Poland), M. Wolski (Warsaw University of Technology, Poland), S. Wroński (Warsaw University of Technology, Poland) • Usuwanie jonów cynku z rozcieńczonych alkalicznych roztworów wodnych metodą flotacji jonowej (Re- moval of zinc ions from dilute aqueous alkaline solutions by ionic flotation) B. Kawalec-Pietrenko (Gdańsk University of Technology, Poland), D. Konopacka-Łyskawa (Gdańsk Uni- versity of Technology, Poland), I. Hołowacz (Gdańsk University of Technology, Poland) • Przemysłowe wykorzystanie komunalnych osadów ściekowych – studium przypadku (Industrial use of municipal sludge – study of the case) J. Latosińska (Kielce University of Technology, Poland), M. Żygadło (Kielce University of Technology, Poland) • Możliwości wykorzystania sznurków wykonanych z odpadów w sektorze sanitarno-medycznym (Possibility of using strings made from wastes in the sanitary-medical sector) Z. Polus (Textile Research Institute, Łódź, Poland), I. Mączka (Textile Research Institute, Łódź, Poland), M. Dulęba-Majek (Textile Research Institute, Łódź, Poland) • Nowoczesne metody planowania sieci pomiarowych w celu obniżenia kosztów remediacji gleby (Modern planning methods from measuring nets in order to reduce costs of soil remedy) J. Zawadzki (Warsaw University of Technology, Poland), A. Targowski (Warsaw University of Technology, Poland) • Wpływ rodzaju warstwy tlenkowej na powierzchni filtrów z ditlenku krzemu na proces oczyszczania emul- sji wodno-olejowych (Influence of the type of oxide layer on the surface of fillers from silicon dioxide on the purification process of water-oil emulsions) K. Perkowski (Warsaw University of Technology, Poland), J. Sokołowski (Warsaw University of Technology, Poland), M. Szafran (Warsaw University of Technology, Poland) • Membranowy rozdział mieszanin gazowych dla potrzeb energetyki gazowej (Membrane separation of gaseous mixtures for the needs of gaseous energetics) A. Polak (Warsaw University of Technology, Poland), A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Rewulkanizacja gumy – sposób wytwarzania wyrobów z odpadów gumowych (Re-vulcanization of rubber – method for obtaining products from rubber scraps) E. Kowalska (Industrial Chemistry Research Institute, Warszawa, Poland), M. Żubrowska (Industrial Chemistry Research Institute, Warszawa, Poland), S. Pasynkiewicz (Industrial Chemistry Research Insti- tute, Warszawa, Poland) • Modyfikacja tworzyw uzyskiwanych z recyklingu oprzyrządowania elektrycznego/elektronicznego (WEEE) (Modification of plastics obtainaed from the recycling of electro-electronic instrumentation) E. Kowalska (Industrial Chemistry Research Institute, Warszawa, Poland), M. Żubrowska (Industrial Chemistry Research Institute, Warszawa, Poland), M. Studziński (Industrial Chemistry Research Institute, Warszawa, Poland) • Właściwości kompozytów poliolefinowych napełnianych różnymi rodzajami odpadów dywanowych (Prop- erties of polyolefine composites filled with carpet scraps of different type) 216 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2008

E. Kowalska (Industrial Chemistry Research Institute, Warszawa, Poland), L. Kuczyńska (Industrial Chemistry Research Institute, Warszawa, Poland) • Wyroby użytkowe z odpadów tworzyw termoplastycznych i gumy (Useful products from thermoplastic and rubber scraps) E. Kowalska (Industrial Chemistry Research Institute, Warszawa, Poland), Z. Wielgosz (Industrial Chem- istry Research Institute, Warszawa, Poland), S. Pasynkiewicz (Industrial Chemistry Research Institute, Warszawa, Poland), M. Żubrowska (Industrial Chemistry Research Institute, Warszawa, Poland) • Technologia otrzymywania nanoproszków miedzi i innych metali ciężkich z elektrolitów odpadowych i ścieków przemysłu miedziowego (Technology for obtaining nanopowders of copper and other heavy metals from discard electrolytes and sewage of the copper industry) A. Łukomska (Industrial Chemistry Research Institute, Warszawa, Poland), A. Plewka (Industrial Chem- istry Research Institute, Warszawa, Poland), D. Wilson-Polit (Industrial Chemistry Research Institute, Warszawa, Poland), P. Łoś (Industrial Chemistry Research Institute, Warszawa, Poland) • Charakterystyka materiałów polimerowych z recyklingu wg. norm EN (Characterization of polymer materials from recycling, according to the EN norms) Z. Dobkowski (Industrial Chemistry Research Institute, Warszawa, Poland), H. Głowala (Industrial Chemistry Research Institute, Warszawa, Poland), M. Choroś (Industrial Chemistry Research Institute, Warszawa, Poland) • Znormalizowana ocena możliwości usuwania tworzyw sztucznych w oczyszczalniach ścieków (Standard estimation of the possibility of removing plastics in sewage-treatment plants) Z. Dobkowski (Industrial Chemistry Research Institute, Warszawa, Poland), H. Głowala (Industrial Chemistry Research Institute, Warszawa, Poland), M. Choroś (Industrial Chemistry Research Institute, Warszawa, Poland) • Frakcja biodegradowalna odpadów komunalnych (The biodegradovable fraction of municipal wastes) R. Wasielewski (Institute for Chemical Processing of Coal, Zabrze, Poland), S. Stelmach (Institute for Chemical Processing of Coal, Zabrze, Poland) • Badanie barier aktywnych stosowanych do dekontaminacji wód gruntowych (Studies of active barriers applied for the decontamination of surface waters) A. Adach (Warsaw University of Technology, Poland), S. Wroński (Warsaw University of Technology, Poland), E. Mikołajewska (Warsaw University of Technology, Poland) • Instalacja do termicznej utylizacji osadów ściekowych (An installation for thermal utilization of sludge) W. Jodkowski (Wrocław University of Technology, Poland), K. Wierzbicki (Institute for Buildings Mecha- nization and Electrification of Agriculture, Warszawa, Poland), S. Zuber (University of Wrocław, Poland) Ph.D. THESES IN 2008 217

Ph.D. THESES IN 2008

1. Michał Gryz (Office for Registration of Medicinal Products, Medical Devices and Biocidal Products, Warszawa, Poland) Badanie koordynacji jonów magnezu i cynku w kompleksach z ligandami kwasów diazynokarboksylowych (Studies of coordination of magnesium and zinc ions in their complexes with the azine dicarboxylate ligands) supervisor: Prof. Janusz Leciejewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 01.02.2008 2. Marek Pruszyński, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Kompleksy 211At jako prekursory radiofarmaceutyków (211At complexes as precursors of radiopharmaceuticals) supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 25.04.2008 3. Wojciech Ozimiński, M.Sc. (National Medicines Institute, Warszawa, Poland) Tautometria pięcioczłonowych pierścieni heterocyklicznych zawierających trzy heteroatomy. Badania obliczeniowe (Tautomerism of five-membered heterocyclic rings containing three heteroatoms. A computational study) supervisor: Jan Cz. Dobrowolski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 20.06.2008 4. Ewelina Chajduk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Prace nad konstruowaniem metod o najwyższej randze metrologicznej dla oznaczania Se i As w materiałach biologicznych za pomocą radiochemicznej neutronowej analizy aktywacyjnej (Studies on development of highly accurate (definitive) methods for the determination of selenium and arsenic in biological materials by radiochemical neutron activation analysis) supervisor: Prof. Rajmund Dybczyński, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 20.06.2008 5. Anna Bojanowska-Czajka, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Analityczne badania przebiegu procesów rozkładu wybranych pestycydów przy użyciu promieniowania jonizującego (Analytical studies of decomposition of selected pesticides using ionizing radiation) supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 20.06.2008 6. Anna Ostapczuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Degradacja wybranych węglowodorów aromatycznych w mieszaninach gazowych pod wpływem wiązki elektronów (Decomposition of selected aromatic hydrocarbons in gaseous mixtures under electron beam irradiation) supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 10.10.2008 218 EDUCATION

EDUCATION

Ph.D. PROGRAMME IN CHEMISTRY

The Institute of Nuclear Chemistry and Technology holds a four-year Ph.D. degree programme for graduates of chemical, physical and biological departments of universities, for graduates of medical universities and to engineers in chemical technology and material science. The main areas of the programme are: • radiation chemistry and biochemistry, • chemistry of radioelements, • isotopic effects, • radiopharmaceutical chemistry, • analytical methods, • chemistry of radicals, • application of nuclear methods in chemical and environmental research, material science and protection of historical heritage. The candidates accepted for the mentioned programme can be employed in the Institute. The candidates can apply for a doctoral scholarship. The INCT offers accommodation in 10 rooms in the guest- house for Ph.D. students not living in Warsaw. During the four-year Ph.D. programme, the students participate in lectures given by senior staff from the INCT, Warsaw University and the Polish Academy of Sciences. In the second year, the Ph.D. students have teaching practice in the Chemistry Department of Warsaw University. Each year the Ph.D. students are obliged to deliver a lecture on topic of his/her dissertation at a seminar. The final requirements for the Ph.D. programme graduates, consistent with the regulation of the Ministry of Science and Higher Education, are: • submission of a formal dissertation, summarizing original research contributions suitable for publication; • final examination and public defense of the dissertation thesis. In 2008, the following lecture series were organized: • “Selected problems of nuclear energetics” – Dr. Andrzej Strupczewski (Institute of Atomic Energy, Otwock-Świerk, Poland); • “Basis of molecular spectroscopy” – Assoc. Prof. Jan Dobrowolski, Ph.D., D.Sc. (National Medicines Institute, Warszawa, Poland). The qualification interview for the Ph.D. programme takes place in the mid of October. Detailed information can be obtained from: • Head: Prof. Aleksander Bilewicz, Ph.D., D.Sc. (phone: (+4822) 504 13 57, e-mail: [email protected]); • Secretary: Dr. Ewa Gniazdowska (phone: (+4822) 504 10 74 or 504 11 78, e-mail: [email protected]).

