Radiochemistry

Team Leaders

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Yuri G. Vlasov
Doctor of Chemical Sciences, Professor, Head of Department of Radiochemistry
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Research areas:
- Analytical chemistry
- Radiochemistry
- Chemical sensors
- Multi-Sensor systems

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Yury E. Ermolenko
Doctor of Chemical Sciences, Professor
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Research areas:
- Solid state chemistry and radiochemistry
- The study of ion transport in solids using radioactive indicators
- New membrane materials for chemical sensors with given electrochemical and analytical characteristics
- Nanoscale biosensor devices for study of enzymes

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Raisa N. Krasikova
Ph.D., Associate Professor
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Research areas:
-Radiochemistry
- Radiopharmaceuticals and effective use of nuclear medicine techniques
-Modern radiochemical technologies for the production of short-lived medical radioisotopes

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Dmitry O. Kirsanov
Ph.D., Associate Professor
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Research areas:
- Radiochemistry
- Qualitative and quantitative analysis of complex systems (e.g. spent nuclear fuel reprocessing)
- Instrumental evaluation of taste and quality of different samples in food industry and pharmacy using “electronic tongue” multisensor systems
- Multivariate data analysis (chemometrics)

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Elena V. Puchkova
Ph.D., Associate Professor
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Research areas:
-monitoring of especially toxic natural radionuclides in the biosphere.

Some representative publications

  1. Flourescence quenching features in non-conjugated diacetylene oligomers. Journal of Applied Chemistry, 86(11), P. 1663-1669(2013); 
  2. Oleylamine-stabilized gold nanostructures for bioelectronic assembly. Direct electrochemistry of cytochrome C. Journal of Physical Chemistry C, 117(27), P. 13944-13951(2013);
  3. Diffusion of Tl-204 isotope and ionic conductivity in Tl 4HgI6 membrane material for chemical sensors. Journal of Applied Chemistry, 81(12), P. 2172-2174(2008); 
  4. Preparation of high specific radioactivity [18F]flumazenil and its evaluation in cynomolgus monkey by positron emission tomography. Nucl. Med. Biol., 32, Р. 109-116(2005); 
  5. No carrier added synthesis of O-(2’-[18F]fluoroethyl)-L-tyrosine via a novel type of chiral enantiomerically pure precursor, NiII complex of a (S)-tyrosine Schiff base. Bioorg. Med. Chem., 16(9), Р.4994-5003(2008); 
  6. A combination of dynamic measurement protocol and advanced data treatment to resolve the mixtures of chemically similar analytes with potentiometric multisensor system. Talanta, 119, P. 226-231(2014). 
  7. Assessment of bitter taste of pharmaceuticals with multisensor system employing 3 way PLS regression // Analytica Chimica Acta. 2013. V. 770. P. 45-52.  

Department of Radiochemistry of Faculty of Chemistry of St.Petersburg (Leningrad) State University was founded in 1945. It was the very first Radiochemistry Department in Soviet Union. Now there is one more Radiochemistry Department in Russia in Moscow State University which was created later.

From the very beginning the main aim of St.Petersburg Radiochemistry Department was to teach students fundamental and applied radiochemistry for development new nuclear industry and the first Russian atomic bomb.

Radiochemistry Department had played a great role in these processes. Now there is considerable cooperation with many research institutes in Russia and also with laboratories and universities abroad. In the Radiochemistry Department there are 23 members of teaching and research staff. The Head of the Radiochemistry Department is Prof. Yuri Vlasov.

The modern research activity of Radiochemistry Department can be seen from the projects on some scientific directions which are now in the processing.

I. Nuclear-chemical Processes

Leading Researcher Tat’jana Kochina, Dr.Sci., Senior researcher Igor Ignat’ev, Dr.Sci., Leading research scientist Evgeniya Sinotova, PhD, Engineer Viktor Avrorin, Scientist researcher Anna Alferova, PhD,  Assistant Dmitriy Myalochkin, PhD, High level teacher Evgeniy Kalinin

One of the most interesting aspect of chemical transformations under the β-decay of tritium (hydrogen isotope) imbedded into the molecule is tritium application for the generation of cations as short-living reactive species that are ubiquitous as intermediates in numerous chemical reactions.

To this class of ions belong tricoordinated cations of elements of 14th group with general formula R3M+  (M=C,Si,Ge,Sn.Pb) bearing positive unity charge.

The nuclear-chemical method based on  the β-decay of tritium incorporated in group 14th molecules is used in our studies.

