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1 ISSN X ANNUAL REPORT 2013 INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY Dorodna 16, Warszawa, Poland phone: , fax: INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

2 ANNUAL REPORT 2013 INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

3 EDITORS Prof. Jacek Michalik, Ph.D., D.Sc. Wiktor Smułek, Ph.D. Ewa Godlewska-Para, M.Sc. Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2014 All rights reserved

4 CONTENTS GENERAL INFORMATION 7 MANAGEMENT OF THE INSTITUTE 9 MANAGING STAFF OF THE INSTITUTE 9 HEADS OF THE INCT DEPARTMENTS 9 SCIENTIFIC COUNCIL ( ) 9 ORGANIZATION SCHEME 11 SCIENTIFIC STAFF 12 PROFESSORS 12 SENIOR SCIENTISTS (Ph.D.) 12 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 15 ONE-ELECTRON OXIDATION AND REDUCTION OF 3-METHYLQUINOXALIN-2-ONE K. Skotnicki, K. Bobrowski, J. De la Fuente, A. Cañete 17 FREE RADICAL OXIDATION OF NICOTINE: A PULSE RADIOLYSIS STUDY K. Kosno, M. Celuch, J. Mirkowski, I. Janik, D. Pogocki 19 RADIATION EFFECTS IN SORPTION MATERIALS WITH Ag + CATIONS EPR STUDY A. Bugaj, J. Sadło, M. Sterniczuk, G. Strzelczak, J. Michalik 21 RADIATION-INDUCED CURING OF EPOXY RESINS AND ITS NANOCARBON COMPOSITES G. Przybytniak, A. Nowicki, K. Mirkowski 23 PREPARATION OF THE FILMS BASED ON STARCH-PVA SYSTEM. PRELIMINARY STUDIES OF THE GAMMA IRRADIATION EFFECTS K. Cieśla, A. Abramowska, M. Buczkowski, P. Tchórzewski, A. Nowicki, J. Boguski 25 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 29 SYNTHESIS, PHYSICOCHEMICAL AND BIOLOGICAL EVALUATION OF NOVEL TECHNETIUM-99m LABELLED LAPATINIB AS A POTENTIAL TUMOUR IMAGING AGENT E. Gniazdowska, P. Koźmiński, L. Fuks, K. Bańkowski, W. Łuniewski, L. Królicki 31 CYCLOTRON PRODUCTION OF 99m Tc. SEPARATION OF 99m Tc FROM 100 Mo TARGET M. Gumiela, E. Gniazdowska, A. Bilewicz 34 THE STRUCTURES OF BISMUTH(III) COMPLEXES WITH TROPOLONE K. Łyczko, M. Łyczko, K. Woźniak, M. Stachowicz 35 SILVER IMPREGNATED NANOPARTICLES OF TITANIUM DIOXIDE AS 211 At CARRIERS E. Leszczuk, M. Łyczko, A. Piotrowska, A. Bilewicz, J. Choiński, J. Jastrzębski, A. Stolarz, A. Trzcińska, K. Szkliniarz, W. Zipper, B. Wąs 37 NANOTITANATE AS A NEW SORBENT FOR 137 Cs SEPARATION FROM RADIACTIVE WASTE B. Filipowicz, S. Krajewski, M. Łyczko, M. Pruszyński, A. Bilewicz 39 SORPTION OF AMERICIUM(III) IONS ON THE BENTONITE OF THE VOLCLAY TYPE A. Oszczak, L. Fuks, A. Gładysz-Płaska, M. Majdan 42 THE STUDY OF SORPTION OF COBALT IONS ON THE RED CLAY AND ZEOLITES G. Zakrzewska-Kołtuniewicz, A. Miśkiewicz, W. Olszewska, B. Sartowska 45 ANALYSIS OF THE POSSIBILITY OF URANIUM SUPPLY FROM DOMESTIC RESOURCES G. Zakrzewska-Kołtuniewicz, K. Kiegiel, D. Gajda, A. Miśkiewicz, P. Biełuszka, K. Frąckiewicz, I. Herdzik-Koniecko, B. Zielińska, A. Jaworska, K. Szczygłów, A. Abramowska, W. Olszewska, M. Harasimowicz, R. Dybczyński, H. Polkowska-Motrenko, B. Danko, Z. Samczyński, E. Chajduk, J. Chwastowska, I. Bartosiewicz, J. Dudek, S. Wołkowicz, J.B. Miecznik 48 STUDIES ON LEACHING COPPER ORES AND FLOTATION WASTES D. Wawszczak, A. Deptuła, W. Łada, T. Smoliński, T. Olczak, M. Brykała, P. Wojtowicz, M. Rogowski, M. Miłkowska 52

