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Vol 60, No 2 (2018)

Article

Heterogeneous Catalytic Synthesis of Organic Compounds Labeled with Hydrogen Isotopes without Using Solvents

Shevchenko V.P., Nagaev I.Y., Myasoedov N.F.

Abstract

Solid-phase procedures for hydrogenolysis, hydrogenation, and isotope exchange are described. The possibilities of the solid-phase method for deuterium or tritium labeling of organic compounds are demonstrated. The influence of the reaction conditions on the yield of the labeled products and on the degree of hydrogen isotope incorporation into them is considered. An attempt is made to rationalize the data obtained by processes occurring in the hydrogen isotope–catalyst–support–substrate system.

Radiochemistry. 2018;60(2):105-139
pages 105-139 views

Synthesis and Structure of Mixed-Cation Salts with [NpO4(OH)2]3– Anions

Grigor’ev M.S., Krot N.N., Charushnikova I.A., Perminov V.P.

Abstract

Mixed-cation salts of the general composition NaM2[NpO4(OH)2]·4H2O, where M = Rb (I, II) and Cs (III), were synthesized and structurally characterized. The compounds differ from each other in the structural organization. The Np central atom in [NpO4(OH)2]3– anions has oxygen surrounding in the form of a tetragonal bipyramid with the O atoms of hydroxide ions in the apical positions. The hydrated Na+ cations have oxygen surrounding in the form of a distorted octahedron. In the structure of I, there are two independent Rb cations with 10- and 12-vertex coordination polyhedra, and in the structures of II and III the framework of large cations is built of 12-vertex Rb and Cs polyhedra. The coordination polyhedra of the Np and Na atoms, sharing a common edge (I, III), or chains of the coordination polyhedra of the Np and Na atoms, sharing common vertices (II), are accommodated in the channels of the frameworks. Hydrogen bonds influence the crystal packing and the geometric characteristics of the [NpO4(OH)2]3– anions.

Radiochemistry. 2018;60(2):140-147
pages 140-147 views

Synthesis and Structure of Mixed Cromate–Nitrate Complexes of Hexavalent Actinides, [(CH3)4N][(AnO2)(CrO4)(NO3)] (An = U, Np, Pu)

Ivanova A.G., Grigor’ev M.S., Fedoseev A.M.

Abstract

Mixed-anion compounds of the general composition [(CH3)4N][(AnO2)(CrO4)(NO3)], where An = U, Np, and Pu, were synthesized and structurally characterized. The structural motif of these compounds is based on anionic ribbons of the composition [AnO2(NO3)(CrO4)]nn–, consisting of seven-vertex An polyhedra linked via oppositely oriented CrO4 tetrahedra and NO3 groups acting in the An polyhedra as terminal bidentate ligands. Every four anionic ribbons form channels oriented along b-axis. Tetramethylammonium cations linked with the O atoms of the ribbons by hydrogen bonds are located in these channels. Actinide contraction is observed in the series U–Np–Pu. It is manifested in a regular decrease in the interatomic distances in the An polyhedra, in parameters b and c, and in the unit cell volume.

Radiochemistry. 2018;60(2):148-151
pages 148-151 views

Reactions of UF6 and HF with Ethanol

Gromov O.B., Khorozova O.D., Travin S.O., Atakhanova E.L.

Abstract

Qualitative studies were performed, and the feasibility of ethanol fluorination by its reactions with anhydrous HF and UF6 was demonstrated. The reaction occurs at temperatures of up to 150°С via replacement of OH groups with probable formation of Freon 161 and substitution of СH groups with the most probable formation of Freon 152. The Freons were identified by IR spectroscopy. The solid reaction products mainly consist of intermediate uranium fluorides. The formation of uranyl fluoride is not proved unambiguously.

Radiochemistry. 2018;60(2):152-157
pages 152-157 views

A CVD Process for Producing Atomic Current Sources Based on 63Ni

Kharitonov I.D., Mazgunova V.A., Babain V.A., Kostylev A.I., Merkushkin A.O., Shemukhin A.A., Balakshin Y.V., Kozhemyako A.V., Kalmykov S.N., Magomedbekov E.P.