TRAINING OF STUDENTS

Institution Country Number of participants Period Rzeszów University of Technology Poland 1 5.5 month Faculty of Chemistry Silesian University of Technology Poland 1 1 month Faculty of Chemistry Poland Technical School of Chemistry No. 3 2 1 month (Warszawa) Technical University of Łódź Poland 1 2 weeks Faculty of Chemistry University of Silesia Poland 13 one-day practice Faculty of Earth Sciences EDUCATION 219

Institution Country Number of participants Period University of Warsaw 1 11 months Poland Faculty of Chemistry 2 4 months Warsaw University of Technology two-day Poland 9 Faculty of Chemical and Process Engineering practice Warsaw University of Technology Poland 1 1 month Faculty of Materials Science and Engineering Warsaw University of Technology 1 1 month Poland Faculty of Physics 40 one-day practice WAT Military University of Technology Poland 1 1.5 month 220 RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008

1. Protection phenomena in radiation chemistry of polypropylene. supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. 2. Analytical studies of decomposition of selected pesticides using ionizing radiation. supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc. 3. Complexes of astatine-211 with metals as potential precursors of radiopharmaceuticals. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. 4. The role of pirin in regulation of NF-kB signalling in response to oxidative stress. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. 5. Studies on development of highly accurate methods for the determination of selenium and arsenic in biological samples by radiochemical neutron activation analysis. supervisor: Prof. Rajmund Dybczyński, Ph.D., D.Sc. 6. The influence of nitric oxide and peroxynitrite on conformation and activity of iron containing proteins. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. 7. Complexes of radionuclides rhodium and scandium as potential precursors of therapeutic radiopharmaceuticals. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. 8. The role of high molecular weight ligands in formation of dinitrosyl iron complexes. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. 9. Elaboration of a criterion and methodology of estimation of inorganic materials applied in the XV-XVIIth centuries icon paintings from South-Eastern Poland. supervisor: Ewa Pańczyk, M.Sc.

DEVELOPMENT PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008

1. Cheap and non-toxic dosimeter for measurement of absorbed dose in radiation processing of fluidized beds and fluid streams. supervisor: Zofia Stuglik, Ph.D. 2. An intelligent system for the measurement of air pollution as a tool to aid the management of ambient air protection. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

IMPLEMENTATION PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008

1. New Polish certified reference materials: Oriental Basma Tobacco Leaves and Polish Virginia Tobacco Leaves for quality control of analytical laboratories. supervisor: Zbigniew Samczyński, Ph.D. RESEARCH PROJECTS AND CONTRACTS 221 RESEARCH PROJECTS ORDERED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008

1. Development and preparation for the implementation technology of VOCs degradation from waste off-gases by using plasma generated electron beam. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. PZB-MEiN-3/2/2006

2. Method elaboration and stable isotope analyses of CO2, CH4, N2O and VOC-Cl emitted in technological processes by the use of mass spectrometry. supervisor: Ryszard Wierzchnicki, Ph.D. PZB-MEiN-3/2/2006 3. Modification of SiC physical properties by irradiation with electron beam. supervisor: Prof. Jacek Michalik, Ph.D., D.Sc. PZB-MEiN-6/2/2006

INTERNATIONAL PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2008

1. A synthesis and investigation of new technetium(III) and rhenium(III) complexes (so-called “4+1”) with the dendritically modified tetradentate ligands NS3 and a monodentate isonitrile ligand. supervisor: Ewa Gniazdowska, Ph.D. 2. Removal of aromatic organic pollutants from gas phase by using electron beam technology. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 3. Examination of the antimutagenic activity of 1,4-dihydropyridine derivatives in X-irradiated mammalian cells. supervisor: Prof. Irena Szumiel, Ph.D., D.Sc. 4. COST D38 Complexes of 44Sc as precursors of radiopharmaceuticals for molecular imaging. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. 5. Functionalization of polymer surfaces by radiation grafting for separation of heavy metals including radioactive lanthanides. supervisor: Assoc. Prof. Grażyna Przybytniak, Ph.D., D.Sc. 6. Validation of Cs-Ba and Ge-Ge generators applicability for laboratory and industrial radiotracer tests. supervisor: Jacek Palige, Ph.D. 7. Transition metal complexes as novel agents of expected biological activity directed towards Auger electron therapy (AET) supervisor: Leon Fuks, Ph.D. 8. Electron beam treatment of organic pollutants contained in gaseous streams. supervisor: Anna Ostapczuk, Ph.D. 9. Advanced system with high energy electron beam for radiation processing and research studies. supervisor: Zbigniew Zimek, Ph.D. 10. Use of ionizing radiation for the manufacture and modification of nanostructure materials. supervisor: Dagmara Chmielewska, M.Sc. 11. Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry. supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc.

IAEA RESEARCH CONTRACTS IN 2008

1. Validation of Cs-Ba and Ge-Ge generators applicability for laboratory and industrial radiotracer tests. 222 RESEARCH PROJECTS AND CONTRACTS

No. 14335 principal investigator: Jacek Palige, Ph.D. 2. Electron beam treatment of organic pollutants contained in gaseous streams. No. 13136 principal investigator: Anna Ostapczuk, M.Sc. 3. Functionalization of polymer surfaces by radiation grafting for separation of heavy metals including radioactive lanthanides. No. 14431 principal investigator: Assoc. Prof. Grażyna Przybytniak, Ph.D., D.Sc.

IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2008

1. Use of ionizing radiation for the manufacture and modification of nanostructure materials. POL/8/020 2. Quality control methods and procedures for radiation technology. RER/8/010 – joint coordination 3. Standard feasibility study for electron beam flue gas treatment technology. RER/8/011 – coordination

PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN 2008

1. FP7 Integrated Project: Actinide recycling by separation and transmutation (ACSEPT) principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc. 2. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Advanced methods for environment research and control (AMERAC). principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc. MTKD-CT-2004-509226 3. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Chemical studies for design and production of new radiopharmaceuticals (POL-RAD-PHARM). principal investigator: Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. MTKD-CT-2004-509224

INTERNATIONAL RESEARCH PROGRAMMES IN 2008

1. European cooperation in the field of scientific and technical research. COST CM0703 Systems chemistry – Chemistry and molecular sciences and technologies. Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry. supervisor: Prof. Zbigniew Zagórski, Ph.D., D.Sc. 2. European cooperation in the field of scientific and technical research. COST P9 – Radiation damage in biomolecular systems (RADAM). Mechanisms of radiation damage transfer in polypep- tide molecules. supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 3. European cooperation in the field of scientific and technical research. COST D38 – Metal based probes for imaging applications. Complexes of 44Sc as precursors of radiopharmaceuticals for molecular imaging. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. 4. Polish-Norwegian Research Fund – Impact of nanomaterials on human health: lessons from in vitro and animal models. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. RESEARCH PROJECTS AND CONTRACTS 223

5. Transition metal complexes as novel agents of expected biological activity directed towards Auger electron therapy (AET) supervisor: Leon Fuks, Ph.D. 6. A synthesis and investigation of new technetium(III) and rhenium(III) complexes (so-called “4+1”) with the dendritically modified tetradentate ligands NS3 and a monodentate isonitrile ligand. supervisor: Ewa Gniazdowska, Ph.D. 7. Removal of aromatic organic pollutants from gas phase by using electron beam technology. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 8. Examination of the antimutagenic activity of 1,4-dihydropyridine derivatives in X-irradiated mammalian cells. supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.

OTHER FOREIGN CONTRACTS IN 2008

1. Elaboration and implementation of a programme of instructions for the interdisciplinary laboratory National Centre of Banking Tissues and Cells within the frame of FF 2006/018-180.03.04 “Intensification of capabilities and possibilities of the National Centre of Banking Tissues and Cells to ensure security and quality human cells used for grafting”. Project financed by the foundation “Cooperation Fund” from the means of Transition Facility. 2. Device for irradiation of cells with alpha particles and X-rays. Contract with European Commission, Joint Research Centre, Institute of Energy

3. Laboratory research on SO2 and NOx removal by electron beam flue gas treatment process with addition of potassium compounds. Contract with Sviloza Power Station, Svishtov, Bulgaria 4. Research on the EBFGT reaction chamber construction with use of CFD methods. Contract with Sviloza Power Station, Svishtov, Bulgaria 5. Basic engineering of electron beam flue gas treatment plant of 6 000 000 Nm3/h nominal flow rate at Sviloza thermal power plant, Svishtov. Contract with Sviloza Power Station, Svishtov, Bulgaria 224 LIST OF VISITORS TO THE INCT IN 2008

LIST OF VISITORS TO THE INCT IN 2008

1. Al-Saqqa Amjad, Atomic Energy Commission of Syria (AECS), Damascus, Syria, 01.01.-04.02. 2. Anderson Robert, University of Auckland, New Zealand, 05-06.09. 3. Bin-Saleem Saud, Atomic Energy Research Institute, King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia, 30.03.-31.05. 4. Bizot Bruno, CEA-CNRS-Ecole Polytechnique, Palaiseau, France, 28-29.05. 5. Bragea Michaela, Institute of Public Health, Timisoara, Romania, 01.02.-01.04. 6. Carmichael Ian, Notre Dame Radiation Laboratory, USA, 04-06.09. 7. Chatgilialoglu Chryssostomos, Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy, 27-29.09. 8. Çiçek Ekrem, Mehmet Akif Ersoy University, Burdur, Turkey, 08.05.-08.08. 9. Clochard Marie-Claude, CEA-CNRS-Ecole Polytechnique, Palaiseau, France, 28-29.05. 10. Cojocaru Corneliu, “Gh. Asachi” Technical University of Iaşi, Romania, 08.06.-31.07. 11. Einav Izaak, Austria, 01.04.-31.05. 12. Ferreri Carla, Institute for the Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bologna, Italy, 27-29.09. 13. Gabelova Alena, Cancer Research Institute, Slovak Academy of Sciences, Slovakia, 15-21.06. 14. Gryzlov Anatolij, NPO “Toriy”, Moscow, Russia, 20-30.10. 15. Houeé-Levin Chantal, Université Paris-Sud, France, 19-24.02. 16. Jurnečka Alexander, Electrotechnicky Vyskumny a Projektovy Ustav a.s. (EVPU), Nová Dubnica, Slovakia, 15-16.05. 17. Kasztovszky Zsolt, Institute of Isotope and Surface Chemistry, Budapest, Hungary, 01-06.07. 18. Kim Jaewoo, Korea Atomic Energy Research Institute, Daejeon, Republic of Korea, 18-19.09. 19. Konczykowski Marcin, CEA-CNRS-Ecole Polytechnique, Palaiseau, France, 28-29.05. 20. Kothari Kanchan Kamalakar, Bhabha Atomic Research Centre, Mumbai, India, 19.04.-08.08. 21. Kraiem Mokhtar, Centre National des Sciences et Technologies Nucléaires, Sidi Thabet, Tunisia, 02-15.11. 22. Kučka Jan, Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Řež, Czech Republic, 25.02.-25.04. 23. Lazurik Valenty, Kharkiv National University, Ukraine, 12-16.05. 24. Lin Jie, Institute of Fluid Mechanics of Toulouse, France, 31.03.-31.08. 25. Lozano Nunez Ana, University of Salamanka, Spain, 26.10.-03.12. 26. Luo Jingyu, Tsinghua University, China, 10-19.09. 27. Miljević Nada, Vinča Institute of Nuclear Sciences, Belgrade, Serbia, 08-14.09, 17-20.09. 28. Neves Maria, Instituto Tecnológico e Nuclear, Sacavém, Portugal, 19-25.05. 29. Nichipor Henrietta, Joint Institute for Power and Nuclear Research “Sosny”, National Academy of Sciences of Belarus, Belarus, 19-20.09. 30. Nievaart Sander, Institute for Energy – Joint Research Centre of the European Commission, Petten, the Netherlands, 28.02. 31. Papagiannopoulou Dionysia, Aristotle University of Thessaloniki, Greece, 20.04.-02.05. 32. Pietzsch Juergen Hans, Institute of Radiopharmacy, Forschungszentrum Dresden-Rossendorf, Germany, 16-18.05. 33. Politkovskij Fiodor, NPO “Toriy”, Moscow, Russia, 20-30.10. 34. Popov Genadij, Kharkiv National University, Ukraine, 12-16.05. LIST OF VISITORS TO THE INCT IN 2008 225