5 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 55 REAL-TIME PCR ANALYSIS OF EXPRESSION OF DNA DAMAGE RESPONSIVE GENES AS A BIOMARKER FOR BIOLOGICAL DOSIMETRY K. Brzóska, I. Buraczewska, I. Grądzka, B. Sochanowicz, T. Iwaneńko, M. Wojewódzka, G. Wójciuk, T. Stępkowski, M. Kruszewski 57 OPTIMIZING THE METAFER IMAGE ACQUISITION AND ANALYSIS SYSTEM FOR ESTIMATION OF DNA DOUBLE STRAND BREAK INDUCTION BY MEANS OF γ-h2ax FOCI ASSAY A. Lankoff, K. Sikorska, I. Buraczewska, I. Wasyk, T. Bartłomiejczyk, T. Iwaneńko, S. Sommer, I. Szumiel, M. Wojewódzka, K. Wójciuk, M. Kruszewski 58 QUICK SCAN OF DICENTRIC CHROMOSOMES FOR EVALUATION OF THE ABSORBED DOSE S. Sommer, I. Buraczewska, K. Sikorska, I. Wasyk, T. Bartłomiejczyk, A. Lankoff, M. Wojewódzka, M. Kruszewski 59 THE EFFECT OF SUPPLEMENTATION WITH CONJUGATED LINOLEIC ACID (CLA) ON Akt1 KINASE PHOSPHORYLATION IN X-IRRADIATED HT-29 CELLS I. Grądzka, I. Buraczewska, K. Sikorska, B. Sochanowicz, I. Szumiel, K. Wójciuk, G. Wójciuk 60 LABORATORY OF NUCLEAR ANALYTICAL METHODS 63 RADIOLYTIC REMOVAL OF SELECTED PHARMACEUTICALS AND BISPHENOL A FROM WATERS AND WASTES A. Bojanowska-Czajka, S. Borowiecka, M. Trojanowicz 64 DETERMINATION OF URANIUM IN FLOW-INJECTION SYSTEM WITH SPECTROPHOTOMETRIC DETECTION K. Kołacińska, M. Trojanowicz 67 LABORATORY OF MATERIAL RESEARCH 71 STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY W. Starosta, J. Leciejewicz 72 FORMATION OF THE SURFACE LAYER WITH IMPROVED TRIBOLOGICAL PROPERTIES ON AUSTENITIC STAINLESS STEEL BY ALLOYING WITH REE USING HIGH INTENSITY PULSED PLASMA BEAMS B. Sartowska, M. Barlak, L. Waliś, J. Senatorski, W. Starosta 76 TECHNOLOGY, PRODUCTION AND CHRONOLOGY OF RED WINDOW GLASS IN THE MEDIEVAL PERIOD REDISCOVERY OF A LOST TECHNOLOGY J.J. Kunicki-Goldfinger, I.C. Freestone, I. McDonald, J.A. Hobot, H. Gilderdale-Scott, T. Ayers 78 POLLUTION CONTROL TECHNOLOGIES LABORATORY 79 PRELIMINARY MODELLING STUDY OF NO x REMOVAL FROM OIL-FIRED OFF-GAS UNDER ELECTRON BEAM IRRADIATION Y. Sun, A.G. Chmielewski, H. Nichipor, S. Bułka, Z. Zimek, E. Zwolińska 81 ANALYSIS OF THE CONSTRUCTION POSSIBILITY OF A LARGE ELECTRON BEAM FLUE GAS TREATMENT PLANT A. Pawelec, S. Witman-Zając 82 STABLE ISOTOPE LABORATORY 85 DETERMINATION OF SULPHUR ISOTOPIC COMPOSITION OF FOOD PRODUCTS R. Wierzchnicki, K. Malec-Czechowska 86 NEW APPROACH OF THE ISOTOPIC METHOD FOR JUICE AUTHENTICITY CONTROL R. Wierzchnicki, K. Malec-Czechowska 87 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 89 RECALIBRATION OF DOSIMETER FILMS CTA A. Korzeniowska-Sobczuk, A. Sterniczuk, M. Karlińska 90 LABORATORY FOR DETECTION OF IRRADIATED FOOD 93 STABILITY OF THE EPR SIGNAL PRODUCED BY IONIZING RADIATION IN DRIED FRUITS G.P. Guzik, W. Stachowicz 95

6 QUANTITY AND QUALITY OF MINERAL FRACTION IN THERMOLUMINESCENCE METHOD FOR THE DETECTION OF IRRADIATION IN ALIMENTARY ARTICLES W. Stachowicz, G. Liśkiewicz 96 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 99 DIAGNOSTICS OF BIOGAS INSTALLATION BY GAMMA RADIATION A. Jakowiuk, Ł. Modzelewski, J. Palige, E. Kowalska, J. Pieńkos 100 PUBLICATIONS IN ARTICLES 102 BOOKS 107 CHAPTERS IN BOOKS 107 THE INCT PUBLICATIONS 108 CONFERENCE PROCEEDINGS 109 CONFERENCE ABSTRACTS 110 SUPPLEMENT LIST OF THE PUBLICATIONS IN NUKLEONIKA 128 POSTĘPY TECHNIKI JĄDROWEJ 134 INTERVIEWS IN THE INCT PATENTS AND PATENT APPLICATIONS IN PATENTS 138 PATENT APPLICATIONS 138 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN Ph.D. THESES IN EDUCATION 143 Ph.D. PROGRAMME IN CHEMISTRY 143 TRAINING OF STUDENTS 143 RESEARCH PROJECTS AND CONTRACTS 145 RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE IN DEVELOPMENT PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN INNOTECH PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN APPLIED RESEARCH PROGRAMME OF THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN STRATEGIC PROJECT TECHNOLOGIES SUPPORTING DEVELOPMENT OF SAFE NUCLEAR POWER ENGINEERING 147 STRATEGIC PROJECT ADVANCED TECHNOLOGIES FOR GAINING ENERGY 147

7 IAEA RESEARCH CONTRACTS IN IAEA TECHNICAL AND REGIONAL CONTRACTS IN PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN EUROPEAN REGIONAL DEVELOPMENT FUND: BALTIC SEA REGION PROGRAMME 149 OTHER INTERNATIONAL RESEARCH PROGRAMMES IN STRUCTURAL FUNDS: OPERATIONAL PROGRAMME INNOVATIVE ECONOMY 149 LIST OF VISITORS TO THE INCT IN THE INCT SEMINARS IN LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN LECTURES 153 SEMINARS 154 AWARDS IN INDEX OF THE AUTHORS 158

8 GENERAL INFORMATION 7 GENERAL INFORMATION Poland decided to start a national nuclear energy programme 55 years ago and the Institute of Nuclear Research (IBJ) was established. Research in nuclear and analytical chemistry, nuclear chemical engineering and technology (including fuel cycle), radiochemistry and radiation chemistry, and radiobiology were carried out mainly in the Chemistry Division, located at Warsaw Żerań, which became the interdisciplinary Institute of Nuclear Chemistry and Technology (INCT) in The INCT is Poland s most advanced institution in the fields of radiochemistry, radiation chemistry, nuclear chemical engineering and technology, application of nuclear methods in material engineering and process engineering, radioanalytical techniques, design and production of instruments based on nuclear techniques, environmental research, cellular radiobiology, etc. The results of work at the INCT have been implemented in various branches of the national economy, particularly in industry, medicine, environmental protection and agriculture. Basic research is focused on: radiochemistry, chemistry of isotopes, physical chemistry of separation processes, cellular radiobiology, and radiation chemistry, particularly that based on the pulse radiolysis method. 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 centres of science and technology in this domain. The Institute has four pilot plants equipped with six electron accelerators: for radiation sterilization of medical devices and transplantation grafts; for radiation modification of polymers; for removal of SO 2 and NO x from flue gases; for food hygiene. The electron beam flue gas treatment in the EPS Pomorzany with the accelerators power over 1 MW is the biggest radiation processing facility ever built. The Institute represents the Polish Government in the Euroatom Fuel Supply Agency, in Fuel Supply Working Group of Global Nuclear Energy Partnership and in Radioactive Waste Management Committee of the Nuclear Energy Agency (Organisation for Economic Co-operation and Development). The INCT Scientific Council has the rights to grant D.Sc. and Ph.D. degrees in the field of chemistry. The Institute carries out third level studies (doctorate) in the field of nuclear and radiation chemistry and in 2013 eight Ph.D. thesis was defended. The Institute trains many of IAEA s fellows and plays a leading role in agency regional projects. Because of its achievements, the INCT has been nominated the IAEA s Collaborating Centre in Radiation Technology and Industrial Dosimetry. The INCT is editor of the scientific journal Nukleonika ( and the scientific-information journal Postępy Techniki Jądrowej. In 2013, the Evaluation Committee of Scientific Units in the Ministry of Science and Higher Education conferred the INCT cathegory A. The collaboration agreement between French Atomic Energy Commission (CEA) and the Institute concerning the chemical aspects of nuclear power was signed in December The consortium agreement with Électricité de France (EDF Polska SA) made possible to prepare NCBR joint grant proposal Integrated radioprotection system for nuclear buildings. The INCT has carried out several projects in the programme Innovative Economy PO IG, granted on the basis of high evaluation of the Institute s achievements: Analysis of the possibilities of uranium extraction from domestic resources (in cooperation with the Polish Geological Institute NRI); Development of a multi-parametric triage approach for an assessment of radiation exposure in a large -scale radiological emergency; New generation of electrical wires modified by radiation.