R3MT ß→R3M+  + He0 (M = C, Si, Ge, Sn, Pb)

This method provides unique possibilities to study ion-molecule reactions between cations and neutrals in gas, liquid, and solid phases. Presently, they carry out investigations applying this method in following fields:

The development of methods of generation of cations elements of of group 14th

R3M+ (M=C,Si,Ge,Sn,Pb).

The study of the reactions of these cations with different classes of compounds. The aim of these studies is to establish the general scheme ofinteraction of R3M+  cations with main types of nucleophiles. Ion-molecule reactions with cations labeled by tritium allow us to synthetize labeled compounds which may be used in medical and biological investigations and which hardly can be produced by conventional methods.

The study of different factors, such as temperature, pressure, aggregate state of the reaction mixture on the course of ion-molecule reactions.

The Quantum-chemistry consideration of the processes.

T.Kochina, D.Vraznov, I.Ignatyev, E.Sinotova, M.Voronkov. Nucleogenic silylium cations and their analogs // J.Organomet. Chem. 2011. V.696. P.1331-1340.

II. Chemical sensors

Prof. Yuri Vlasov, Dr.Sci., Prof. Yuri Ermolenko, Dr.Sci., Leading Science Andrey Legin, PhD, Docent Dmitry Kirsanov, PhD, Researcher Dmitry Kalyagin, Researcher Andrey Kruchinin, PhD, Researcher Vasiliy  Kolodnikov

This scientific direction plays a leading role in the domestic and world sensor science. It includes research and development of new types of chemical sensors, membrane  and sensor arrays such as “artificial electronic tongue”, investigations of the mechanism of their operation on the basis of fundamental study of the physical and chemical properties of the membranes. The state of art and the last achievements in the field are published in the monograph “Chemical Sensors”, Editor Yu.Vlasov, Nauka, Moscow, 2011, pp.399. There are some various types of sensors under investigation: solid state glass, single crystal and polycrystalline potentiometric sensors, polymer membrane sensors, optical sensors on the base of amplifying fluorescent polymer (AFP). Sensor investigations consist of analytical properties determination and conductivity, radionuclide diffusion, structure measurements of sensor membranes.

Special attention is paid to multivariate data processing both from the electrochemical sensor arrays and also of optical spectroscopic data, such as possible modalities of multicomponent analysis of several radioactive elements in spent nuclear fuel reprocessing solutions. Other topics include the analysis of water toxicity in terms of biological organisms, the analysis of various foodstuffs, medical diagnostics, etc.

A.V. Legin, D.O. Kirsanov, V.A. Babain, L.N. Gall, N.R. Gall Promising analytical techniques for HLW analysis in “Radioactive Waste: Sources, Types and Management”, pp.77-96, Editors: Satoshi Yuan and Wenxu Hidaka, Total Pages: 224.pp    ISBN: 978-1-62100-188-1 Nova Science Publishers, NY 11788 USA.

Yu.Ermolenko, Dm.Kalyagin, V.Kolodnikov, Yu.Vlasov Tl-selective sensor with membrane on the base of Tl4HgI6 ionic conductor Russ.J.Appl.Chem.,  2013, v.86, N 2, p.209.

III. Nuclear Medicine

Docent Raisa Krasikova, Ph.D. (also Head of Radiochemistry Lab of the N.P. Bechtereva Institute of the Human Brain of the Russian Academy of Sciences (IHB RAS), Saint-Petersburg (Russia)

The area of the research belongs to development of new synthetic methods for radiopharmaceuticals (radiotracers) for Positron Emission Tomography (PET). PET diagnostic agents are radiopharmaceuticals (RPs) labeled with short-lived positron emitting radionuclides. Development of new classes of RPs is an emerging area of PET methodology researches. In the recent years the original labeling and purification strategies for 18F-fluorinated amino acids with potential application in tumors imaging by PET have been developed by Raisa N. Krasikova and her colleagues in the IHB RAS in co-operation with leading Russian groups in asymmetric synthesis institutions (INEOS, Moscow) and Bayer Shering Pharma (Germany). Raisa N. Krasikova is world recognized specialist in development of rapid, reliable and fully automated synthesis approaches and automated synthesis modules for different clinically useful 11C- and 18F-labelled radiotracers. The current interest is focused on development of nucleophilic synthesis methods for 18F-labelled hydroxyl acids (6-16F-L-FDOPS for diagnostics of pheochromocytoma and neuroblastoma) and various 18F-fluorinated receptors PET radioligands. The latter researches are performed in co-operation with Karolinska Institute, Stockholm, Sweden.

