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Ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Based on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log Ksp = -59.3 ± 0.3 in 0.01 M NaClO4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO2 in aqueous media.

Neptunium is a toxic component of radioactive waste whose migration in the environment must be illuminated. The interaction of Np(V) with a peaty-podzolic-gleyic soil profile comprising six horizons was extensively studied. Differences in the shape of the sorption dependencies indicate different mechanisms for the reactions occurring. X-ray absorption spectroscopy provided detailed insights into this interaction, identifying the reduction of Np(V) to Np(IV) in the upper horizons owing to soil organic matter. These findings were compared with sequential extraction results and analyses of soil organic matter dissolution. This comprehensive approach enabled the development of a neptunium interaction scheme across all soil horizons, including the reduction of Np(V) and its complexation with soluble organic matter., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Anna Romanchuk reports a relationship with Lomonosov Moscow State University that includes: employment., (Copyright © 2025 Elsevier Ltd. All rights reserved.)

In the present study, the dissolution and microstructural transformation of CeO 2 nanoparticles (NPs) in a phosphate-containing milieu were investigated. The dissolution behaviour of 2 nm and 5 nm CeO 2 NPs in phosphate buffer solutions was found to differ markedly from that observed in 0.01 M NaClO 4 . Through synchrotron X-ray diffraction analysis and X-ray absorption spectroscopy, the interaction between CeO 2 NPs and phosphate species was examined, revealing the transformation of the oxide into sodium-cerium double phosphate, with cerium predominantly existing in the Ce(IV) state. According to scanning and transmission electron microscopy observations, thus formed Na-Ce(IV) phosphate consists of spindle-like aggregates of nanocrystalline rods, presumably formed during phosphate anions sorption on the initial CeO 2 surface. Pair distribution function analysis revealed that Na-Ce(IV) phosphate has a three-dimensional framework crystal structure, similar to NaTh 2 (PO 4 ) 3 , as reported earlier, with large channels along the c-axis containing disordered sodium atoms. This study represents the first detailed analysis of phosphate-induced speciation and microstructural transformation of CeO 2 NPs, resulting in the formation of Ce(IV) phosphate. Similar processes may occur in natural ecosystems upon the introduction of CeO 2 NPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Sorption of Pu(VI) onto synthesized goethite under oxidizing and normal conditions was investigated, which revealed its pH dependence on different solid/liquid ratios. Pu speciation upon sorption on the solid phase was characterized via extended X-ray absorption fine structure (EXAFS) spectroscopy, while that in solution was assessed using ultraviolet-visible (UV-Vis) spectroscopy and liquid-liquid extraction. The obtained results demonstrate differences in plutonium behavior in the studied systems. Pu(VI) remains hexavalent on the goethite surface and in solution under oxidizing conditions. While Pu(IV) is stabilized on the mineral and Pu(V) is found in solution under normal conditions. This study provides the thermodynamic descriptions of these reactions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Transuranium elements such as Np, Pu and Am, are considered to be the most important radioactive elements in view of their biological toxicity and environmental impact. Concentrations of 237 Np, Pu isotopes and 241 Am in two sediment cores collected from Peter the Great Bay of Japan Sea were determined using radiochemical separation combined with inductively coupled plasma mass spectrometry (ICP-MS) measurement. The 239,240 Pu and 241 Am concentrations in all sediment samples range from 0.01 Bq/kg to 2.02 Bq/kg and from 0.01 Bq/kg to 1.11 Bq/kg, respectively, which are comparable to reported values in the investigated area. The average atomic ratios of 240 Pu/ 239 Pu (0.20 ± 0.02 and 0.21 ± 0.01) and 241 Am/ 239+240 Pu activity ratios (3.32 ± 2.76 and 0.45 ± 0.17) in the two sediment cores indicated that the sources of Pu and Am in this area are global fallout and the Pacific Proving Grounds through the movement of prevailing ocean currents, and no measurable release of Np, Pu and Am from the local K-431 nuclear submarine incident was observed. The extremely low 237 Np/ 239 Pu atomic ratios ((2.0-2.5) × 10 -4 ) in this area are mainly attributed to the discrepancy of their different chemical behaviors in the ocean due to the relatively higher solubility of 237 Np compared to particle active plutonium isotopes. It was estimated using two end members model that 23% ± 6% of transuranium radionuclides originated from the Pacific Proving Grounds tests, and the rest (ca. 77%) from global fallout., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Though uranium is usually present in its +6 oxidation state (as uranyl ion) in aqueous solutions, its conversion to oxidation states such as +4 or +5 is a challenging task. Electrochemical reduction and axial oxo activation are the preferred methods to get stable unusual oxidation states of uranium in an aqueous medium. In previous studies, dicarboxylic acid has been used to stabilize UO 2 + in aqueous alkaline solutions. In the present work, a diphosphonate ligand was chosen due to its higher complexing ability compared to that of the carboxylate ligands. Neptunium complexation studies with 2,6-pyridinediphosphonic acid (PyPOH) indicated the formation of different species at different pH values and the complexation facilitates disproportionation of NpO 2 + to Np 4+ and NpO 2 2+ at pH 2. Hexavalent actinides form insoluble complexes in aqueous media at pH = 2, as confirmed by UO 2 2+ complexation studies. The in situ complexation-driven precipitation resulted in conversion to pure Np 4+ in aqueous media as the Np 4+ -PyPOH complex. A strong complexing ability of the PyPOH ligand toward the Np 4+ ion is also seen for the stabilization of the electrochemically generated U 4+ in aqueous medium under aerobic conditions. The U 4+ -PyPOH complex was found to be stable for 3 months. Raman, UV-vis, fluorescence, and cyclic voltametric studies along with density functional theory (DFT) calculations were done to get structural insights into the PyPOH complexes of actinides in different oxidation states.