9 8 GENERAL INFORMATION The INCT is the leading institute in Poland regarding the implementation of nuclear energy related EU projects. Its expertise and infrastructure was the basis for participation in FP7-EURATOM grants: ADVANCE: Ageing diagnostics and prognostics of low-voltage I&C cables; IPPA: Implementing public participation approaches in radioactive wastes disposal; MULTIBIODOSE: Multidisciplinary biodosimetric tools to manage high scale radiological casualties; ASGARD: Advanced fuels for generation IV reactors: reprocessing and dissolution; RENEB: Realizing the European Network in Biodosimetry; NEWLANCER: New MS linking for an advanced cohesion in Euratom research; ARCADIA: Assessment of regional capabilities for new reactors development through an integrated approach; EAGLE: Enhancing education, training and communication processes for informed behaviors and decision-making related to ionizing radiation risks; PLATENSO: Building a platform for enhanced societal research related to nuclear energy in Central and Eastern Europe; SACSESS: Safety of actinide separation processes; TALISMAN: Transnational access to large infrastructure for a safe management of actinide. In 2013, the INCT scientists published 55 papers in scientific journals registered in the Philadelphia list, among them 36 papers in journals with an impact factor (IF) higher than 1.0. Two scientific books and 11 chapters were written by the INCT research workers. The following annual awards of the INCT Director-General for the best publications and application achievements in 2013 were granted: first degree team award to Jacek Palige, Katarzyna Wawryniuk, Otton Roubinek, Agata Urbaniak, Henryk Burliński, Andrzej G. Chmielewski for the application achievements elaboration of the project of mobile membrane installation for enrichment of biogas in methane; second degree team award to Andrzej Pawelec, Sylwia Witman-Zając, Janusz Licki, Andrzej G. Chmielewski for the application achievements realization of the project Studies of the technology of purification of flue gases with electron beam method on a pilot scale ; second degree team award to Grażyna Zakrzewska-Kołtuniewicz, Agnieszka Miśkiewicz, Marian Harasimowicz for a series of four articles concerning the removal of harmful impurities from waters and sewages with membrane technology; third degree team award to Janusz Kraś, Cezary Nobis, Tadeusz Bilka, Mirosław Gurniak, Mariusz Wieczorek, Grażyna Giers, Natalia Pawlik for the application achievements implementation of new measurement methods related to the tightness of installations and industrial pipelines; third degree individual award of Director of the Institute of Nuclear Chemistry and Technology to Yongxia Sun for a series of works concerning the removal of volatile organic compounds from gases emitted to the atmosphere third degree team award of Director of the Institute of Nuclear Chemistry and Technology to Agnieszka Majkowska-Pilip, Marek Pruszyński, Barbara Bartoś, Aleksander Bilewicz for a series of three articles concerning the application of radionuclides of scandium to the diagnosis and radionuclide theraphy. In 2013, the research teams in the INCT were involved in the organization of 12 scientific meetings.

10 MANAGEMENT OF THE INSTITUTE 9 MANAGEMENT OF THE INSTITUTE MANAGING STAFF OF THE INSTITUTE Director Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Deputy Director for Research and Development Prof. Jacek Michalik, Ph.D., D.Sc. Deputy Director of Finances Wojciech Maciąg, M.Sc. Deputy Director of Maintenance and Marketing Roman Janusz, M.Sc. Accountant General Maria Małkiewicz, M.Sc. HEADS OF THE INCT DEPARTMENTS Centre for Radiation Research and Technology Zbigniew Zimek, Ph.D. Centre for Radiochemistry and Nuclear Chemistry Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. Centre for Radiobiology and Biological Dosimetry Prof. Marcin Kruszewski, Ph.D., D.Sc. Laboratory of Nuclear Control Systems and Methods Jacek Palige, Ph.D. Laboratory of Material Research Wojciech Starosta, Ph.D. Laboratory of Nuclear Analytical Methods Halina Polkowska-Motrenko, Ph.D., D.Sc, professor in INCT Stable Isotope Laboratory Ryszard Wierzchnicki, Ph.D. Pollution Control Technologies Laboratory Andrzej Pawelec, Ph.D. Laboratory for Detection of Irradiated Food Wacław Stachowicz, Ph.D. Laboratory for Measurements of Technological Doses Anna Korzeniowska-Sobczuk, M.Sc. SCIENTIFIC COUNCIL ( ) 1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. University of Łódź 2. Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. (Vice-chairman) Institute of Nuclear Chemistry and Technology 4. Marcin Brykała, Ph.D. Institute of Nuclear Chemistry and Technology 5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 6. Andrzej Chwas, M.Sc. Ministry of Economy 7. Jadwiga Chwastowska, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 8. Krystyna Cieśla, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology

