An SPS-RS Technique for the Fabrication of SrMoO4 Powellite Mineral-like Ceramics for 90Sr Immobilization.

This paper reports a method for the fabrication of mineral-like SrMoO4 ceramics with a powellite structure, which is promising for the immobilization of the high-energy 90Sr radioisotope. The reported method is based on the solid-phase "in situ" interaction between SrO and MoO3 oxides initiated under spark plasma sintering (SPS) conditions. Dilatometry, XRD, SEM, and EDX methods were used to investigate the consolidation dynamics, phase formation, and structural changes in the reactive powder blend and sintered ceramics. The temperature conditions for SrMoO4 formation under SPS were determined, yielding ceramics with a relative density of 84.0-96.3%, Vickers microhardness of 157-295 HV, and compressive strength of 54-331 MPa. Ceramic samples demonstrate a low Sr leaching rate of 10-6 g/cm2·day, indicating a rather high hydrolytic stability and meeting the requirements of GOST R 50926-96 imposed on solid radioactive wastes. The results presented here show a wide range of prospects for the application of ceramic matrixes with the mineral-like composition studied here to radioactive waste processing and radioisotope manufacturing.

7Be Recovery from Seawater by Sorbents of Various Types.

For the first time, a comprehensive study of sorbents based on manganese dioxide was carried out for beryllium sorption from seawater in laboratory and expeditionary conditions. The possibility of using several commercially available sorbents based on manganese dioxide (Modix, MDM, DMM, PAN-MnO2) and phosphorus(V) oxide (PD) for 7Be recovery from seawater for solving oceanological problems was evaluated. Beryllium sorption under static and dynamic conditions was studied. The distribution coefficients and dynamic and total dynamic exchange capacities were determined. Sorbents Modix (Kd = (2.2 ± 0.1) × 103 mL/g) and MDM (Kd = (2.4 ± 0.2) × 103 mL/g) showed high efficiency. The dependences of the degree of recovery on time (kinetics) and the capacity of the sorbent on the beryllium equilibrium concentration in solution (isotherm) were established. The data obtained were processed using kinetic models (intraparticle diffusion, pseudo-first and pseudo-second orders, Elovich model) and sorption isotherm equations (Langmuir, Freindlich, Dubinin-Radushkevich). The paper contains results of expeditionary studies to evaluate the sorption efficiency of 7Be from large volumes of the Black Sea water by various sorbents. We also compared the sorption efficiency of 7Be for the considered sorbents with aluminum oxide and previously obtained sorbents based on iron(III) hydroxide.

Radionuclides' Recovery from Seawater Using FIC and FIC A Sorbents.

To solve radioecological and oceanological problems (estimate the vertical transport, flows of particulate organic carbon, phosphorus biodynamics, submarine groundwater discharge, etc.), it is necessary to determine the natural values of the radionuclides' activity in seawater and particulate matter. For the first time, the radionuclides' sorption from seawater was studied using sorbents based on activated carbon modified with iron(III) ferrocyanide (FIC) and based on activated carbon modified with iron(III) hydroxide (FIC A-activated FIC) obtained by FIC sorbent treatment with sodium hydroxide solution. The possibility of trace amounts of phosphorus, beryllium, and cesium recovery in laboratory conditions has been investigated. Distribution coefficients, dynamic, and total dynamic exchange capacities were determined. The physicochemical regularities (isotherm and kinetics) of sorption have been studied. The results obtained are characterized via Langmuir, Freindlich, and Dubinin-Radushkevich isotherm equations, as well as pseudo-first and pseudo-second-order kinetic models, intraparticle diffusion, and the Elovich model. Under expeditionary conditions, the sorption efficiency of 137Cs using FIC sorbent, 7Be, 32P, and 33P-using FIC A sorbent with a single-column method by adding a stable tracer, as well as the sorption efficiency of radionuclides 210Pb and 234Th with their natural content by FIC A sorbent in a two-column mode from large volumes of seawater was assessed. High values of efficiency of their recovery by the studied sorbents were achieved.