R.N. Krasikova, O.F. Kuznetsova, O.S. Fedorova, Yu.N. Belokon, V.I. Maleev, L. Mu, S. Ametamey, P.A. Schubiger, M. Friebe, M. Berndt, N. Koglin, A. Mueller, K. Graham, L. Lehmann, L.M. Dinkelborg. 4-[18F]fluoro glutamic acid (BAY 85-8050) - a new amino acid radiotracer for PET imaging of tumors: Synthesis and in vitro characterization. J. Med. Chem. 2011; 54: 406-410. 

IV. Natural Radionuclides and Nuclear Waste

1. Researcher Mariia Karavan, PhD

Efficient reprocessing of wastes remains one of the most crucial problems in industry nowadays. Long-lived radionuclides, especially actinides, are the most hazardous components of these wastes. Their recovery from the total waste mass, before disposal or reprocessing (transmutation), should enable significantly to raise the ecological safety and efficiency of the nuclear fuel cycle.

One of research tasks is to acquire basic data for the separation of long-lived radionuclides by using novel polyfunctional macrocyclic compounds based on phosphorylated calix[n]arene derivatives. This type of ligands, particularly those substituted at the wide rim and the phosphonate derivatives have been very little investigated so far. Metal ions usually investigated are three trivalent lanthanides (La3+, Eu3+ and Yb3+), one trivalent actinide (Am3+), two tetravalent actinides (Pu4+ and Th4+) one hexavalent actinide (UO22+) and one transition metal under its anionic form, pertechnetate TcO4-.

Main approaches are:

- Extraction of the metal ions from aqueous phases of different acidities into organic phases (meta-nitrobenzotrifluoride (m-NBTF), dichloromethane, dichloroethane). Different experimental protocols are used, according to the nature of salts and of diluents, in order to obtain distribution coefficients or the percentage extraction. They differ mainly by the technique used to monitor the metal ion concentrations in both phases: a- and g-radiometry, absorption spectrometry. In some cases these experiments are completed by tests on real wastes.

- Thermodynamic characterization of complexes formed in homogeneous media using the technique of isothermal titration calorimetry (ITC). This method allows evaluation of stability constants, complexation enthalpy and entropy contributions and stoichiometry of forming complexes. ITC method can also be successfully extended to determine liquid-liquid extraction thermodynamic parameters.

The new task is to develop a microcalorimetric method to understand better the liquid-liquid extraction of radioactive elements using calixarene-based ligands.

Karavan, M., Arnaud-Neu, F., Hubscher-Bruder, V., et al. “Novel phosphorylated calixarenes for the recognition of f-elements“,Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2010, 66 (1), pp. 113-123.

2. Docent Roman Bogdanov, PhD, Docent Elena Puchkova, PhD

Metamict minerals as natural analogues of radioactive waste matrices. Natural radionuclides in the environment.

R. V. Bogdanov, E. V. Puchkova, N. G. Parnikov, and A. S. Sergeev. Radiogenic Uranium in Paragenetic Mineral Associations. Radiokhimiya, 2011, Vol. 53, No. 6, pp. 549–558.

3. Leading Science Rafail Kuznetsov, Dr.Sci.

Briefly problem can be formulated as follows - « a theoretical and experimental substantiation of effective technology of consolidation   toxic radionuclides of nuclear power in a proof matrix with finishing isolation in deep formations of an earth's crust ».

The ultra dispersive technology immobilization fission products and actinides in aluminiumsilicaphosphorus and iron(aluminum)silicaphosphorus matrixes was developed and checked up in practice.

Now work on development of perspective technology of consolidation of nuclear waste in ironpyrophosphrus matrixes, which are formed directly in proof ceramic containers, is conducted. After full hermetic sealing the prepared blocks are a subject to accommodation in a superdeep chink. Estimations show, that such approach can economically provide profitable and absolutely reliable isolation of radioactive waste of high-power nuclear energy.

Kuznetsov R.A. Cosmoschemistry of Th, Sm and Cs and the problems of radioactive waste saving in the earth’s crust. Radiochemistry, 2011, v.51, N 1, p.81-86.

4. Docent Sergey Timofeev, PhD

Held isotope fractionation U-234 and -238 in natural uranium oxides.

Using the emission variant of nuclear gamma resonance investigated the valence state of "hot" atoms of neptunium 237Np, arising from the -decay of 241Am in quenched melts of alkali metal nitrates and adsorbed on various ion exchange materials.