11 10 MANAGEMENT OF THE INSTITUTE 9. Jakub Dudek, Ph.D. Institute of Nuclear Chemistry and Technology 10. Prof. Rajmund Dybczyński, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 11. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. (Chairman) Warsaw University of Technology 12. Prof. Zbigniew Galus, Ph.D., D.Sc. University of Warsaw 13. Prof. Henryk Górecki, Ph.D., D.Sc. Wrocław University of Technology 14. Prof. Leon Gradoń, Ph.D., D.Sc. Warsaw University of Technology 15. Jan Grodkowski, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 16. Edward Iller, Ph.D., D.Sc., professor in NCBJ National Centre for Nuclear Research 17. Adrian Jakowiuk, M.Sc. Institute of Nuclear Chemistry and Technology 18. Prof. Marcin Kruszewski, Ph.D., D.Sc. (Vice-chairman) Institute of Nuclear Chemistry and Technology 19. Anna Lankoff, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc. AGH University of Science and Technology 21. Prof. Janusz Lipkowski, Ph.D., D.Sc. Institute of Physical Chemistry, Polish Academy of Sciences 22. Zygmunt Łuczyński, Ph.D. Institute of Electronic Materials Technology 23. Prof. Jacek Michalik, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 24. Wojciech Migdał, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 25. Prof. Jarosław Mizera, Ph.D., D.Sc. Warsaw University of Technology 26. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 27. Andrzej Pawlukojć, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 28. Dariusz Pogocki, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 29. Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 30. Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 31. Prof. Janusz Rosiak, Ph.D., D.Sc. Technical University of Łódź 32. Lech Waliś, Ph.D. Institute of Nuclear Chemistry and Technology 33. Maria Wojewódzka, Ph.D. Institute of Nuclear Chemistry and Technology 34. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT (Vice-chairman) Institute of Nuclear Chemistry and Technology 35. Zbigniew Zimek, Ph.D. Institute of Nuclear Chemistry and Technology HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL ( ) 1. Prof. Sławomir Siekierski, Ph.D. 2. Prof. Zbigniew Szot, Ph.D., D.Sc. 3. Prof. Irena Szumiel, Ph.D., D.Sc. 4. Prof. Zbigniew Paweł Zagórski, Ph.D., D.Sc.

12 MANAGEMENT OF THE INSTITUTE 11 ORGANIZATION SCHEME DIRECTOR Scientific Council Accountant General Deputy Director of Finances Deputy Director of Maintenance and Marketing Deputy Director for Research and Development Laboratory of Nuclear Analytical Methods Centre for Radiation Research and Technology Stable Isotope Laboratory Centre for Radiobiology and Biological Dosimetry Pollution Control Technologies Laboratory Laboratory for Detection of Irradiated Food Centre for Radiochemistry and Nuclear Chemistry Laboratory for Measurements of Technological Doses Laboratory of Material Research Laboratory of Nuclear Control Systems and Methods

13 12 SCIENTIFIC STAFF SCIENTIFIC STAFF PROFESSORS 1. Bilewicz Aleksander radiochemistry, inorganic chemistry 2. Bobrowski Krzysztof radiation chemistry, photochemistry, biophysics 3. Chmielewski Andrzej G. chemical and process engineering, nuclear chemical engineering, isotope chemistry 4. Chwastowska Jadwiga, professor in INCT analytical chemistry 5. Cieśla Krystyna, professor in INCT physical chemistry 6. Dobrowolski Jan spectroscopy and molecular modelling 7. Dybczyński Rajmund analytical chemistry 8. Grigoriew Helena, professor in INCT solid state physics, diffraction research of non-crystalline matter 9. Grodkowski Jan, professor in INCT radiation chemistry 10. Kruszewski Marcin radiobiology 11. Lankoff Anna, professor in INCT biology 13. Michalik Jacek radiation chemistry, surface chemistry, radical chemistry 14. Migdał Wojciech, professor in INCT chemistry, science of commodies 15. Ostyk-Narbutt Jerzy radiochemistry, coordination chemistry 16. Pawlukojć Andrzej, professor in INCT chemistry 17. Pogocki Dariusz, professor in INCT radiation chemistry, pulse radiolysis 18. Polkowska-Motrenko Halina, professor in INCT analytical chemistry 19. Przybytniak Grażyna, professor in INCT radiation chemistry 20. Siekierski Sławomir physical chemistry, inorganic chemistry 21. Szumiel Irena cellular radiobiology 22. Trojanowicz Marek analytical chemistry 23. Zagórski Zbigniew physical chemistry, radiation chemistry, electrochemistry 12. Leciejewicz Janusz Tadeusz crystallography, solid state physics, material science 24. Zakrzewska-Kołtuniewicz Grażyna, professor in INCT process and chemical engineering SENIOR SCIENTISTS (Ph.D.) 1. Bartłomiejczyk Teresa biology 5. Brzóska Kamil biochemistry 2. Bojanowska-Czajka Anna chemistry 6. Buczkowski Marek physics 3. Borowik Krzysztof chemistry 7. Chajduk Ewelina chemistry 4. Brykała Marcin chemistry 8. Danilczuk Marek chemistry

14 SCIENTIFIC STAFF Deptuła Andrzej chemistry 31. Męczyńska-Wielgosz Sylwia chemistry 10. Dobrowolski Andrzej chemistry 32. Mirkowski Jacek nuclear and medical electronics 11. Dudek Jakub chemistry 33. Miśkiewicz Agnieszka chemistry Fuks Leon chemistry Głuszewski Wojciech chemistry Gniazdowska Ewa chemistry Grądzka Iwona biology Harasimowicz Marian technical nuclear physics, theory of elementary particles Nowicki Andrzej organic chemistry and technology, high-temperature technology Ostrowski Stanisław chemistry Palige Jacek metallurgy Pawelec Andrzej chemical engineering Pruszyński Marek chemistry 17. Herdzik-Koniecko Irena chemistry 39. Ptaszek Sylwia chemical engineering 18. Kciuk Gabriel chemistry 40. Rafalski Andrzej radiation chemistry 19. Kiegiel Katarzyna chemistry 41. Roubinek Otton chemistry 20. Kierzek Joachim physics 42. Sadło Jarosław chemistry 21. Kocia Rafał chemistry 43. Samczyński Zbigniew analytical chemistry 22. Kornacka Ewa chemistry 44. Sartowska Bożena material engineering 23. Koźmiński Przemysław chemistry 45. Skwara Witold analytical chemistry 24. Krajewski Seweryn chemistry 46. Sochanowicz Barbara biology 25. Kunicki-Goldfinger Jerzy conservator/restorer of art 47. Sommer Sylwester radiobiology, cytogenetics 26. Latek Stanisław nuclear physics 48. Stachowicz Wacław radiation chemistry, EPR spectroscopy 27. Lewandowska-Siwkiewicz Hanna chemistry 49. Starosta Wojciech chemistry 28. Łyczko Krzysztof chemistry 50. Sterniczuk Macin chemistry 29. Łyczko Monika chemistry 51. Strzelczak Grażyna radiation chemistry 30. Majkowska-Pilip Agnieszka chemistry 52. Sun Yongxia chemistry

15 14 SCIENTIFIC STAFF 53. Szreder Tomasz chemistry 59. Wiśniowski Paweł radiation chemistry, photochemistry, biophysics 54. Waliś Lech material science, material engineering 60. Wojewódzka Maria radiobiology 55. Walo Marta chemistry 61. Wójciuk Grzegorz chemistry 56. Warchoł Stanisław solid state physics 62. Wójciuk Karolina chemistry Wawszczak Danuta chemistry Wierzchnicki Ryszard chemical engineering 63. Zimek Zbigniew electronics, accelerator techniques, radiation processing