Estimation of 226Ra and 228Ra Content Using Various Types of Sorbents and Their Distribution in the Surface Layer of the Black Sea.

Radium isotopes have traditionally been used as tracers of surface and underground fresh waters in land-ocean interactions. The concentration of these isotopes is most effective on sorbents containing mixed oxides of manganese. During the 116 RV Professor Vodyanitsky cruise (22 April-17 May 2021), a study about the possibility and efficiency of 226Ra and 228Ra recovery from seawater using various types of sorbents was conducted. The influence of seawater flow rate on the sorption of 226Ra and 228Ra isotopes was estimated. It was indicated that the Modix, DMM, PAN-MnO2, and CRM-Sr sorbents show the best sorption efficiency at a flow rate of 4-8 column volumes per minute. Additionally, the distribution of biogenic elements (dissolved inorganic phosphorus (DIP), silicic acid, and the sum of nitrates and nitrites), salinity, and 226Ra and 228Ra isotopes was studied in the surface layer of the Black Sea in April-May 2021. Correlation dependencies between the concentration of long-lived radium isotopes and salinity are defined for various areas of the Black Sea. Two processes control the dependence of radium isotope concentration on salinity: conservative mixing of riverine and marine end members and desorption of long-lived radium isotopes when river particulate matter meets saline seawater. Despite the high long-lived radium isotope concentration in freshwater in comparison with that in seawater, their content near the Caucasus shore is lower mainly because riverine waters meet with a great open seawater body with a low content of these radionuclides, and radium desorption processes take place in an offshore area. The 228Ra/226Ra ratio derived from our data displays freshwater inflow spreading over not only the coastal region, but also the deep-sea region. The lowered concentration of the main biogenic elements corresponds to high-temperature fields because of their intensive uptake by phytoplankton. Therefore, nutrients coupled with long-lived radium isotopes trace the hydrological and biogeochemical peculiarities of the studied region.

Assessment of Seasonal Variability in Phosphorus Biodynamics by Cosmogenic Isotopes 32P, 33P around Balaklava Coast.

The sorption efficiency of phosphorus from seawater by aluminum oxide and sorbents based on Fe(OH)3 obtained by various methods (using prepared sodium ferrate or precipitation of Fe(OH)3 with ammonia) was assessed. It was shown that phosphorus was recovered most efficiently at a seawater flow rate of one-to-four column volumes per minute with a sorbent based on hydrolyzed polyacrylonitrile fiber with a precipitation of Fe(OH)3 with ammonia. Based on the results obtained, a method for phosphorus isotopes recovery with this sorbent was suggested. Using this method, the seasonal variability of phosphorus biodynamics in the Balaklava coastal area was estimated. For this purpose, the short-lived isotopes of cosmogenic origin 32P and 33P were used. Volumetric activity profiles of 32P and 33P in particulate and dissolved forms were obtained. Based on 32P and 33P volumetric activity, indicators of phosphorus biodynamics were calculated: the time, rate, and degree of phosphorus circulation to inorganic and particulate organic forms. In spring and summer, elevated values of phosphorus biodynamic parameters were determined. This is explained by the peculiarity of the economic and resort activities of Balaklava, which negatively affect the state of the marine ecosystem. The results obtained can be used to assess the dynamics of changes in the content of forms of dissolved and suspended phosphorus, and the biodynamic parameters when performing a comprehensive environmental assessment of the state of coastal waters.

Photonuclear Alchemy: Obtaining Medical Isotopes of Gold from Mercury Irradiated on Electron Accelerators.

In our work, the photonuclear production of 198,199Au isotopes for nuclear medicine purposes was studied, and a method for their recovery from irradiated mercury was developed. The yields of the corresponding nuclear reactions were determined, and a comparison of various methods of obtaining gold radioisotopes was provided. New sorbents based on benzo-15-crown-5, which selectively binds gold, were studied, and the optimal conditions for Au recovery with a high degree of purification from mercury were found. It was established that, for the fast and quantitative recovery of Au isotopes, it was necessary to add at least 0.1 mg of the carrier. As a result, the developed method can be regularly used to obtain 198,199Au for the research of radiopharmaceuticals based on them.