35. Resnizky Sara Manuela, Argentina National Atomic Energy Commission, Bueons Aires, Argentina, 20-29.09. 36. Sabharwal Sunil, Bhabha Atomic Research Centre, Mumbai, India, 04-17.05. 37. Santos Lucas Carla, Instituto Tecnológico e Nuclear, Sacavém, Portugal, 19-25.05. 38. Sarkar Sisir, Bhabha Atomic Research Centre, Mumbai, India, 12-14.09. 39. Smal Marharita, Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk, Belarus, 01-13.09. 40. Stefanova Maja, Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria, 18-21.09. 41. Styervoyedow Sergiej, Kharkiv National University, Ukraine, 24.09.-04.10. 42. Suleymanova Aygun, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Baku, Azerbaijan, 25.08.-24.09. 43. Uzal Nigmet, Kocaeli University, Turkey, 30.06.-26.08. 44. Videnovic Ivan, International Atomic Energy Agency, Vienna, Austria, 03.12. 226 THE INCT SEMINARS IN 2008

THE INCT SEMINARS IN 2008

1. Prof. Marc Rosen (Engineering Institute of Canada, University of Ontario Institute of Technology, Canada) Thermochemical water decomposition to produce hydrogen from nuclear energy 2. Halina Polkowska-Motrenko, Ph.D., Leon Fuks, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Badania biegłości: oznaczanie stężenia aktywności wybranych izotopów promieniotwórczych w żywności i materiałach środowiskowych dla laboratoriów tworzących sieć monitoringu radiacyjnego kraju (Profi- ciency testing: determination of radioactivity concentrations of selected radionuclides in food and environmental samples for the laboratories from the national radiation monitoring network) 3. Marie-Claude Clochard, Ph.D. (CEA, École Polytechnique, France) Functionalized nanoporous track-etched membranes: synthesis and applications 4. Bruno Bizot, Ph.D. (CEA, CNRS, École Polytechnique, France) Ionizing radiation effects in oxide glasses 5. Zbigniew Zimek, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Application of INCT electron accelerators in the field of radiation chemistry and technology 6. Isaac Einav (International Atomic Energy Agency expert) Model strategic business plan for nuclear technologies 7. Sunil Sabharwal, Ph.D. (Bhabha Atomic Research Centre, Mumbai, India) Current status of radiation technology applications and R&D in India 8. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Centrum Radiochemii i Chemii Jądrowej. Wstępne studium koncepcyjne (Centre for Radiochemistry and Nuclear Chemistry – general outline) 9. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Centrum Badań i Technik Radiacyjnych. Badania podstawowe (Centre of Radiation Research and Tech- nology. Basic research) 10. Halina Polkowska-Motrenko, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Program Laboratorium Jądrowych Technik Analitycznych (Field of activity of Laboratory of Nuclear Analytical Techniques) 11. Prof. Piotr Urbański, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Program Zespołu Radiometrii, Radiodiagnostyki i Technik Jądrowych (Research programme of the Nuclear Technique Group at the Institute of Nuclear Chemistry and Technology) 12. Prof. Marcin Kruszewski, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Program Centrum Radiobiologii i Dozymetrii Biologicznej (Programme of the Centre of Radiobiology and Biological Dosimetry) 13. Sylvia Ritter, Ph.D. (Gesellschaft für Schwerionenforschung mbH, Darmstadt, Germany) Heavy ion research in GSI: in vitro studies and cancer therapy 14. Bronisław Machaj, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Gamma skaner (GS-08) – założenia (Gamma scanner – assumptions) 15. Agnieszka Majkowska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Kompleksy 44/47Sc z multidentnymi ligandami jako prekursory radiofarmaceutyków (Complexes of 44/47Sc with multident ligands as precursors for radiopharmaceuticals) THE INCT SEMINARS IN 2008 227

16. Sander Nievaart, Ph.D. (Institute for Energy, Joint Research Centre, European Commission, Petten, the Netherlands) Boron neutron capture therapy (BNCT) of disseminated liver metastases 17. Alina Sionkowska, Ph.D., D.Sc. (Nicolaus Copernicus University, Toruń, Poland) Promieniowanie UV jako czynnik modyfikujący właściwości biomateriałów polimerowych (UV radiation as a modifying factor of properties of polymer biomaterials) 18. Prof. Marcin Kruszewski, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Labilna pula żelaza: wróg czy przyjaciel? (Labile iron pool: friend or foe?) 19. Prof. Grzegorz Bartosz, Ph.D., D.Sc. (University of Łódź, Poland) Reaktywne pochodne tlenu w komórce i jej otoczeniu (Reactive derivative of oxygen in a cell and its surrounding) 228 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2008

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2008

LECTURES

1. Deptuła A.

Synthesis of U-Th oxides, also doped e.g. ZrO2 by sol-gel processes. Kick Off Meeting of Actinide Recycling by Separation and Transmutation (ACSEPT) – Collaborative Project of the EC FP7-Euratom, Nimes, France, 30.03.-04.04.2008. 2. Kacprzak J., Kuszewski T., Lankoff A., Lisowska H., Müller W.-U., Wójcik A. Validation of the micronucleus assay for biological dosimetry after high dose exposure. 36th Annual Meeting of the European Radiation Research Society, Tours, France, 31.08.-04.09.2008. 3. Kornacka E.M., Przybytniak G., Święszkowski W. The influence of crystallinity on radiation stability of UHMWPE. 2008 Gordon Conference on Radiation Chemistry, Waterville Valley, USA, 06-11.07.2008. 4. Narbutt J. Energia jądrowa – zagrożenie czy szansa? Co robić z odpadami promieniotwórczymi? (Nuclear energy – threat or chance? How to manage nuclear waste?). Konferencja Koła Naukowego Sozologów “Alternatywne źródła energii”, Warszawa, Poland, 18.04.2008. 5. Narbutt J. Radionuklidy w przyrodzie – część I. Pierwiastki i izotopy promieniotwórcze (Radionuclides in nature – part I. Radioactive elements and isotopes). Kurs szkoleniowy “Ochrona radiologiczna w odniesieniu do przemysłowych i medycznych zastosowań promieniowania jonizującego, Otwock-Świerk, Poland, 25-26.11.2008. 6. Narbutt J. Radionuklidy w przyrodzie – część II. Radionuklidy w środowisku naturalnym (Radionuclides in nature – part II. Radionuclides in the environment). Kurs szkoleniowy “Ochrona radiologiczna w odniesieniu do przemysłowych i medycznych zastosowań promieniowania jonizującego, Otwock-Świerk, Poland, 25-26.11.2008. 7. Narbutt J. Radionuklidy sztuczne – część I. Reakcje jądrowe. Otrzymywanie radionuklidów (Anthropogenic radionuclides – part I. Nuclear reactions. Production of radionuclides). Kurs szkoleniowy “Ochrona radiologiczna w odniesieniu do przemysłowych i medycznych zastosowań promieniowania jonizującego, Otwock-Świerk, Poland, 25-26.11.2008. 8. Narbutt J. Właściwości substancji promieniotwórczych (Properties of radioactive species). Kurs szkoleniowy “Ochrona radiologiczna w odniesieniu do przemysłowych i medycznych zastosowań promieniowania jonizującego, Otwock-Świerk, Poland, 25-26.11.2008. 9. Narbutt J. Skażenia promieniotwórcze, degradacja i rekultywacja środowiska naturalnego (Radioactive contamination, degradation and recultivation of the environment). Kurs szkoleniowy “Ochrona radiologiczna w odniesieniu do przemysłowych i medycznych zastosowań promieniowania jonizującego, Otwock-Świerk, Poland, 25-26.11.2008. 10. Pawelec A. Electron beam flue gas treatment as multi pollutant control technology – present state and perspectives focusing on the Bulgarian project. The 3rd International Power Plant Emission Conference – Exploring Power Plant Emissions Reduction: Technologies and Strategies EXPPERTS 2008, Brussels, Belgium, 07-09.10.2008. 11. Wójcik A. Biological dosimetry. LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2008 229

Annual Meeting of EURADOS Network, 2nd Winter School on Retrospective Dosimetry, Paris, France, 24.01.2008. 12. Wójcik A. Analysis of chromosomal aberrations in cells exposed to ionizing radiation for the purpose of retrospective dose estimation and the assessment of DNA damage. 2008 Meeting of the Nordic Society for Radiation Protection, Ålesund, Norway, 26-30.05.2008. 13. Wójcik A. Accidental overexposure of radiotherapy patients in Bialystok. Causes and follow up. The small radiation accident – medical aspects, Bad Münstereifel, Germany, 25-26.09.2008. 14. Wójcik A. Radiation sensitivity of lymphocytes from patients with breast and gynecological cancer treated with radiotherapy: in search of prognostic and predictive markers. Jahrestagung der Gesellschaft für Biologische Strahlenforschung GBS, Tübingen, Germany, 06-08.10.2008.