16 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY Electron beams (EB) offered by the Centre for Radiation Research and Technology located at the Institute of Nuclear Chemistry and Technology (INCT) are dedicated to basic research, R&D and radiation technology applications. The Centre, in collaboration with the universities from Poland and abroad, apply EB technology for fundamental research on the electron beam-induced chemistry and transformation of materials. Research in the field of radiation chemistry includes studies on the mechanism and kinetics of radiation-induced processes in liquid and solid phases by the pulse radiolysis method. The pulse radiolysis experimental set-up allows direct time-resolved observation of short-lived intermediates (typically within the nanosecond to millisecond time domain), is complemented by steady-state radiolysis, stop-flow absorption spectrofluorimetry and product analysis using chromatographic methods. Studies on radiation-induced intermediates are dedicated to energy and charge transfer processes and radical reactions in model compounds of biological relevance aromatic thioethers, peptides and proteins, as well as observation of atoms, clusters, radicals by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR), also focused on research problems in nanophase chemistry and radiation-induced cross-linking of selected and/or modified polymers and copolymers. This research has a wide range of potential applications, including creating more environmentally friendly and sustainable packaging, improving product safety, and modifying material properties. Electron accelerators provide streams of electrons to initiate chemical reactions or break of chemical bonds more efficiently than the existing thermal and chemical approaches, helping to reduce energy consumption and decrease the cost of the process. The Centre may offer currently four electron accelerators for study of the effects of accelerated electrons on a wide range of chemical compounds with a focus on electron beam-induced polymerization, polymer modification and controlled degradation of macromolecules. EB technology has a great potential to promote innovation, including new ways to save energy and reduce the use of hazardous substances as well as to enable more eco-friendly manufacturing processes. Advanced EB technology offered by the Centre provides a unique platform with the application for: sterilization medical devices, pharmaceutical materials, food products shelf-life extension, polymer advanced materials, air pollution removal technology and others. EB accelerators replace frequently thermal and chemical processes for cleaner, more efficient, lower-cost manufacturing. EB accelerators sterilize products and packaging, improve the performance of plastics and other materials, and eliminate pollution for industries such as pharmaceutical, medical devices, food, and plastics. The Centre offers EB in the energy range from 0.5 to 10 MeV with an average beam power up to 20 kw and three laboratory-size gamma sources with Co-60. Research activity are supported by such unique laboratory equipment as: nanosecond pulse radiolysis and laser photolysis set-ups, stop-flow experimental set-up, EPR paramagnetic spectroscopy for solid material investigation, pilot installation for polymer modification, laboratory experimental stand for removal of pollutants from gas phase, laboratory of polymer and non-material characterization, microbiological laboratory, pilot facility for radiation sterilization, polymer modification and food product processing.

17 The unique technical basis makes it possible to organize a wide internal and international cooperation in the field of radiation chemistry and radiation processing including programmes supported by the European Union and the International Atomic Energy Agency (IAEA). It should be noticed that currently there is no other suitable European experimental basis for study radiation chemistry, physics and radiation processing in a full range of electron energy and beam power. Since 2010, at the INCT on the basis of the Centre for Radiation Research and Technology, an IAEA Collaborating Centre for Radiation Processing and Industrial Dosimetry is functioning. That is the best example of capability and great potential of concentrated equipment, methods and staff working towards application of innovative radiation technology.

18 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY ONE-ELECTRON OXIDATION AND REDUCTION OF 3-METHYLQUINOXALIN-2-ONE Konrad Skotnicki, Krzysztof Bobrowski, Julio De la Fuente 1/, Alvaro Cañete 2/ 1/ Universidad de Chile, Santiago de Chile, Chile 2/ Pontificia Universidad Católica de Chile, Chile 17 Quinoxalin-2-ones are the class of compounds showing a variety of pharmacological properties, such as antimicrobial [1], antiviral [2], anti-inflammatory [3], antithrombotic [4, 5], anticancer [6-9] activity. A key factor decisive about their biological activity is a substitution at the carbon-3 in the pyrazine ring and at the carbons 6 and 7 in the benzene ring in a primary quinoxalin-2-one structure (Chart 1). Nearly all biologically active derivatives are substituted in these specific positions. Chart 1. Structural formula of quinoxalin-2-one. The structure activity relationship (SAR) studies have revealed that quinoxalin-2-ones derivatives bound to proteins receptors are generally located close to the adenosine triphosphate (ATP) binding pocket [6, 10], e.g. in cyclin-dependent kinases (Cdk). The fact that these compounds are bound in the very specific position in proteins may have serious consequences in their interactions with either amino acid residues or radicals derived from them. Certain amino acid residues tyrosine (Tyr), tryptophan (Trp), and cysteine (Cys) are particularly vulnerable to oxidation. Therefore, the radical cations derived from quinoxalin-2-ones can modify these amino acids which are reasonably good electron donors and can be oxidized to tyrosyl (TyrO ), tryptophyl (Trp ), and thiyl (Cys ) radicals, respectively. On the other hand, these radicals are reasonably good electron acceptors and can act potentially as oxidants. Reactive oxygen and nitrogen species (ROS and RNS) are produced in excess during the oxidative and nitrosative stress in living organisms. ROS and RNS can react with various biological targets (proteins, DNA, lipids), the most important of them being proteins and peptides because of their high concentration in cells [11]. In principle, oxidation and reduction processes in proteins can occur everywhere and involve the protein backbone, amino acid residues and also intercalated molecules (e.g. quinoxalin-2-ones). The primary steps leading to these modifications are extremely fast, consist of one electron loss and very often a subsequent one electron capture, resulting in creation of very reactive transients (radicals and radical ions) which are responsible for secondary re- Fig.1. Transient absorption spectra obtained by OH attack on 3-methylquinoxalin-2-one recorded 4 μs ( ), 80 μs ( ), 300 μs ( ) and 800 μs ( ) after the pulse in the N 2 O-saturated 0.1 mm 3-methylquinoxalin-2-one, at ph 8. Insets: kinetics traces of formation and decay recorded at 370 and 460 nm.