Abstract

A CVD process was developed for producing 63Ni-based atomic batteries by deposition of active 63Ni layers onto semiconductor silicon supports. Tetrakis(trifluorophosphine)nickel synthesized from 63Ni metal and phosphorus trifluoride was used as the volatile precursor. The influence of the support temperature and working pressure on the characteristics of the 63Ni coating was examined.

Radiochemistry. 2018;60(2):158-163
pages 158-163 views

New Procedure for Wet Crude Yellowcake Purification

Morsy A.M., Ali A.H., Elgammal E.M.

Abstract

The ability of sodium nitrate/urea mixture in the presence of tetrahydrofuran to enhance the purity of uranium produced from crude yellowcake with the subsequent preparation of different forms of highly pure uranium oxides (UO4·4H2O, U3O8, UO3) was examined. The methods of X-ray fluorescence, X-ray diffraction, and energy-dispersive X-ray analysis and inductively coupled plasma optical emission spectrometry were used. The highest uranium purity was reached using 1 M NaNO3 + 1 or 2 M urea. The uranium loss from the crude yellowcake was insignificant.

Radiochemistry. 2018;60(2):164-169
pages 164-169 views

Extraction of REE(III), U(VI), and Th(IV) from Nitric Acid Solutions with Carbamoylmethylphosphine Oxides in the Presence of Bis[(trifluoromethyl)sulfonyl]imide Ions

Turanov A.N., Karandashev V.K., Yarkevich A.N.

Abstract

Extraction of microamounts of REE(III), U(VI), and Th(IV) with solutions of carbamoylmethylphosphine oxides (CMPOs) in organic diluents from aqueous HNO3 solutions containing lithium bis[(trifluoromethyl) sulfonyl]imide (LiTf2N) was studied. The efficiency of the REE(III), U(VI), and Th(IV) extraction from nitric acid solutions with CMPO solutions considerably increases in the presence of Tf2N ions in the aqueous phase. The stoichiometry of the extractable complexes was determined, and the influence of the structure of the CMPO molecule, kind of organic diluent, and aqueous phase composition on the efficiency of the U(VI), Th(IV), and REE(III) extraction into the organic phase was considered.

Radiochemistry. 2018;60(2):170-176
pages 170-176 views

Problems of Describing Complex Sorption Equilibria

Polyakov E.V.

Abstract

Problems of choosing a model for describing empirical sorption data in a system consisting of an energetically nonuniform sorbent and a chemically uniform sorbate in the case when the distribution of energetically nonuniform sorption sites in the material is unknown a priori are considered. The advantages and drawbacks of choosing a sorption model adequate to the experimental data on the basis of analysis of variance are analyzed taking into account the estimated boundaries of the minimum necessary accuracy of the primary experimental data. Statistical methods do not always allow unambiguous choice of an adequate model because of limited accuracy of the experimental data. In such cases, the check of the physicochemical consequences of the model is the best argument in favor of its adequacy.

Radiochemistry. 2018;60(2):177-185
pages 177-185 views

Sorption of Radionuclides from the Primary Circuits of Reactors with Pb–Bi Coolant onto the Surface of Structural Materials of the Reactor Core

Naumov V.S., Konovalov E.E.

Abstract

Sorption and phase distribution of 54Mn, 59Fe, 60Со, 106Ru, 125Sb, 137Cs, 144Се, 154,155Eu, and 235,238U radionuclides in contact of the Pb–Bi melt with the steel surface were studied. Radionuclides of the elements with the minimal oxygen affinity (Ru, Te, and Sb) remain mainly in the coolant melt and are weakly sorbed onto the solid phase. The other fission product radionuclides having higher oxygen affinity are sorbed onto the surface of steel structural materials. The sorption increases at 350–400°С.

Radiochemistry. 2018;60(2):186-194
pages 186-194 views

Uranium Preconcentration with a Chelating Sorbent Based on Maleic Anhydride–Styrene Copolymer

Hajiyeva S.R., Bahmanova F.N., Alirzaeva E.N., Shamilov N.T., Chyragov F.M.