SEMINARS

1. Krzysztof Bobrowski Free radical research in Pulse Radiolysis Laboratory. Tata Institute of Fundamental Science, Mumbai, India, 16.01.2008. 2. Krzysztof Bobrowski Conformational and geometric factors controlling the type of stabilization of sulfur radical cations in peptides. Heart Research Institute, Sydney, Australia, 30.07.2008. 3. Iwona Kałuska Audyt u dostawcy usługi sterylizacji radiacyjnej dla produktów leczniczych (Audit at the premises of radiation sterilization services contactor for medicinal products). Polish Chamber of Pharmaceutical Industry and Medical Devices POLFARMED, Warszawa, Poland, 29.10.2008. 4. Ewa M. Kornacka The effect of radiation sterilization on UHMWPE of various degree of crystallinity. University of Maryland, College Park, USA, 19.05.2008. 5. Jerzy Narbutt Hydration and solvation of metal chelates. Hydrophilicity and lipophilicity of the chelates. Institute of Radiopharmacy, Forschungszentrum Dresden-Rossendorf, Germany, 17.07.2008. 6. Grażyna Przybytniak Functionalization of polymer surfaces by radiation-induced grafting for separation of heavy metal ions. Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania, 19.02.2008. 7. Grażyna Przybytniak Contribution of radiation processing in polymeric biomaterials. Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest, Romania, 20.02.2008. 8. Grażyna Przybytniak Podstawy chemii radiacyjnej (Fundamentals of radiation chemistry). Institute of Atomic Energy, Otwock-Świerk, Poland, 02.12.2008. 9. Sylwester Sommer Dozymetria biologiczna do oceny dawki biologicznej w procedurach medycznych (Biological dosimetry for dose assessment in medical procedures). The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland, 11.06.2008. 10. Sylwester Sommer Dozymetria biologiczna (Biological dosimetry). Centre of Oncology – Maria Skłodowska-Curie Memorial Institute, Warszawa, Poland, 05.09.2008. 230 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2008

11. Irena Szumiel Historia i osiągnięcia Katedry Biochemii (1958-1968) (History and achievements of the Chair of Bio- chemistry (1958-1968)). University of Warsaw, Poland, 08.12.2008. 12. Andrzej Wójcik Indukowane przez promieniowanie aberracje chromosomowe w limfocytach krwi obwodowej - nie tylko biodozymetr (Radiation-induced chromosomal aberrations in human peripheral blood lymphocytes - a biodosimeter and not only). AGH University of Science and Technology, Kraków, Poland, 17.04.2008. 13. Andrzej Wójcik Searching for markers of individual radiosensitivity in patients treated with external beam radiation therapy. Karolinska Institute, Stockholm, Sweden, 11.06.2008. AWARDS IN 2008 231

AWARDS IN 2008

1. Method of production of titanium dioxide metal titanates from titanium tetrachloride Copper medal and diploma at the 6th International Exhibition (SuZhou) of Inventions, Shanghai, China, 16-20.10.2008 A. Deptuła, W. Łada, T. Olczak, A.G. Chmielewski, S. Casadio, C. Alvani, F. Croce 2. Silica sorbents effectively binding heavy metals Bronze medal at the 57th World Exhibition of Innovation, Research and New Technology “Brussels Eureka 2008”, Belgium, 13-15.11.2008 A. Łukasiewicz, L. Rowińska, L. Waliś 3. The Officer Cross, by the High Commission of the Invention, award at the 57th World Exhibition of Innovation, Research and New Technology “Brussels Eureka 2008”, Belgium, 13-15.11.2008 A.G. Chmielewski 4. Method for modification of mineral pigments and fabrics with silver Gold prize at the Seoul International Invention Fair 2008, Seoul, Korea, 11-15.12.2008 A. Łukasiewicz, D. Chmielewska, L. Waliś, J. Michalik 5. Special prize of Korea Invention Promotion Association for commending excellent efforts to create invention(s) exhibited at the Seoul International Invention Fair 2008, Seoul, Korea, 11-15.12.2008 A. Łukasiewicz, D. Chmielewska, L. Waliś, J. Michalik 6. Method for modification of mineral pigments and fabrics with silver Special prize of Asian Patent Attorneys Association (APAA) Korea Group at the Seoul International Invention Fair 2008, Seoul, Korea, 11-15.12.2008 A. Łukasiewicz, D. Chmielewska, L. Waliś, J. Michalik

211 7. At complexes as precursors of radiopharmaceuticals Second degree award for the best thesis in the field of chemistry in 2008 in the Grzegorz Białkowski competition organized by the Foundation for Polish Science and the Society for Advancement and Propaga- tion of Sciences M. Pruszyński

8. Use of a polymer membrane to the separation of a CH4/CO2 mixture First place in the competition for young scientists organized during the VII Scientific Conference on Membranes and Membrane Processes in Environmental Protection, Ustroń, Poland, 04-07.06.2008 A. Polak 9. Planning approach applied to experiments aiming at the determination of optimal conditions for the function of a membrane for ultrafiltration in the process of removal copper ions Distinction in the competition for young scientists organized during the VII Scientific Conference on Membranes and Membrane Processes in Environmental Protection, Ustroń, Poland, 04-07.06.2008 A. Jaworska 10. Diploma of the Ministry of Science and Higher Education for the project “Method of obtaining titanium dioxide, lithium and barium titanates from titanium tetrachloride” A. Deptuła, W. Łada, T. Olczak, A.G. Chmielewski, S. Casadio, C. Alvani, F. Croce 11. Diploma of the Ministry of Science and Higher Education for the project “Method for enhancement of purification effectiveness of radioactive wastes concentrated by means of reverse osmosis” A.G. Chmielewski, M. Harasimowicz, B. Tymiński, G. Zakrzewska-Trznadel 12. First degree group award of Rector of Warsaw University of Technology for scientific achievements in the years 2006-2007 R. Szabatin, J. Mirkowski, W. Smolik, T. Olszewski 13. Response suface methodology for modelling removal of copper from aqueous systems via micellar enhanced ultrafiltration 232 AWARDS IN 2008

Diploma for the best poster at the International Conference on Recent Developments and Applications of Nuclear Technologies, Białowieża, Poland, 15-17.09.2008 A. Jaworska 14. Sucrose as double signal high dose dosimeter for ionizing radiation Conference Award of Poster Committee at the International Meeting on Radiation Processing IMRP 15, London, the United Kingdom, 21-24.09.2008 Z. Peimel-Stuglik, S. Fabisiak 15. First degree team award of Director of the Institute of Nuclear Chemistry and Technology for a series of six articles concerning mechanisms of radiation-induced free-radical reactions in chemical compounds important from the biological point of view K. Bobrowski, D. Pogocki, G. Strzelczak, J. Mirkowski 16. Second degree team award of Director of the Institute of Nuclear Chemistry and Technology for a series of eight publications summing the achievements of the team in the field of application of activation analysis to verify the content of trace elements in reference materials R. Dybczyński, H. Polkowska-Motrenko, B. Danko, Z. Samczyński, E. Chajduk 17. Third degree team award of Director of the Institute of Nuclear Chemistry and Technology for a set of five publications on surface engineering concerning the modification of steel surface structure and enhancement its usable quality by nitrogen pulsed plasma treatment B. Sartowska, J. Piekoszewski, L. Waliś 18. Diploma for participation in the progress of “Postępy Techniki Jądrowej” on the occassion of 50-ieth anniversary of the Journal I. Grądzka 19. Diploma for participation in the progress of “Postępy Techniki Jądrowej” on the occassion of 50-ieth anniversary of the Journal I. Szumiel 20. Diploma for participation in the progress of “Postępy Techniki Jądrowej” on the occassion of 50-ieth anniversary of the Journal M. Wojewódzka INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 233

INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

I. DEPARTMENT OF NUCLEAR METHODS OF MATERIALS ENGINEERING 1. Laboratory of Materials Research Activity profile: Studies of the structure and properties of materials and historical art objects. Modi- fication of surface properties of materials by means of intense plasma pulses and ions beams. Syn- thesis and studies of new type of materials with predetermined properties (biocidal, fungicidal, sorptional). Characterization of structural properties of materials using SEM (scanning electron microscopy), X-ray diffraction (powder and single crystal). Determination of elemental content of environmental and geological samples, industrial waste materials, historic glass objects and other materials by energy dispersive X-ray fluorescence spectrometry using a radioisotope excitation source as well as a low power X-ray tube and using a 2 kW X-ray tube in total reflection geometry. Determination of radioactive isotope content in environmental samples and historical glass objects by gamma spectrometry. • Scanning electron microscope DSM 942, LEO-Zeiss (Germany) Technical data: spatial resolution – 4 nm at 30 kV, and 25 nm at 1 kV; acceleration voltage – up to 30 kV; chamber capacity – 250x150 mm. Application: SEM observation of various materials such as metals, polymers, ceramics and glasses. Determination of characteristic parameters such as molecule and grain size. • Scanning electron microscope equipped with the attachment for fluorescent microanalysis BS-340 and NL-2001, TESLA (Czech Republic) Application: Observation of surface morphology and elemental analysis of various materials. • Vacuum evaporator JEE-4X, JEOL (Japan) Application: Preparation of thin film coatings of metals or carbon. • Gamma radiation spectrometer HP-Ge, model GS 6020; Canberra-Packard (USA) Technical data: detection efficiency for gamma radiation – 60.2%, polarization voltage – 4000 V, energy resolution (for Co-60) – 1.9 keV, analytical program “GENIE 2000”. Application: Neutron activation analysis, measurements of natural radiation of materials. • Gamma spectrometer in low-background laboratory EGG ORTEC Technical data: HPGe detector with passive shield; FWHM – 1.9 keV at 1333 keV, relative efficiency – 92%. • Total reflection X-ray spectrometer Pico TAX, Institute for Environmental Technologies (Berlin, Germany) Technical data: Mo X-ray tube, 2000 W; Si(Li) detector with FHWM 180 eV for 5.9 keV line; analyzed elements – from sulphur to uranium; detection limits – 10 ppb for optimal range of analyzed elements, 100 ppb for the others. Application: XRF analysis in total reflection geometry. Analysis of minor elements in water (tap, river, waste and rain water); analysis of soil, metals, raw materials, fly ash, pigments, biological samples. • X-ray spectrometer SLP-10180-S, ORTEC (USA) Technical data: FWHM – 175 eV for 5.9 keV line, diameter of active part – 10 mm, thickness of active part of detector – 5.67 mm. Application: X-ray fluorescence analysis. • Coulter Porometer II Coulter Electronics Ltd (Great Britain) Application: Pore size analysis in porous media. 234 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