Mathematical model and a computer program based on it to simulate the radiometric method of extraction separation of parent and daughter isotopes. The program allows you to calculate the activity of the daughter isotope selected depending on the time of accumulation, the initial activity of the parent isotope and the perceived effectiveness of the method of separation. It is shown that these computer simulations correspond to the actual processes of radioactive decay and accumulation of isotopes, which adequately reflect the random nature of these processes. 

Experimental studies of radiochemical pollutants in environmental waters and in tap water.

The efficiency of the method of freezing zone for drinking water purification from impurities of inorganic nature. To measure the content of impurities  before and after freeze-band used neutron activation analysis to form radionuclides 56Mn, 116mIn, 198Au. It is shown that the method of freezing zone most effective at very low speeds of the front ice (not higher than 0.15 cm / hr).

Investigating the feasibility of thermonuclear reactions  with deuterons by initiating its powerful electric discharge without the use of uranium or plutonium "detonator", ie in a controlled manner and without the formation of large amounts of radioactive fission products of uranium (plutonium).

Investigating the feasibility of thermonuclear reactions  with deuterons by initiating its powerful electric discharge without the use of uranium or plutonium "detonator", ie in a controlled manner and without the formation of large amounts of radioactive fission products of uranium (plutonium).

The search continues for the optimal conditions for the thermonuclear reactions   based on the isotopic composition of the target, on the basis of which will be developed methods for the detection of related electromagnetic radiation and streams of fast neutrons.

G.A.Srobogatov,V.I.Kusin,M.V.Kaduka,N.S.Shvydko,S.A.Timofeev,Yu.N.Goncharova-

Radiochemical Analysis of  Potable Water from Some Underground Sources of  Leningrad Oblast. Radiochemistry, 2010, Vol. 52, No.5, pp. 542-549.

5. Leading Science Igor Alekseev, PhD

The study of diffusion mobility of impurity "hot" atoms at phase structural transitions.

V. Fundamental Investigations

1. Docent Vyacheslav Eremin, PhD

In his works experimental methods based on the interaction of the processes occurring in the nucleus and the electron shell are  used. Some methods include: nuclear gamma-resonance spectroscopy (Mossbauer Effect), spectroscopy of electron internal conversion, as well as different variants of the “method Δλ/λ“  (λ- the probability of the decay, s-1).

1. The investigation of influence of  different  extranuclear  factors  on l: as a result of numerous experiments have been developed a new method of research of dependence l from the chemical environment of radioactive atoms.
2. The study of the induced gamma-radiation nuclei of long-lived nuclear isomers: experimental testing of the possibility of creation on this basis of the generator of coherent gamma radiation was undertaken.
3. Development of new ecologically safe methods of separation of radionuclides from metal matrices, irradiated in a reactor and cyclotron: the aim is the preparation of sources of nuclear radiation intended for use in the above investigations.
4. The study of the possibilities of implementation of nucleosynthesis reactions in heavy water with the help of a powerful electric discharge: the selected address will be implemented by the organization of small electro-discharge explosions in the liquid phase.
5. The study of the behavior of hot atoms using emission option nuclear resonance spectroscopy: for example, the behavior of atoms of some of transuranic elements in real-world environments.
Skorobogatov G.A., Bondarevskii S.I., Eremin V.V., Timofeev S.A. Consequences of Am-241 a-Decay in Some Solid Matrices, Radiochemistry, 2011, Vol.53, No.5, pp.523-528.

2. Docent Natalia Sablina, PhD

Chemistry and structure of complex compounds of 4d-elements, lanthanides, actinides. Preparation of  ionofores for selective definition of rare-earth elements on the base imprignate polymers.

V.Yu. Smutin, V.A. Gindin, N. O. Sablina, Direction of isomerization of 3 -propargiltio-5-hydroxy-1 ,2,4-triazines according 1H/15N HMBC spectra. Chemistry of Heterocyclic Compounds, 2006, № 3,453-457.

3. Docent Marina Myagkova-Romanova, PhD

Computer modeling of the radioactive decay , extraction and separation of isotopes,  isotope exchange and other radiochemical processes. Development of calculation and training programs for the computer class of the Radiochemistry Department.

Myagkova-Romanova M. A. , Timofeev S.A.  Computer simulation of radiometric for radioactive isotope extraction. Vestnik St.Petersburg University. Ser. 4. 2011. Issue. 4. P. 24–35.