19 18 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY actions. For these reasons it is important to characterize spectral properties of transients derived from quinoxalin-2-ones (those derived from amino acids are mostly known) and to measure kinetic parameters of the primary and secondary reactions involving quinoxalin-2-ones and amino acid residues. These reactions lead to production of various free radicals, including those derived either from amino acids or quinoxalin-2-ones. after the pulse are characterized by two distinct absorption maxima located at λ = 370 and 460 nm (Fig.1). The first one is stable within 1.5 ms time domain. Complementry steady-state γ-radiolysis experiments revealed that this absorption is stable and is associated with a stable reaction product. The second-order rate constants k Q+OH were determined from the kinetic traces at 370 and 460 nm in pseudo first-order conditions and were found Fig.2. Transient absorption spectra obtained by e solv attack on 3-methylquinoxalin-2-one recorded 2 μs ( ), 10 μs ( ), 20 μs ( ), 40 μs ( ) and 100 μs ( ) after the pulse in the Ar-saturated 0.1 mm 3-methylquinoxalin-2-one, at ph 8. Insets: kinetics traces of formation and decay recorded at 370 and 430 nm. Radical oxidation and reduction of 3-methylquinoxalin-2-one and kinetics of its reactions with hydroxyl radicals ( OH) and solvated electrons (e aq ), respectively, were studied by pulse radiolysis technique coupled with the time-resolved UV/Vis spectrophotometric detection system. Reactions were studied in aqueous solutions saturated either with N 2 O or argon. Pulse radiolysis studies in N 2 O-saturated aqueous solution at ph 8 has been performed in order to check whether 3-methylquinoxalin-2-one is able to scavenge OH radicals. OH-induced oxidation generally leads to one-electron oxidation products. However, it is well known, that the formation of OH adducts is another possible reaction pathway. Transient absorption spectra observed 4 μs H N O H e solv N O H + to be equal to k 370 = 4.6 ± M 1 s 1 and k 460 = 4.4 ± M 1 s 1. Reaction with e aq has been performed in Ar-saturated aqueous solution containing tert-butanol at ph 8. One-electron reduction of 3-methylquinoxalin-2-one leads to the formation of at least two products, with the respective absorption maxima at λ = 370 and 430 nm (Fig.2). The second- -order rate constant k Q+e was determined from the kinetic traces at 720 nm (absorption maximum of solvated electron absorption in water) in pseudo first-order conditions and was found to be equal to k 720 = 2.8 ± M 1 s 1. Additional experiments performed in different ph values and with similar compounds allow to assume that one-electron reduction results in the for- N C N - C N H Scheme 1. A proposed mechanism for one-electron reduction of 3-methylquinoxalin-2-one. H N O

20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 19 mation of a radical anion followed by a rapid protonation to a neutral protonated radical. Proposed reaction mechanism is presented in Scheme 1. Obtained results indicated that quinoxalin-2- -ones are able to scavenge OH radicals with high rate constants (k = M 1 s 1 ) which is a very promising result for their possible medical use. One-electron reductions leads to the formation of radical anion and protonated radical with a rate constant close to a diffusion control (k = M 1 s 1 ). Further studies concerning interactions of quinoxalin-2-ones with amino acids will be performed. References [1]. Ajani O.O. et al.: Bioorg. Med. Chem., 18(1), (2010). [2]. Xu B.L. et al.: Bioorg. Med. Chem., 17(7), (2009). [3]. El-Sabbagh O.I. et al.: Med. Chem. Res., 18(9), (2009). [4]. Ries U.J. et al.: Bioorg. Med. Chem. Lett., 13(14), (2003). [5]. Willardsen J.A. et al.: J. Med. Chem., 47(16), (2004). [6]. Hirai H. et al.: Invest. New Drugs, 29(4), (2011). [7]. Kotb E.R. et al.: Phosphorus, Sulfur Silicon Relat. Elem., 182(5), (2007). [8]. Lawrence D.S., Copper J.E., Smith C.D.: J. Med. Chem., 44(4), (2001). [9]. Yuan H.Y. et al.: Med. Chem. Res., 18(8), (2009). [10]. Mori Y. et al.: Chem. Pharm. Bull., 56(5), (2008). [11]. Dean R.T. et al.: Free Radical Biol. Med., 11(2), (1991). FREE RADICAL OXIDATION OF NICOTINE: A PULSE RADIOLYSIS STUDY Katarzyna Kosno, Monika Celuch, Jacek Mirkowski, Ireneusz Janik, Dariusz Pogocki Nicotine (3-(1-methyl-2-pyrrolidinyl)pyridine) is a commonly known natural alkaloid present mainly in tobacco plants and is characterized by a stimulant action. It interacts with the nicotinic acetylcholine receptors and cause the release of many neurotransmitters responsible for mood (e.g. noradrenaline, serotonin and dopamine). This is the main reason of its strong addictive power. However, nicotinic stimulation has also positive effects as it is used in the therapy of some neurodegenerative disorders and diseases [1]. Because of its antioxidative properties, nicotine has the potential to be widely used as a free radical scavenger. It can be used to protect nerve cells in some major neurodegenerative disorders and diseases such as Alzheimer s and Parkinson s diseases, Tourette s syndrome or schizophrenia. Neurodegeneration associated with these diseases is accompanied by an extensive oxidative stress, caused by the imbalance in the production of reactive oxygen species and the biological system s inability to detoxify them. Nervous tissue is continuously exposed to the presence of toxic oxygen radicals beyond a threshold for proper antioxidant neutralization. Nicotine can easily pass through the blood-brain barrier and prevent this destructive radical action thanks to its antioxidative properties. There are some evidence that nicotine can react with the most dangerous OH radical producing neutral or less aggressive radical products [2]. However, it has not been confirmed so far and more data about the mechanism of nicotine radical processes should be obtained. The knowledge about the reactions kinetic is also important, because the rate of nicotine radical reactions need to be high enough to exclude competitive reactions. Nicotine molecule is made of two rings: aromatic pyridine and aliphatic pyrrolidine with chiral carbon C2 atom (Fig.1). The OH radical reacts through a variety of reaction mechanisms, including direct electron transfer, hydrogen abstraction, and addition to unsaturated bonds. In case of nicotine every three pathways are possible N Considering the electron density and favourable energetic effect, substitution occurs mainly at the meta position, the most probable product of hydrogen abstraction is radical located at a chiral carbon and the cation radical is formed at pyrrolidine nitrogen. However, nicotine is a weak base with a pk a1 of 8.02 (pk a2 = 3.12) in aqueous solution at 25 o C [3] and the protonation state has the influence on its radical reactions. According to DFT calculations, protonation of pyrrolidine nitrogen increases the dissociation enthalpy of the C2 -H bond. Some reaction pathways can be even blocked in acidic solutions. The main experimental technique used to study the radical oxidation of nicotine was pulse radiolysis coupled with a time-resolved UV/Vis detection system, which enables to study molecular processes close to or even beyond the diffusion controlled reaction limit. Experiments were performed with the LAE 10 [4] (Institute of Nuclear Chemistry and Technology) and Titan Beta Model TBS-8/16-1 [5] (Notre Dame Radiation Laboratory) linear accelerators. Analysis was done in the broad range of ph giving data for protonated and unprotonated forms of nicotine. Using pyridine 2' 3' N 1' Fig.1. Structural formula of nicotine. 4' 5' CH 3 6'