• Vacuum chamber for plasma research POLVAC Technika Próżniowa Technical data: dimensions – 300x300 mm; high voltage and current connectors, diagnostic windows. Application: Studies on plasma discharge influence on physicochemical surface properties of polymer films, particularly TEM (track-etched membranes). 2. Laboratory of Diffractional Structural Research Activity profile: X-ray diffraction structural studies on metal-organic compounds originating as degradation products of substances naturally occurring in the environment. Röntgenostructural phase analysis of materials. Studies on interactions in a penetrant-polymer membrane system using small angle scattering of X-rays, synchrotron and neutron radiation. Studies of structural changes occurring in natural and synthetic polymers under influence of ionizing radiation applying X-ray diffraction and differential scanning calorimetry. • KM-4 X-ray diffractometer KUMA DIFFRACTION (Poland) Application: 4-cycle diffractometer for monocrystal studies. • CRYOJET - Liquid Nitrogen Cooling System Oxford Instruments Application: Liquid nitrogen cooling system for KM-4 single crystal diffractometer. • HZG4 X-ray diffractometer Freiberger Präzisionsmechanik (Germany) Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphous materials. • URD 6 X-ray diffractometer Freiberger Präzisionsmechanik (Germany) Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphous materials. 3. Sol-Gel Laboratory of Modern Materials Activity profile: The research and production of advanced ceramic materials in the shape of powders, monoliths, fibres and coatings by classic sol-gel methods with modifications – IChTJ Process or by CSGP (Complex Sol-Gel Method) are conducted. Materials obtained by this method are the following powders: alumina and its homogeneous mixtures with Cr2O3, TiO3, Fe2O3, MgO+Y2O3, MoO3, Fe, Mo, Ni and CaO, CeO2, Y2O3 stabilized zirconia, β and β’’ aluminas, ferrites, SrZrO3, ceramic superconductors, type YBCO (phases 123, 124), BSCCO (phases 2212, 2223), NdBa2Cu3Ox, their nanocomposites, Li-Ni-Co-O spinels as cathodic materials for Li rechargeable batteries and fuel cells MCFC, BaTiO3, LiPO4, Li titanates: spherical for fusion technology, irregularly shaped as superconductors and cathodic materials, Pt/WO3 catalyst. Many of the mentioned above systems, as well as sensors, type SnO2, were prepared as coatings on metallic substrates. Bioceramic materials based on calcium phosphates (e.g. hydroxyapatite) were synthesized in the form of powders, monoliths and fibres. • DTA and TGA thermal analyser OD-102 Paulik-Paulik-Erdey, MOM (Hungary) Technical data: balance fundamental sensitivity – 20-0.2 mg/100 scale divisions, weight range – 0-9.990 g, galvanometer sensitivity – 1x10–10 A/mm/m, maximum temperature – 1050oC. Application: Thermogravimetric studies of materials up to 1050oC. • DTA and TGA thermal analyser 1500 MOM (Hungary) Technical data: temperature range – 20-1500oC; power requirements – 220 V, 50 Hz. Application: Thermal analysis of solids in the temperature range 20-1500oC. • Research general-purpose microscope Carl Zeiss Jena (Germany) Technical data: General purpose microscope, magnification from 25 to 2500 times, illumination of sample from top or bottom side. • Metallographic microscope EPITYP-2, Carl-Zeiss Jena (Germany) Technical data: magnification from 40 to 1250 times. Application: Metallographic microscope for studies in polarized light illumination and hardness measurements. INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 235

• Laboratory furnace CSF 12/13, CARBOLITE (Great Britain) Application: Temperature treatment of samples in controlled atmosphere up to 1500oC with automatic adjustment of final temperature, heating and cooling rate.

II. DEPARTMENT OF RADIOISOTOPE INSTRUMENTS AND METHODS Laboratory of Industrial Radiometry Activity profile: Research and development of non-destructive methods and measuring instruments utilizing physical phenomena connected with the interaction of radiation with matter: development of new methods and industrial instruments for measurement of physical quantities and analysis of chemical composition; development of measuring instruments for environmental protection (dust monitors, radon meters); implementation of new methods of calibration and signal processing (multivariate models, artificial neural networks); designing, construction and manufacturing of measuring instruments and systems; testing of industrial and laboratory instruments. • Multichannel analyser board with software for X and γ-ray spectrometry Canberra • Function generator FG-513, American Reliace INC

III. DEPARTMENT OF RADIOCHEMISTRY 1. Laboratory of Coordination and Radiopharmaceutical Chemistry Activity profile: Preparation of novel technetium(I, III, V) complexes with chelating ligands (mono- and bifunctional), labelled with 99mTc, as potential diagnostic radiopharmaceuticals or their precursors. Studying of their hydrophilic-lipophilic properties, structure and their interactions with peptides. Also analogous rhenium(I) complexes are synthesized and studied. Novel platinum and palladium complexes with organic ligands, analogs of cisplatin, are synthesized and studied as potential antitumor agents. Solvent extraction separation of trivalent actinides from lanthanides is studied, directed towards nuclear waste treatment. Studies on chemical isotope effects of metal ions – search of correlations between isotope separation factor and structure of species exchanging the isotopes in two-phase chemical systems. (For the research equipment, common for both Labo- ratories, see below.) 2. Laboratory of Heavy Elements Activity profile: Synthesis of novel macrocyclic complexes of 47Sc, 103m,105Rh and 212Bi radionuclides – potential precursors for therapeutic radiopharmaceuticals. Elaboration of new methods for astatination (211At) of biomolecules via metal complexes. Design of new medically important radionuclide generators, e.g. 82Sr/82Rb, 103Ru/103mRh, 44Ti/44Sc. Structural studies on the complexes and solvates of heavy p-block elements in the solid state and in solution. • Spectrometric set ORTEC Multichannel analyser, type 7150, semiconductor detector Application: Measurements and identification of γ- and α-radioactive nuclides. • Gas chromatograph 610, UNICAM (England) Application: Analysis of the composition of mixtures of organic substances in the gas and liquid state. • High performance liquid chromatography system Gradient HPLC pump L-7100, Merck (Germany) with γ-radiation detector, INCT (Poland) Application: Analytical and preparative separations of radionuclides and/or various chemical forms of radionuclides. • High performance liquid chromatography system Gradient HPLC pump LC-10ADvp, with a UV-VIS detector SPD-10Avp/10AVvp, Shimadzu (Japan) Application: Analytical and preparative separations of radionuclides and/or various chemical forms of radionuclides. • Capillary electrophoresis system PrinCE Technologies with a UV-VIS detector (Bischoff Lambda 1010) and a radiometric detector Activity Gauge type Tc-99m (INCT, Poland) Application: Analytical separation of various radiochemical and chemical species, in particular, charged ones. 236 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

• Gamma isotope TLC analyser SC-05 (INCT, Poland) Application: Measurements of gamma radioactivity distribution along thin-layer-chromatography plates and electrophoretic strips. • UV-VIS spectrophotometer DU 68, Beckman (Austria), modernized and computerized Application: Recording of electronic spectra of metal complexes and organic compounds in solution. Analytical determination of the concentration of these compounds. • FT-IR spectrophotometer EQUINOX 55, Bruker (Germany) Application: Measurements of IR spectra of metal complexes and other species in the solid state and in solution.

IV. DEPARTMENT OF NUCLEAR METHODS OF PROCESS ENGINEERING 1. Laboratory for Flue Gases Analysis

Activity profile: Experimental research connected with elaboration of removal technology for SO2 and NOx and other hazardous pollutants from flue gases. • Ultrasonic generator of aerosols TYTAN XLG • Gas chromatograph Perkin-Elmer (USA) • Gas analyser LAND

Application: Determination of SO2, NOx, O2, hydrocarbons, and CO2 concentrations. • Impactor MARK III Andersen (USA) Application: Measurement of aerosol particle diameter and particle diameter distribution. 2. Laboratory of Stable Isotope Ratio Mass Spectrometry Activity profile: Study of isotope ratios of stable isotopes in hydrogeological, environmental, medical and food samples. • Mass spectrometer DELTAplus Finnigan MAT (Bremen, Germany) Technical data: DELTAplus can perform gas isotope ratio measurements of H/D, 13C/12C, 15N/14N, 18O/16O, 34S/32S. Application: For measurements of hydrogen (H/D) and oxygen (18O/16O) in water samples with two automatic systems: H/Device and GasBench II. The system is fully computerized and controlled by the software ISODAT operating in multiscan mode (realtime). The H/Device is a preparation system for hydrogen from water and volatile organic compounds determination. Precision of hydrogen isotope ratio determination is about 0.5‰ for water. The GasBench II is a unit for on-line oxygen isotope ratio measurements in water samples by “continuous flow” techniques. With GasBench II, water samples (0.5 ml) can be routinely analyzed with a precision and accuracy of 0.05‰. The total volume of water sample for oxygen and hydrogen determination is about 2 ml. • Elemental Analyzer Flash 1112 NCS Thermo Finnigan (Italy) Application: For measurement of carbon, nitrogen and sulphur contents and their isotope composition in organic matter (foodstuff and environmental samples). • Gas chromatograph mass spectrometer GC MS-QP 5050A, GC-17A, Shimadzu (Japan) Technical data: capillary column – SPB 5, HP-5MS, SUPELCOWAX™-10. 3. Radiotracers Laboratory Activity profile: Radiotracer research in the field of: environmental protection, hydrology, underground water flow, sewage transport and dispersion in rivers and sea, dynamic characteristics of industrial installations and waste water treatment stations. • Heavy lead chamber (10 cm Pb wall thickness) for up to 3.7x1010 Bq (1 Ci) radiotracer activity preparations in liquid or solid forms • Field radiometers for radioactivity measurements INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 237

• Apparatus for liquid sampling • Turner fluorimeters for dye tracer concentration measurements • Automatic devices for liquid tracer injections • Liquid-scintillation counter Model 1414-003 ”Guardian”, Wallac-Oy (Finland) Application: Extra low-level measurements of α and β radionuclide concentrations, especially for H-3, Ra-226, Rn-222 in environmental materials, e.g. underground waters, surface natural waters; in other liquid samples as waste waters, biological materials, mine waters, etc. 4. Membrane Laboratory Activity profile: Research in the field of application of membranes for radioactive waste processing, separation of isotopes and gas separation. • Membrane distillation plant for concentration of solutions Technical data: output ~0.05 m3/h, equipped with spiral-wound PTFE module G-4.0-6-7 (SEP GmbH) with heat recovery in two heat-exchangers. • Ultrafiltration plant equipped with replaceable ceramic multichannel modules • US 150 laboratory stand (Alamo Water) for reverse osmosis tests Technical data: working pressure – up to 15 bar, flow rate – 200 dm3/h, equipped with two RO modules. • Laboratory stand with different ceramic replaceable tubular UF modules • Laboratory set-up for small capillary and frame-and-plate microfiltration and membrane distillation module examination (capillary EuroSep, pore diameter 0.2 μm and frame-and-plate the INCT modules) • The system for industrial waste water pretreatment Technical data: pressure – up to 0.3 MPa; equipped with ceramic filters, bed Alamo Water filters with replaceable cartridge (ceramic carbon, polypropylene, porous or fibrous) and frame-and-plate microfiltration module. • Gas separation system equipped with UBE capillary module • Laboratory stand for pervaporation and vacuum membrane distillation tests • Automatic refractometer J357, Rudolph Technologies Inc. (USA)

Technical data: nD=1.29-1.70 , 0-95 BRIX. • Spectrophotometer HACH 2000 (Germany)