Abstract

The ability of a chelating sorbent based on maleic anhydride–styrene copolymer to take up uranium was studied. The sorbent was prepared by modification of the copolymer with Norsulfazolum in the presence of formaldehyde. The dependence of the sorption capacity on the solution acidity was studied. At pH 5, the degree of sorption passes through a maximum. As the uranium concentration in the solution is increased, the amount of the sorbed metal increases, reaching a maximum at a concentration of 8 × 10–3 M (SC = 1253 mg g–1). The influence of the solution ionic strength on the uranium sorption was examined. The ionic strength of up to 0.4 M does not affect the sorption, but as the ionic strength is increased further, the sorption decreases, first gradually and then sharply. The desorption of the sorbed uranium ions was studied. The effect of mineral and organic acids on the uranium desorption was examined. The desorption is maximal with HClO4.

Radiochemistry. 2018;60(2):195-200
pages 195-200 views

Synthesis, Characterization, and Radiolabeling of Heterocyclic Bisphosphonate Derivative as a Potential Agent for Bone Imaging

Motaleb M.A., Sanad M.H., Selim A.A., El-Tawoosy M., Abd-Allah M.

Abstract

1-Hydroxy-2-(2-pyridyl)ethanedisphosphonic acid monosodium salt (HPEDP) was prepared and labeled with 99mTc using two different reducing agents: SnCl2·2H2O and NaBH4; NaBH4 gave better results. The radiochemical purity of 99mTc(NaBH4)-HPEDP was 96 ± 4%, and the complex was stable in vitro for 6 h. The in vivo biodistribution studies performed in mice show highly selective uptake of the labeled compound in the skeletal system and rapid elimination via the urinary pathway. The maximum bone uptake was 32.3 ± 2.1% ID/organ.

Radiochemistry. 2018;60(2):201-207
pages 201-207 views

Formulation and Biodistribution of 99mTc-Dacarbazine, a Radioligand for Neoplasm Imaging

Amin A.M., Abd El-Halim S.M., El-Sabagh H.A., Abdel-Mottaleb M.S.

Abstract

A method for preparing 99mTc-Dacarbazine, a potential cancer diagnostic agent, was developed. The method is based on direct labeling of Dacarbazine with 99mTc in the presence of stannous chloride as reducing agent. The reaction conditions were optimized to obtain the radiochemical yield of 99mTc-Dacarbazine higher than 90%. The biodistribution of 99mTc-Dacarbazine in normal and tumor-bearing Albino Swiss mice was studied. 99mTc-Dacarbazine has a high tumor affinity and shows promise for cancer imaging. Quantitative relationship between the optimized structures and computed molecular properties related to Dacarbazine binding sites was analyzed using molecular modeling.

Radiochemistry. 2018;60(2):208-214
pages 208-214 views

Radionuclide Enrichment Near Coal Processing in Southern Brazil

Campaner V.P., Luiz-Silva W., Smoak J.M., Sanders C.J.

Abstract

This work highlights environmental radionuclide enrichment as a result of coal mining activity, including disbursement related to the coal processing in southern Brazil. Soil cores collected near the coal mining area showed 238U, 226Ra and 210Pb activities approximately 2 times greater than the background values. The highest activities were found at the surface and decrease downcore, indicating recent enrichment. Furthermore, atmospheric analyses of particulate matter indicated radionuclide enrichment up to 352 and 463 μBq m–3 of 226Ra and 210Pb, respectively, at the sites nearest to the coal-fired power plant. The atmospheric particulate material showed 210Pb/226Ra ratios similar to the fly ash near the coal-fired power plant, suggesting an enhanced source of 222Rn to the atmosphere likely associated with the power plant. However, no risk to the population near the coal processing was found, as noted by the total air absorbed γ-ray dose rate in the topsoil samples, 74 ± 19 nGy h–1, statistically similar to the background radioactivity (60 nGy h–1).

Radiochemistry. 2018;60(2):215-220
pages 215-220 views

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