Development of Novel Tetrapyrrole Structure Photosensitizers for Cancer Photodynamic Therapy.

The effectiveness of photodynamic therapy (PDT) is based on the triad effects of photosensitizer (PS), molecular oxygen and visible light on malignant tumors. Such complex induces a multifactorial manner including reactive-oxygen-species-mediated damage and the killing of cells, vasculature damage of the tumor, and activation of the organism immunity. The effectiveness of PDT depends on the properties of photosensitizing drugs, their selectivity, enhanced photoproduction of reactive particles, absorption in the near infrared spectrum, and drug delivery strategies. Photosensitizers of the tetrapyrrole structure (porphyrins) are widely used in PDT because of their unique diagnostic and therapeutic functions. Nevertheless, the clinical use of the first-generation PS (sodium porfimer and hematoporphyrins) revealed difficulties, such as long-term skin photosensitivity, insufficient penetration into deep-seated tumors and incorrect localization to it. The second generation is based on different approaches of the synthesis and conjugation of porphyrin PS with biomolecules, which made it possible to approach the targeted PDT of tumors. Despite the fact that the development of the second-generation PS started about 30 years ago, these technologies are still in demand and are in intensive development, especially in the direction of improving the process of optimization split linkers responsive to input. Bioconjugation and encapsulation by targeting molecules are among the main strategies for developing of the PS synthesis. A targeted drug delivery system with the effect of increased permeability and retention by tumor cells is one of the ultimate goals of the synthesis of second-generation PS. This review presents porphyrin PS of various generations, discusses factors affecting cellular biodistribution and uptake, and indicates their role as diagnostic and therapeutic (theranostic) agents. New complexes based on porphyrin PS for photoimmunotherapy are presented, where specific antibodies are used that are chemically bound to PS, absorbing light from the near infrared part of the spectrum. Additionally, a two-photon photodynamic approach using third-generation photosensitizers for the treatment of tumors is discussed, which indicates the prospects for the further development of a promising method antitumor PDT.

Recovery of Uranium by Se-Derivatives of Amidoximes and Composites Based on Them.

An Se-derivative of amidoxime was synthesized for the first time as a result of the reaction of oxidative polycondensation of N'-hydroxy-1,2,5-oxadiazole-3-carboximidamide with SeO2: its elementary units are linked to each other due to the formation of strong diselenide bridges. The element composition of the material was established, and the structure of the elementary unit was suggested. The sorption-selective properties were evaluated, and it was found that the adsorbent can be used for the selective recovery of U (VI) from liquid media with a pH of 6-9. The effect of some anions and cations on the efficiency of recovery of U (VI) was estimated. Composite materials were fabricated, in which silica gel with a content of 35, 50, and 65 wt.% was used as a matrix to be applied in sorption columns. The maximum values of adsorption of U (VI) calculated using the Langmuir equation were 620-760 mg g-1 and 370 mg g-1 for the composite and non-composite adsorbents, respectively. The increase in the kinetic parameters of adsorption in comparison with those of the non-porous material was revealed, along with the increase in the specific surface area of the composite adsorbents. In particular, the maximum sorption capacity and the rate of absorption of uranium from the solution increased two-fold.

Chemically Induced Polytypic Phase Transitions in the Mg[(UO2)(TO4)2(H2O)](H2O)4 (T = S, Se) System.

Chemically induced polytypic phase transitions have been observed during experimental investigations of crystallization in the mixed uranyl sulfate-selenate Mg[(UO2)(TO4)2(H2O)](H2O)4 (T = S, Se) system. Three different structure types form in the system, depending upon the Se:S ratio in the initial aqueous solution. The phases with the Se/(Se + S) ratios (in mol %) in the ranges 0-9, 16-47, and 58-100 crystallize in the space groups P21, Pmn21, and P21/c, respectively. The structures of the phases are based upon the same type of uranyl-based sulfate/selenate chains that, through hydrogen bonds, are linked into pseudolayers of the same topological type. The layers are linked into three-dimensional structures via interlayer Mg-centered octahedra. The three structure types contain the same layers but with different stacking sequences that can be conveniently described as belonging to the 1M, 2O, and 2M polytypic modifications. The Se-for-S substitution demonstrates a strong selectivity with preferential incorporation of Se into less tightly bonded T1 site. The larger ionic radius of Se6+ relative to S6+ induces rotation of (T1O4) tetrahedra in the adjacent layers and reconstruction of the structure types. From the information-theoretic viewpoint, the intermediate Pmn21 structure type is more complex than the monoclinic end-member structure types.