V. DEPARTMENT OF RADIATION CHEMISTRY AND TECHNOLOGY 1. Laboratory of Radiation Modified Polymers Activity profile: Modification of polymers by ionizing radiation. Radiation-induced radicals in polymers. Optimization of mechanical and chemical properties of biocompatible materials following electron beam and gamma irradiation, biological application of polymers. Nanocomposites and nanofillers modified by ionizing radiation. • Extruder PLV-151, BRABENDER-DUISBURG (Germany) Technical data: Plasti-Corder consists of: driving motor, temperature adjustment panel, thermostat, crusher, mixer, extruder with set of extrusion heads (for foils, rods, sleevs, tubes), cooling tank, pel- leting machine, collecting device. Application: Preparation of polymer samples. • Equipment for mechanical testing of polymer samples INSTRON 5565, Instron Co. (England) Technical data: high performance load frame with computer control device, equipped with Digital Signal Processing and MERLIN testing software; max. load of frame is 5000 N with accuracy better than 0.4% in full range; max. speed of testing 1000 mm/min in full range of load; total crosshead travel – 1135 mm; space between column – 420 mm; the environmental chamber 319-409 (internal dimensions – 660x230x240 mm; temperature range – from -70 to 250oC). Application: The unit is designed for testing of polymer materials (extension testing, tension, flexure, peel strength, cyclic test and other with capability to test samples at low and high temperatures). 238 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

• Viscosimeter CAP 2000+H, Brookfield (USA) Technical data: range of measurements – 0.8-1500 Pa*s, temperature range – 50-235oC, cone rotation speed – 5-1000 rpm, sample volume – 30 μl. Computer controlled via Brookfield CALPCALC® software. Application: Viscosity measurements of liquids and polymer melts. • Differential scanning calorimeter MDSC 2920 CE, TA Instruments Technical data: equipped with liquid nitrogen cooling adapter (LNCA) for 60 l of liquid nitrogen and sample encapsulating press for open or hermetically sealed pans. Module for Modulated DSC™ is included. Working temperature – from -150oC with the LNCA to 725oC. Application: Determines the temperature and heat flow associated with material phase transitions as a function of time and temperature. It also provides qualitative data on endothermic (heat absorption) and exothermic (heat evolution) processes of materials during physical transitions that are caused by phase changes, melting, oxidation, and other heat-related changes. • Processor tensiometer K100C Technical data: supplied with the thermostatable sample vessel. Working temperature is from -10 to +100oC. The height of the sampler carrier is adjusted with the help of a high-precision motor. The balance system is automatically calibrated by a built-in reference weight with a high precision. Resolutions of measurement is 0.01 mN/m. Application: Surface and interfacial tension measurement of liquids – Du Noüy Ring method and Dynamic Wilhelmy method with range 1-1000 mN/m; dynamic contact angle measurements; surface energy calculations on solids, powders, pigments, fibers, etc.; sorption measurements with the Washburn method for determining the surface energy of a powder-form solid. Controlled by LabDesk™ software. • Spectrophotometer UV-VIS UNICAM SP 1800 with linear recorder UNICAM AR 25 Technical data: Wavelength – 190-850 nm. • Equipment for gel electrophoresis System consists of: horizontal electrophoresis apparatus SUBMINI Electrophoresis Mini-System, transilluminator UV STS-20M JENCONS (United Kingdom), centrifuge EBA 12 Hettich/Zen- trifugen, microwave oven KOR 8167 Daewoo. • Melt flow tester ZWICK 4105, Zwick GmbH (Germany) Technical data: temperature of measurements – 150, 190 and 230oC; press load – 2.16 and 5.00 kg; manual operating. Application: Determination of standard values of melt-mass flow rate (MFR) of the thermoplastic materials (polymers) under specified conditions of temperature and load (according to standards: PN-EN ISO 1133:2005, ASTM 1328); comparison of rheological properties of polymers, including filled materials; comparison of degree of degradation; testing of catalogue data. • Termogravimetric analyser TGA Q500, TA Instruments Technical data: equipped with responsive low-mass furnace, ultra-sensitive thermobalance, efficient horizontal purge gas system (with mass flow control), two sets of pans (platinum or ceramic), two purging gases: nitrogen or air; wide range of heating velocity – to 50oC/min, max. temperature – 1000oC, max. sample weight – 200-1000 mg; software: Advantage for Q Series, Thermal Analysis. Application: Determination of thermal stability, velocity of thermal destructions, rate of oxidation at eleven temperatures; determination of water, other solvents, minerals and ash contents. 2. Radiation Sterilization Pilot Plant of Medical Devices and Tissue Grafts Activity profile: Research and development studies concerning new materials for manufacturing single-use medical devices (resistant to radiation up to sterilization doses). Elaboration of monitoring systems and dosimetric systems concerning radiation sterilization processing. Introducing specific procedures based on international recommendations of ISO 13485:2003 and ISO 11137:2006 standards. Sterilization of medical utensils, approx. 70 million pieces per year. • Electron beam accelerator UELW-10-10, NPO TORIJ (Moscow, Russia) Technical data: beam energy – 10 MeV, beam power – 10 kW, supply power – 130 kVA. Application: Radiation sterilization of medical devices and tissue grafts. INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 239

• Spectrophotometer UV-VIS Model U-1100, Hitachi Technical data: wavelength range – 200-1100 nm; radiation source – deuterium discharge (D2) lamp, and tungsten-iodine lamp. • Spectrophotometer UV-VIS Model SEMCO S/EC Technical data: wavelength range – 340-1000 nm, radiation source – halogen lamp. Application: Only for measurements of dosimetric foils. • Bacteriological and culture oven with temperature and time control and digital reading Incudigit 80L Technical data: maximum temperature – 80oC, homogeneity – ±2%, stability – ±0.25%, thermometer error – ±2%, resolution – 0.1oC. 3. Laboratory of Radiation Microwave Cryotechnique Activity profile: Radiation processes in solids of catalytic and biological importance: stabilization of cationic metal clusters in zeolites, radical reactions in polycrystalline polypeptides, magnetic properties of transition metals in unusual oxidation states; radical intermediates in heterogeneous catalysis. • Electron spin resonance (ESR) Q-band spectrometer Bruker Elexsys E-500, equipped with continuous flow helium cryostat Oxford Instruments CF935 O and DICE cw ENDOR/TRIPLE unit Bruker E-560 with rf amplifier 10 kHz-220 MHz. • Electron spin resonance (ESR) X-band spectrometer Bruker ESP-300, equipped with: frequency counter Hewlett-Packard 5342A, continuous flow helium cryostat Oxford Instruments ESR 900, continuous flow nitrogen cryostat Bruker ER 4111VT, ENDOR-TRIPLE unit Bruker ESP-351. Application: Studies of free radicals, paramagnetic cations, atoms and metal nanoclusters as well as stable paramagnetic centres. • Spectrophotometer UV-VIS LAMBDA-9, Perkin-Elmer Technical data: wavelength range – 185-3200 nm, equipped with 60 nm integrating sphere. 4. Pulse Radiolysis Laboratory Activity profile: Studies of charge and radical centre transfer processes in thioether model compounds of biological relevance in liquid phase by means of time-resolved techniques (pulse radiolysis and laser flash photolysis) and steady-state γ-radiolysis. • Accelerator LAE 10 (nanosecond electron linear accelerator) INCT (Warszawa, Poland) Technical data: beam power – 0.2 kW, electron energy – 10 MeV, pulse duration – 7-10 ns and about 100 ns, repetition rate – 1, 12.5, 25 Hz and single pulse, pulse current – 0.5-1 A, year of installation 1999. Application: Research in the field of pulse radiolysis. • Gas chromatograph GC-14B, Shimadzu (Japan) Specifications: two detectors: thermal conductivity detectors (TCD) and flame ionization detector (FID). Column oven enables installation of stainless steel columns, glass columns and capillary columns. Range of temperature settings for column oven: room temperature to 399oC (in 1oC steps), rate of temperature rise varies from 0 to 40oC/min (in 0.1oC steps). Dual injection port unit with two lines for simultaneous installation of two columns. Application: Multifunctional instrument for analysis of final products formed during radiolysis of sulphur and porphyrin compounds and for analysis of gaseous products of catalytic reactions in zeolites. • Dionex DX500 chromatograph system Dionex Corporation Specifications: The ED40 electrochemical detector provides three major forms of electrochemical detection: conductivity, DC amperometry and integrated and pulsed amperometry. The AD20 absorbance detector is a dual-beam, variable wavelength photometer, full spectral capability is provided by two light sources: a deuterium lamp for UV detection (from 190 nm) and a tungsten lamp for VIS wavelength operation (up to 800 nm). The GP40 gradient pump with a delivery system designed to blend and pump mixtures of up to four different mobile phases at precisely controlled flow rates. The system can be adapted to a wide range of analytical needs by choice of the chromatography columns: AS11 (anion exchange), CS14 (cation exchange) and AS1 (ion exclusion). 240 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

Application: The state-of-the-art analytical system for ion chromatography (IC) and high-performance liquid chromatography (HPLC) applications. Analysis of final ionic and light-absorbed products formed during radiolysis of sulphur compounds. The system and data acquisition are controlled by a Pentium 100 PC computer. • Digital storage oscilloscope 6051A Wave Runner, LeCroy Specifications: Bandwidth – 500 MHz; rise time – 750 ps; sample rate - up to 5 Gs/s (by combining 2 channels); acquisition memory – 16 Mpt with 8 Mpt per channel; sensitivity – 2 mV/div to 10 V/div; fully variable, fully programmable; standard ports – 10/100Base-T Ethernet, Parallel, GPiB –IEEE 488.2, USB 2.0 (5), RS-232, SVGA Video Out, Audio in/out; Windows XP Professional operating system. Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulse radiolysis system dedicated to the nanosecond electron linear accelerator (LAE 10). The multiple time scales can be generated by a computer from a single kinetic trace originating from DSO since the oscilloscope produces a sufficient number of time points (up to 16 M points record length). • Digital storage oscilloscope 9354AL, LeCroy Specifications: Bandwidth DC to 500 MHz; sample rate – 500 Ms/s up to 2 Gs/s (by combining 4 channels); acquisition memory – up to 8 Mpt with 2 Mpt per channel; time/div range – 1 ns/div to 1000 s/div; sensitivity – 2 mV/div to 5 V/div; fully variable, fully programmable via GPIB and RS-232C. Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulse radiolysis system dedicated to the nanosecond laser flash photolysis. The multiple time scales can be generated by a computer from a single kinetic trace originating from DSO since the oscilloscope produces a sufficient number of time points (up to 8 M points record length). • Digital storage oscilloscope 9304C, LeCroy Specifications: Bandwidth DC to 200 MHz; sample rate – 100 Ms/s up to 2 Gs/s (by combining 4 channels); acquisition memory – up to 200 kpt per channel; time/div range – 1 ns/div to 1000 s/div; sensitivity – 2 mV/div to 5 V/div; fully variable. Application: Digital oscilloscope (DO) is used in pulse radiolysis system dedicated to the nanosecond electron linear accelerator (LAE 10). • Nd:YAG laser Surelite II-10, Continuum (USA) Specifications: energy (mJ) at 1064 nm (650), 532 nm (300), 355 nm (160) and 266 nm (80); pulse width – 5-7 ns (at 1064 nm) and 4-6 ns (at 532, 355 and 266 nm); energy stability – 2.5-7%; can be operated either locally or remotely through the RS-232 or TTL interface. Application: A source of excitation in the nanosecond laser flash photolysis system being currently under construction in the Department. • Potentiostat/Galvanostat VersaStat II Princeton Applied Research (USA) Specifications: Power amplifier compliance voltage single channel – ±20 V, maximum current – ±200 mA, rise time – 100 μs, slew rate – 1 V/μs; system performance: minimum timebase – 100 μs, minimum potential step – 250 μV, noise and ripple <50 μV rms typically, minimum current range – 1 μA (hardware), minimum current range – 100 nA (software), minimum current resolution – 200 pA, drift – vs. time <50 μV/°C vs. time: <200 μV/week. iR compensation: current interrupt 12-bit potential error correction total int. time <50-2000 μs. Accuracy: applied potential – 0.2% of reading ±2 mV, applied current – 0.2% of full-scale current. Computer interface: GPIB IEEE-488, RS-232. Differential electrometer: input bias current <50 pA at 25oC, typically <20 pA at 25oC. Max. voltage range – ±2 V, max. input voltage differential – ±10 V. Bandwidth – -3 dB at>4 MHz. Offset voltage <100 μV. Offset temperature stability <5 μV/°C. Common mode rejection >70 dB at 100 Hz and >60 dB at 100 kHz. Input impedance >1010 Ω, typically 1011 Ω in parallel with <50 pF. • Monochromator/spectrograph MSH3001 LOT-Oriel Group Specifications: 260 mm, f/3.9 motorized with two optical output parts; 0.15 nm resolution with a 12001/mm grating, fully automated (IEE488, RS232) with integrated electronic shutter; supports 3 gratings simultaneously (300 l/mm 500 nm centered, 1200 l/mm 350 nm centered, 1200 l/mm 750 centered). Application: Dedicated to the nansecond electron linear accelerator (LAE 10)/ pulse radiolysis set-up. INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 241