21 20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY A B C D Fig.2. Reaction scheme for the oxidation of nicotine by azide radical. and N-methylpyrrolidine as nicotine model compounds enabled to divide radical reactions into occurring with aromatic and aliphatic part of the molecule. In order to check if nicotine oxidation can proceed with single-electron transfer, its reaction with azide radical has been studied. Azide radical is a strong one-electron oxidant and it can be readily prepared radiolytically by OH oxidation of azide anions in aqueous solution (Fig.2A,B). It exhibits moderate absorption only in the UV range with a sharp maximum at 274 nm. Reaction of one-electron oxidation can only occur with the aliphatic nitrogen (Fig.2C). Azide radical will not react with aromatic ring, because according to data obtained by Schuler, the rate of its reaction with pyridine is lower than M 1 s 1 [6]. Although there are no reports that azide radicals reacts by hydrogen abstraction, theoretically in favourable reaction conditions there is such a possibility (Fig.2D). The bond dissociation energy for a bond between hydrogen atom and asymmetric car- 1.3x10 4 5x10 5 k (Nic + N3. ) = 5.23 x 107 M -1 s -1 4x10 5 G ε [m 2 /J] 1.0x x x10 3 k app (s -1 ) 3x10 5 2x10 5 1x [Nic] (10-3 mol dm -3 ) 2.5x mm Nic + 10 mm NaN 3 ph 10 ph λ [nm] Fig.3. Transient absorption spectra recorded 10 μs after the electron pulse in N 2 O-saturated, 10 mm aqueous solution of NaN 3 containing 1 mm nicotine recorded at ph 10 and 5.6. Inset: rate constant determined from the pseudo first-order growths of the 330 nm signals generated in 0.1 M NaN 3, N 2 O-saturated, aqueous solution at ph 10 as a function of nicotine concentration.

22 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 21 bon in nicotine molecule is about 25 kj/mol lower than the N-H bond dissociation energy in hydrazoic acid. The reaction of nicotine with azide radical was studied for two protonation states of the pyrrolidinyl nitrogen. Transients obtained in the reaction of unprotonated nicotine at ph 10 gave spectrum with one distinct absorption band with λ max = 330 nm and a broad absorption band with λ max ca. 460 nm, both growing with the same rate (Fig.3). It is very similar to the spectrum obtained for nicotine reaction with hydroxyl radicals, what may suggest that we also observe here mainly radical at chiral carbon. For the protonated aliphatic nitrogen at ph 5.6, the absorption at 330 nm is almost 20 times lower and we observed a weak band at A B Fig.4. Mechanism of the azide radical reaction with tryptophan and N-methylpyrrolidine. 280 nm, which can be assigned to azide radicals. This indicates that azide radical does not react with protonated form of nicotine, because the electron transfer is blocked. Hydrogen abstraction from chiral carbon is also inhibited because of the higher C* H bond dissociation energy than in unprotonated form. The reaction with the unprotonated form is second order with a rate constant of M 1 s 1. To confirm that azide radical can oxidize the pyrrolidinyl nitrogen, we studied its reaction with N-methylpyrrolidine in the presence of tryptophan. Tryptophan is a natural amino acid existing in proteins. Its reaction with azide radical is well known (Fig.4A). It proceeds with electron transfer and generates radicals absorbing at 320 and 520 nm with high extinction coefficients. The rate of this reaction at ph 11.4 is M 1 s 1. Azide radical should react with N-methylpyrrolidine also by electron transfer (Fig.4B). After the pyrrolidinyl nitrogen protonation this way of reaction is blocked. N-methylpyrrolidine has a pk a of 10.46, so the experiments were done at ph 11.4, where there is about 90% of the unprotonated form. The kinetic studies of the 520 nm absorbance changes have been done using a competition method. N-methylpyrrolidine will compete with tryptophan and react with azide radicals, what causes a decrease in the absorbance with increasing alkaloid concentration. The rate constant for the reaction of N-methylpyrrolidine with azide radical was determined to be M 1 s 1. Such a low reaction rate suggest that the electron transfer will have a minor contribution to the mechanism of nicotine reaction with azide radical. Obtained results indicate that azide radical, although is a well-known one-electron oxidant, in energetically favourable conditions it can also abstract hydrogen atoms. References [1]. Pogocki D., Ruman T., Danilczuk M., Danilczuk M., Celuch M., Wałajtys-Rode E.: Eur. J. Pharm., 563, (2007). [2]. Wang S.-L., Wang M., Sun X.-Y., Li W., Ni Y.: Spectrosc. Spect. Anal., 23, (2003). [3]. CRC Handbook of Chemistry and Physics on CD-ROM. CRC Press, [4]. Bobrowski K.: Nukleonika, 50, 3, (2005). [5]. Hug G.L., Wang Y., Schöneich Ch., Jiang P.-Y., Fessenden R.W.: Radiat. Phys. Chem., 54, (1999). [6]. Schuler R.H., Alfassi Z.B.: J. Phys. Chem., 89, (1985). RADIATION EFFECTS IN SORPTION MATERIALS WITH Ag + CATIONS EPR STUDY Anna Bugaj, Jarosław Sadło, Marcin Sterniczuk, Grażyna Strzelczak, Jacek Michalik Removal of radionuclides from aqueous nuclear wastes is a challenging task for the management of waste disposal. Sorbents containing radionuclides are exposed to high level of radiation dose which generates changes in sorbent structure. It is expected that new sorption materials will be not only effective and highly selective but also resistant to radiation for very long time [1-3]. In this report we present the studies on paramagnetic species formed in γ-irradiated saponite and crystalline sitinakite (Fig.1) containing exchangeable Ag + cations. Saponite is a layered clay