Macrocyclic receptor for pertechnetate and perrhenate anions.

The design and synthesis of a neutral macrocyclic host that is capable of perrhenate and pertechnetate recognition is described. The anion affinities and underlying coordination modes were estimated by several experimental and theoretical methods including a new technique--reverse (99)Tc NMR titration.

Interaction of transuranium elements with biologically important ligands: structural and spectroscopic evidence for nucleotide coordination to plutonium.

The first complex of a transuranium element (tetravalent plutonium) with nucleotide (deoxycytidinemonophosphate, dCMP) was synthesized and structurally characterized. The crystal structure of [Pu(4)(NO(3))(8)(HdCMP)(4)(H(2)O)(8)](NO(3))(4).2H(2)O consists of complex cations [Pu(4)(NO(3))(8)(HdCMP)(4)(H(2)O)(8)](4+), NO(3)(-) anions, and water molecules. There are two crystallographically independent Pu atoms in the structure, both having similar surroundings. Each of the Pu atoms is coordinated by three O atoms of phosphate groups belonging to three different (HdCMP)(-) anions, two bidentate nitrate anions, and two water molecules. The crystal structure is confirmed by IR and UV/vis/near-IR spectroscopic data.

Interaction of transuranium elements with biologically important molecules: structural and spectroscopic study of NP(V) complexes with imidazole.

New Np(V) complexes with imidazole, [NpO(2)(CH(3)COO)(Im)(2)(H(2)O)], [(NpO(2))(2)(C(2)O(4))(Im)(6)] x 5 Im x H(2)O, and [NpO(2)(NO(2))(Im)(4)], were synthesized. Their crystal structures were determined using X-ray single-crystal diffractometry. The crystal structures are confirmed by IR and UV-vis spectroscopic data. In all three complexes, neptunium coordinates the imidazole molecule through the nitrogen atom. These complexes are the first example of direct bonding of the imidazole molecule to the actinide atom. These results suggest that coordination of histidine residue in proteins or other imidazole-containing biologically important molecules could occur under usual biological conditions.

First structural evidence of actinide-nitrite coordination.

The first nitrite complex of actinide metal, {C(NH 2)3}2[NpO 2(NO 2)(Pic)2], was synthesized, and its crystal structure was determined using X-ray diffractometry and confirmed by NIR and IR spectroscopies. Main crystallographic data: space group P1, triclinic, a = 8.9329(1) A, b = 11.6669(2) A, c = 11.6698(2) A, alpha = 68.080(1) degrees, beta = 88.213(1) degrees, gamma = 73.254(1) degrees, V = 1076.45(3) A (3), and Z = 2.

Highly porous uranyl selenate nanotubules.

A first amine-templated uranyl selenate based upon highly porous uranyl selenate nanotubules, (C4H12N)14[(UO2)10(SeO4)17(H2O)], has been prepared in the room-temperature reaction of uranyl nitrate, butylamine, and H2SeO4 in aqueous solution. The structure consists of nanometer-scale tubular [(UO2)10(SeO4)17(H2O)]14- units packed in a hexagonal-type fashion. The tubules have elliptical cross section with outer dimensions of 25 x 23 A = 2.5 x 2.3 nm. The internal free crystallographic diameter of the tubules is 12.6 A = 1.26 nm, which is comparable to the effective pore size in large-pore zeolites. This finding demonstrates the possibility of nanostructures for actinides in higher oxidation states and opens up a new area of research and exploration.