• iStar ICCD Detector DH720-18F-03, Andor Technology Specifications: number of pixels 1024x256, active pixels 690x256; CCD front illuminated; dynamic range – 16 bits; thermoelectric cooling – -10oC; fiber optic coupling to 18 mm MCP image intensi- fier; spectral range – 18-850 nm; min. optical gate – 5 ns; remote control. Application: Upgrade dedicated to the nanosecond electron linear accelerator (LAE 10)/ pulse radiolysis set-up. It gives possibilities in the research: collecting all spectra in one shot. 5. Research Accelerator Laboratory Activity profile: The Laboratory is equipped with accelerators providing electron beams which make capable to perform irradiation of the investigated objects within a wide range of electron energy from 100 keV to 13 MeV and an average beam power from 0.1 W to 20 kW, as well as with Co-60 gamma sources with an activity from 1.9x1010 to 1.3x1014 Bq and a dose rate from 0.015 to 1 kGy/h. The described above irradiators are completed in a unique in world scale set of equipments which can be applied in a wide range of electron beam and gamma-ray research and radiation processing. • Accelerator ILU-6 INP (Novosibirsk, Russia) Technical data: beam power – 20 kW, electron energy – 0.7-2 MeV. Application: Radiation processing. • Linear electron accelerator LAE 13/9, Institute of Electro-Physical Equipment (Russia) Technical data: electron energy – 10-13 MeV; electron beam power – 9 kW. Application: Radiation processing. • Cobalt source I Issledovatel (Russia) Technical data: 32 sources, actual dose rate – 1 kGy/h. Application: Radiation research. • Cobalt source II Mineyola 1000, INR (Świerk, Poland) Technical data: 8 rods with an initial activity of 2.66x1013 Bq, actual dose rate – 0.42 kGy/h. Application: Radiation research. • Electron accelerator AS-2000 (the Netherlands) Technical data: energy – 0.1-2 MeV, max. beam current – 100 μA. Application: Irradiation of materials. • Spectrometer DLTS-82E, SEMITRAP (Hungary) Application: Research in radiation physics of semiconductors. • Argon laser ILA-120, Carl Zeiss (Jena, Germany) Application: Measurements of optical properties. • Spectrometer DLTS-81 (Hungary) Application: Measurements of semiconductor properties. • Argon laser LGN-503 (Russia) Application: Measurements of optical properties.

VI. DEPARTMENT OF ANALYTICAL CHEMISTRY 1. Laboratory of Spectral Atomic Analysis Activity profile: atomic absorption and emission spectroscopy, studies on interference mechanisms, interpretation of analytical signals, service analysis. • Atomic absorption spectrometer SH-4000, Thermo Jarrell Ash (USA); equipped with a 188 Controlled Furnace Atomizer (CTF 188), Smith-Heftie background correction system and atomic vapor (AVA-440) accessory. 242 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

Application: For analyses of samples by flame and furnace AAS. • Atomic absorption spectrometer SP9-800, Pye Unicam (England); equipped with SP-9 Furnace Power Supply, PU-9095 data graphics system, PU-9095 video furnace programmer and SP-9 furnace autosampler. Application: For analyses of samples by flame and furnace AAS. • Atomic absorption spectrometer SOLAR M6 MK II (Thermo Electron Corporation), equipped with: graphite furnace GF 95 with D2 and Zeeman background correction system, autosampler FS 95 and hydride and cold vapour generator. Application: For analyses of samples by flame and furnace AAS. 2. Laboratory of Neutron Activation Analysis Activity profile: The sole laboratory in Poland engaged for 40 years in theory and practice of neutron activation analysis in which the following methods are being developed: reactor neutron activation analysis (the unique analytical method of special importance in inorganic trace analysis), radiochemical separation methods, ion chromatography. The laboratory is also the main Polish producer of CRMs and the provider for Proficiency Testing exercises. • Laminar box HV mini 3, Holten (Denmark) Technical data: air flow rate 300 m3/h. Application: Protection of analytical samples against contamination. • Ion chromatograph 2000i/SP, Dionex (USA) Technical data: data evaluating program AI-450, ion exchange columns of type Dionex Ion Pac, conductivity detector, UV/VIS detector.

Application: Analyses of water solutions, determination of SO2, SO3 and NOx in flue gases and in air, determination of metals in biological and environmental samples. • HPGe detector, well-type CGW-3223, Canberra, coupled with analog line (ORTEC) and multichannel gamma-ray analyser TUKAN Application: Instrumental and radiochemical activation analysis. • Coaxial HPGe detector POP-TOP, ORTEC (USA), coupled with analog line (ORTEC) and multichannel gamma-ray analyser TUKAN • HPGe detector, well-type CGW-5524, Canberra, coupled with multichannel gamma-ray analyser (hardware and software) Canberra Application: Instrumental and radiochemical activation analysis. • Analytical balance Sartorius BP2 215 Application: For weighing sample of mass >10 mg to 220 g. • Analytical micro-balance Sartorius MC5 Application: Preparation of mono- and multi-elemental standards as well as for weighing small mass samples, less than 10 mg. • Balance WPX 650, RADWAG (Poland) Application: For weighing sample of mass >10 mg to 650 g. • Liquid Scintillation Analyser TRI-CARB 2900TR, Packard BioScience Company Application: α- and β-ray measurements. • Planetary Ball Mill PM 100, Retsch Application: Grinding and mixing: soft, medium hard to extremly hard, brittle or fibrous materials. • Balance-drier ADS50, AXIS (Poland) INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 243

Application: Determination of mass and humidity of samples. • Microwave digestion system UnicleverTMII, PLAZMATRONIKA (Poland) Application: Microwave digestion of samples. • Microwave digestion system BM-1S/II, PLAZMATRONIKA (Poland) Application: Microwave digestion of samples. • Homogenizer INCT (Poland) Application: Homogenization of the material used for preparation of CRMs. • Peristaltic pump REGLO ANALOG MS-4/6-100, ISMATEC (Switzerland) Application: Regulation of flow of eluents during elution process. 3. Laboratory of Chromatography Activity profile: Development of HPLC methods for determination of environmental pollutants, application of HPLC and ion-chromatography monitoring of degradation organic pollutants in waters and wastes using ionizing radiation, development of chromatographic methods, preconcen- tration of organic environmental pollutants, development of chromatographic methods of identification of natural dyes used for ancient textiles. • Apparatus for biological oxygen demand determination by respirometric method and dissolved oxygen measurement method WTW-Wissenschaftlich-Technische Wersttätten (Germany) Application: Analyses of water and waste water samples. • Apparatus for chemical oxygen demand determination by titrimetric method Behr Labor-Technik (Germany) Application: Analyses of water and waste water samples. • Setup for solid phase-extraction (vacuum chamber for 12 columns and vacuum pump) Application: Analyses of water and waste water samples. • Shimadzu HPLC system consisting of: gradient pump LC-10AT, phase mixer FCV-10AL, diode- -array detector SPD-M10A, column thermostat CTO-10AS Application: Analyses of natural dyes, radiopharmaceuticals, water and waste water samples. • Laboratory ozone generator 301.19, Erwin Sander Elektroapparatebau GmbH (Uetze-Eltze, Germany) Application: Ozone production for degradation of pollutants in waste water samples. 4. Laboratory of General Analysis Activity profile: Preparation and application of new chelating sorbents to the separation of metal traces from environmental materials for their determination by atomic absorption spectrometry, speciation analysis, service analysis. • Spectrophotometer PU8625 Series UV/Visible, Philips Technical data: wavelength range – 200-1100 nm. Application: Measurements of absorbance in spectrophotometric analysis. • Spectrophotometer UV-160, Shimadzu (Japan) Technical data: wavelength range – 200-1100 nm, with automatic baseline correction and graphic printer. Application: Routine spectrophotometric analysis and research works.