23 22 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY mineral belonging to smectite group composed of polyhedral sheets with Si 4+ in tetrahedral sites and Al 3+ and/or Mg 2+ in octahedral ones. The structure of sitinakite [molecular formula Na 2 Ti 2 O 3 (SiO 4 ) 2H 2 O] is similar to commercially available synthetic titanosilicate IONSIV * IE-911. Both materials are successfully used for sorption of radionuclides from Fukushima radioactive wastewaters. A B Fig.2. EPR spectra at 130 K of γ-irradiated sitinakite: (a) dehydrated sample with Na + cations, (b) hydrated sample with Ag + cations, (c) dehydrated sample with Ag + cations. Fig.1. Crystal structure of saponite (A) and sitinakite (B). Electron paramagnetic resonance (EPR) spectroscopy is very useful tool for characterization of paramagnetic species like radicals and paramagnetic atoms or cations generated by radiation in sorbent materials. Fission product radioisotopes can get into reactor primary cooling system as a result of zirconium cladding damage. Silver 110m Ag together with 60 Co, 137 Cs and others belongs to long-lived radioisotopes which for safety reasons should be removed from cooling water. Sorption on microporous materials like zeolites or clays is usually used for that purpose. For model studies of radiation changes of metal valence state by EPR we use silver as an exchangeable cation. Both silver isotopes 107 Ag and 109 Ag have nuclear spin ½ and large magnetic moments which usually makes possible to identify paramagnetic silver species like silver atoms, cations and clusters produced by radiation. Saponite and sitinakite samples after degassing on vacuum line at room temperature or dehydrating at 120 o C were irradiated at 77 K with dose of 10 kgy in Co-60 source. EPR spectra were measured using EPR Bruker X-band ESP 300 spectrometer in the temperature range K. In all cases samples before irradiation did not show any EPR signals. The EPR spectra of γ-irradiated sitinakite measured at 130 K are presented in Fig.2. Dehydrated Na-sitinakite shows strong anisotropic singlet T with orthorhombic symmetry of g-factor: g 1 = 2.003, g 2 = and g 3 = (Fig.2a). Hydrated Na-sitinakite sample shows the same signal. Similar EPR signal was recorded in TiO 2 colloids and was assigned to the hole trapped on the colloidal surface Ti 4+ O 2 Ti 4+ O * [4]. In Ag-sitinakite both in hydrated and dehydrated form, signal T is also recorded but then is accompanied by strong signals of paramagnetic silver species. In hydrated Ag-sitinakite the most pronounced signal is anisotropic doublet with g = 2.039, g II = 2.242, A = 3.2 mt, A II = 4.0 mt (Fig.2b). Doublet with similar g-factors and hyperfine splitting values was earlier observed after irradiation of hydrated zeolite A and was assigned to Ag 2+ divalent cation [5]. In dehydrated Ag-sitinakite perpendicular component of Ag 2+ signal shows additional splittings which indicate the overlapping of Ag 2+ EPR line with unknown signal (Fig.2c). We speculate that three lines labelled x with splitting ~10 mt belongs to the same signal but at this moment we are unable to identify its origin. Doublet H with hyperfine splitting equal ~50 mt present in all spectra in Fig.2 represents hydrogen atoms trapped in spectrosil tubings. Figure 3 shows the EPR spectra of γ-irradiated samples of hydrated saponite synthetized in NIMS, Tsukuba, Japan. The exchangeable cations were introduced into gel before synthesis. In Na-saponite (Fig.3a) three major lines W, Y, Z showing asymmetric shape and additional splitting represent unidentified radiation-induced paramagnetic defects in clay layers. Moreover, in the

24 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 23 sample with exchanged Ag + ions (Fig.3b) appears a weak doublet with hyperfine splitting 64 mt. It represents silver atoms Ag 0. In saponite sample Fig.3. EPR spectrum at 160 K of γ-irradiated hydrated saponite with: (a) Na + ; (b) Na + and Ag + ; (c) Na +, Ag + and Cs +. containing Na +, Ag + and Cs + cations (Fig.3c) the Ag 0 lines clearly shows additional splittings labelled 1, 2, 3 and 4. They are not only due to the different hyperfine splittings of 107 Ag 0 and 109 Ag 0 because then only two lines should be observed at high magnetic field and two ones at low field. In conrast both field regions show four lines which indicates that Ag 0 atoms are stabilized at two different sites. Further experiments will be carried out to specify direct locations of silver trapping sites. This information is crucial to speculate about stability of 110m Ag cations in saponite clays. The research described herein was supported by the National Centre for Research and Development, Poland in the framework of the strategic research project Technologies supporting development of safe nuclear power engineering task 8 Study of processes occurring under regular operation of water circulation systems in nuclear power plants with suggested actions aimed at upgrade of nuclear safety. References [1]. Cabrera C., Gabaldón C., Marzal P.: J. Chem. Technol. Biotechnol., 80(4), (2005). [2]. Allard T., Calas G.: Appl. Clay Sci., 43(2), (2009). [3]. Anthony R.G. et al.: Ind. Eng. Chem. Res., 33(11), (1994). [4]. Micic O.I. et al.: J. Phys. Chem., 97(28), (1993). [5]. Sadlo J., Wasowicz T., Michalik J.: Radiat. Phys. Chem., 45(6), (1995). RADIATON-INDUCED CURING OF EPOXY RESINS AND ITS NANOCARBON COMPOSITES Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski (2) (1) Scheme 1. Formulae of DGEBA (1) and cationic initiator used for radiation-induced curing Rhodorsil 2074 (IPB) (2). Recently published papers have reported that curing of epoxy resins might be supported by ionizing radiation and that such a treatment provides materials with high glass transition temperatures. Although flexural strength of radiation cured epoxy resin is comparable to thermally cured ones, other mechanical parameters are more advantageous. Enhanced toughness and unusual long-term stability make the resins usable under harsh/degradable conditions for many years. In order to obtain good quality material usually a photoinitiator at a concentration of 1% or more is required. The final product shows better features than the resins based on polyamine hardeners [1-3]. In our studies primary objective was to estimate if radiation technique might be applied for the high performance ionizing radiation curable nanocarbon composites based on thermoset. Such products are interesting from the practical point of view as they can be applied in automobile, aircraft and aerospace industry [4]. The work was focused on the studies related to radiation curing of epoxy resins based on diglycidyl ether of bisphenol A (DGEBA) in the presence of cationic photoinitiator Rhodorsil in the form of [4(1-methylethyl)phenyl][4-methylphenyl]iodonium tetrakis(pentafluorophenyl)borate salt [5] (Scheme 1). Carbon nanotubes (CNT) in the form of suspension in epoxy resin were obtained from NA- NOMATERIALS (Warszawa, Poland). Graphene oxide (GO) was synthesized by Hummer s method at the Institute of Electronic Materials Technology (ITME, Poland), whereas the reduced form of the material (RGO) was obtained at the Institute of Nuclear Chemistry and Technology (INCT) as a suspension in dichloromethane (CH 2 Cl 2 ). The ini-

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