VII. DEPARTMENT OF RADIOBIOLOGY AND HEALTH PROTECTION • Equipment for electrophoretic analysis of DNA CHEF III, BIO-RAD (Austria) Application: Analysis of DNA fragmentation as a result of damage by various physical and chemical agents. • Microplate reader 244 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

ELISA, ORGANON TEKNICA (Belgium) Application: For measurement of optical density of solutions in microplates. • Hybridization oven OS-91, BIOMETRA (Germany) Technical data: work temperatures from 0 to 80oC; exchangeable test tubes for hybridization. Application: For polymerase chain reaction (PCR). • Spectrofluorimeter RF-5000, Shimadzu (Japan) Application: For fluorimetric determinations. • Transilluminator for electrophoretic gels Biodoc, BIOMETRA (Great Britain) Application: For analysis of electrophoretic gels. • Laminar flow cabinet NU-437-400E, Nu Aire (USA) Application: For work under sterile conditions. • Liquid scintillation counter LS 6000LL, BECKMAN (USA) Application: For determinations of radioactivity in solutions. • Research microscope universal NU, Carl Zeiss Jena (Germany) Application: For examination of cytological preparations. Comments: Universal microscope for transmission and reflected light/polarized light. Magnifica- tion from 25x to 2500x. Possibility of applying phase contrast. • Incubator T-303 GF, ASSAB (Sweden) Technical data: 220 V, temperature range – 25-75oC. Application: For cell cultures under 5% carbon dioxide. • Incubator NU 5500E/Nu Aire (USA) Technical data: 220 V, temperature range from 18 to 55oC. Application: For cell cultures under 0-20% carbon dioxide. • Laminar flow cabinet V-4, ASSAB (Sweden) Application: For work under sterile conditions. • Image analysis system Komet 3.1, Kinetic Imaging (Great Britain) Application: For comet (single cell gel electrophoresis) analysis. • ISIS 3 Metasystem (Germany) Application: Microscopic image analysis system for chromosomal aberrations (bright field and fluorescence microscopy). • Spectrophotometer Cary 50 UV-Vis, Varian (USA) Application: For spectrophotometric determination. • Luminometer TD20/20, Turner Biosystems (USA) Application: To run bioluminescent assays, such as reporter gene assays, as well as chemilumines- cent assays. • PTC-1148 MJ Mini Termal Cycler BIO-RAD (USA) Application: For in vitro DNA amplification by polymerase chain reaction. • Sunrise™ Absorbance Reader Tecan (Austria) INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 245

Application: ELISA microplate reader. • Fluorescence microscope with automatic table and image analysis system including metaphase finder, Metafer 3,4 and ISIS3 Zaiss, Metasystems (Germany) Application: For aberration assay, comet assay, gamma H2AX assay used in biodosimetry and radiobiological studies. • 7500 Real-Time PCR System Applied Biosystems (USA) Application: Amplification, detection and quantification of nucleic acids.

VIII. LABORATORY FOR DETECTION OF IRRADIATED FOOD Activity profile: Detection of irradiated foods. European standards (CEN), adapted as analytical methods to be routinely used in the Laboratory, are based on electron paramagnetic resonance (EPR/ESR) spectroscopy, photostimulated luminescence (PSL) and thermoluminescence measurements (TL). The research work is focused mainly on the development of five detection methods based on the above three techniques and the enlargement of their ability of the detection of irradiation in the variety of foodstuffs. The quality assurance system was adapted in the Laboratory in 1999 and in 2006 was actualized and documented in agreement with the PN-EN 1SO/IEC 17025:2005 standard. Actually Laboratory possesses Accreditation Certificate of Testing Laboratory nr AB 262 issued by the Polish Centre for Accreditation and valid until 24.10.2010. • Thermoluminescence reader TL-DA-15 Automated, Risoe National Laboratory (Denmark) Technical data: turntable for 24 samples, heating range – 50÷500oC, heating speed – 0.5÷10.0oC/s, optical stimulated luminescence (OSL) system. Application: Detection of irradiated foods containing silicate minerals, e.g. spices, vegetables shrimps etc., research work on irradiated foods. • Compact EPR spectrometer EPR 10-MINI, St. Petersburg Instruments Ltd. (Russia) Technical data: sensitivity – 3x1010, operating frequency (X band) – 9.0-9.6 GHz, max. microwave power – 80 mW, magnetic field range – 30-500 mT, frequency modulation – 100 kHz. Application: Detection of irradiated foods, bone and alanine dosimetry, research work on irradiated foods and bone tissues. • Pulsed photostimulated luminescence system SURRC (United Kingdom) Technical data: pulsed light source – diodes IR LED; detector – photomultiplier ETL; pulse on and off periods – 15 μs; sample holder – 50 mm diameter disposable Petri dishes; set up – sample chamber and detector head assembly, contol unit, on line computer, optional. Application: Irradiated food screening system.

IX. EXPERIMENTAL PLANT FOR FOOD IRRADIATION 1. Microbiological Laboratory Activity profile: optimization of food irradiation process by microbiological analysis. • Sterilizer ASUE, SMS (Warszawa, Poland) Application: Autoclaving of laboratory glass, equipment, and microbiological cultures. • Fluorescence microscope BX, Olimpus (Germany) Application: Quantitative and qualitative microbiological analysis. 2. Experimental Plant for Food Irradiation Activity profile: Development of new radiation technologies for the preservation and hygienization of food products. Development and standarization of the control system for electron beam processing of food. Development of analytical methods for the detection of irradiated food. Organization of consumer tests with radiation treated food products. • Accelerator ELEKTRONIKA (10 MeV, 10 kW) UELW-10-10, NPO TORIJ (Moscow, Russia) Application: Food irradiation. 246 INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

A Grötzschel Rainer 149 Anuszewska Elżbieta 81 Guzik Grzegorz P. 55, 57, 60 Apel Pavel Yu. 145 H B Harasimowicz Marian 134 Bańkowski Krzysztof 77 Herdzik Irena 86 Barlak Marek 143, 148, 149 Hoser Grażyna 27 Bartoś Barbara 68 I Bilewicz Aleksander 65, 66, 68, 69 Iller Edward 102 Bobrowski Krzysztof 21 Bocheńska Katarzyna 149 J Boczkowska Anna 155 Jaegermann Zbigniew 27 Bojanowska-Czajka Anna 51 Jahreis Gerhard 123 Brykała Marcin 102 Jakowiuk Adrian 157 Brzozowska Kinga 120, 121 Jaskóła Marian 146 Brzóska Kamil 117, 122, 123 Jaworska Agnieszka 137 Buczkowski Marek 150 K Bułka Sylwester 127, 158 Buraczewska Iwona 115, 122, 123 Kciuk Gabriel 21 Khayet Mohamed 134 C Kierzek Joachim 149, 150 Chajduk Ewelina 88, 90, 93 Kocia Rafał 23 Chmielewska Dagmara K. 152 Kolitsch Andreas 149 Chmielewski Andrzej G. 127, 128, 130 Korman Andrzej 146 Chóścicka Anna 27 Kornacka Ewa M. 38 Chwastowska Jadwiga 98 Koźmiński Przemysław 74, 77 Cieśla Krystyna 43, 46 Krajewski Seweryn 66 Cook Andrew R. 23 Kruszewski Marcin 117, 118, 119 Czerska Elżbieta 90, 96 Kučera Jan 88 Czub Joanna 115 Kuehn Thorsten 146 D L Danko Bożena 88, 96 Laubsztejn Magdalena 55 Dąbrowska Maria 98 Leciejewicz Janusz 105, 106, 107, 108, 110, 111 Dąbrowski Ludwik 148 Lehner Katarzyna 55, 60 Degen Christian 123 Lewandowska-Siwkiewicz Hanna 119 Deptuła Andrzej 100, 102, 153 Lewandowska-Szumieł Małgorzata 27 Dobrowolski Andrzej 128, 130, 136 Loktionova Natalia S. 71 Drzewicz Przemysław 51 Lo Presti Roberto 153 Dudek Jakub 90, 98 Ł Dybczyński Rajmund 88, 96 Łada Wiesława 100, 102, 153 Dźwigalski Zygmunt 158 Łukasiewicz Andrzej 152 F Łyczko Krzysztof 43, 73 Fabisiak Sławomir 53 M Fuente Julio R. De la 21 Majkowska Agnieszka 65 Fuks Leon 74, 81, 93 Malec-Czechowska Kazimiera 55, 60, 131 G Malinowska Aneta 146 Głuszewski Wojciech 40, 42 Męczyńska-Wielgosz Sylwia 119 Gniazdowska Ewa 74, 77 Michalik Jacek 28, 29 Goncharova Rose L. 122 Michałowski Sławomir 27 Grądzka Iwona 122, 123 Mieczkowski Józef 74 Grigoriew Helena 155 Mirkowski Jacek 23 Grodkowski Jan 23 Mirkowski Krzysztof 38 INDEX OF THE AUTHORS 247

Miśkiewicz Agnieszka 136 Sommer Sylwester 116 Mizera Jiři 88 Stachowicz Wacław 55, 57, 60 N Starosta Wojciech 33, 105, 106, 107, 108, 110, 111, 148, 149, 150 Narbutt Jerzy 74, 86 Sterniczuk Marcin 29 Nasonova Elena 116 Stępkowski Tomasz 117 Nowicki Andrzej 33 Stoch Paweł 148 O Strzelczak Grażyna 28, 29 Obe Günter 120 Sun Yongxia 127 Olczak Tadeusz 100, 102, 153 Szewczyk Krzysztof 127 Olszewska-Świetlik Justyna 139 Szreder Tomasz 23 Orelovitch Oleg L. 145 Szumiel Irena 122, 123 Szydłowski Adam 146 P Ś Palige Jacek 127 Pańczyk Ewa 139 Świstowski Edward 158 Pawelec Andrzej 130 T Peimel-Stuglik Zofia 53 Trojanowicz Marek 51 Piekoszewski Jerzy 143, 148, 149 Pieńkos Jan P. 158 U Pietzsch Hans-Jürgen 77 Usidus Janusz 127 Plewka Krzysztof 131, 133 W Pochrybniak Cezary 148 Waliś Lech 139, 143, 148, 149 Polkowska-Motrenko Halina 90, 93 Walo Marta 35 Połosak Magdalena 69 Warchoł Stanisław 158 Presz Adam 145 Wawszczak Danuta 100, 102 Pruszyński Marek 71 Werner Zbigniew 143, 148, 149 Przybylski Jacek 27 Wiegart Lutz 155 Przybytniak Grażyna 33, 35, 38 Wierzchnicki Ryszard 131, 133 Pszonicki Leon 98 Wishart James F. 23 Pyszynska Marta 93, 96 Wojewódzka Maria 122, 123 R Wojciechowski Piotr 127, 128, 131 Ratajska Anna 27 Woźniak Krztsztof 73 Ritter Sylvia 116 Wójcik Andrzej 115, 120, 121 Roman Karol 158 Wójcik Lena 51 Rösch Frank 71 Wójciuk Grzgorz 117 Rumianek Karolina 118, 119 Wójtowicz Joanna 27 Wychowański Piotr 27 S X Sadlej-Sosnowska Nina 81 Sadło Jarosław 27, 28, 29, 118, 119 Xiarchos Ioannis 137 Sadowska-Bratek Monika 96, 98 Z Samczyński Zbigniew 88 Zagórski Zbigniew P. 31, 40, 42 Sartowska Bożena 46, 143, 145, 146, 148, 149, 150 Zakrzewska-Trznadel Grażyna 134, 136, 137 Siekierski Sławomir 81 Zaza Fabio 102 Simonetti Elisabetta 100, 153 Zimek Zbigniew 127, 158 Składnik-Sadowska Elżbieta 149 Skrzypczak Andrzej 23 Ż Skwara Witold 98 Żuchowska Krystyna 68 Sobarzo-Sanchez Eduardo 21