The concentration and sorption behavior of 237 Np on the bottom sediments of water bodies in the Far East region of Russia (Lake Khanka and Peter the Great Bay) were studied for the first time. The 237 Np concentrations vary from 1.06 × 10 -6 to 4.43 × 10 -5 mBq g -1 in the bottom sediments of Lake Khanka and from 1.05 × 10 -4 to 2.52 × 10 -3 mBq g -1 for Amur Bay. The experiment on the adsorption of Np on marine and lake sediment showed that it is sorbed through complexation with silicates (albite, leucite). The Np sorption isotherm on marine sediments is described by the Langmuir equation; the distribution coefficients (Kd) of Np vary from 57 to 588 mL g -1 . For lake sediments, the isotherm is described by the Henry equation; the Kd value reaches 935 mL g -1 ., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Kuzmenkova Natalia reports financial support was provided by Russian Science Foundation. Hou Xiaolin reports financial support was provided by National Natural Science Foundation of China. Co-author is an assocaited editor in Journal of Environmental radioactivity., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

A variant of microfluidic setup design for the study of extraction kinetics has been proposed. Mass transfer constants for Am(III) and Eu(III) and observed rate constants were obtained for N-,O-donor ligands featuring phenanthroline and bipyridyl cores. The possibility of determining rate constants for cations independently of each other makes it possible to observe the kinetic effect of separation. The extraction rate was found to be lower for the bipyridyl ligand, compared to phenanthroline. The values of the rotation barriers for the ligands were calculated using the DFT method. The values correlate with the obtained low extraction rate for the bipyridyl ligand. Also, crystallographic data showing anti-conformation for the bipyridyl ligand align with the kinetic data. Surface tension was also determined for the systems with the studied ligands. It is shown that at equal ligand concentrations, the value of surface tension agrees with the extraction rate. Furthermore, it is shown that for the bipyridyl ligand, prior contact of the organic phase with nitric acid significantly affects the surface tension.

Herein, neptunium(V) carbonates containing sodium or potassium cations were synthesized via chemical precipitation. Various techniques such as scanning electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetry combined with differential scanning calorimetry, X-ray diffraction, and X-ray absorption spectroscopy were used to analyze the microstructures and elemental compositions of these samples. The crystal structures of hydrated NaNpO 2 CO 3 ·3H 2 O ( P 1, a = 4.3420(2) Å, b = 4.8962(2) Å, c = 10.0933(11) Å, α = 91.014(7)°, β = 77.834(11)°, and γ = 90.004(10)°) and KNpO 2 CO 3 ( P 6 3 / mmc , a = b = 5.0994(2) Å, c = 10.2210(15) Å) were determined for the first time using the Rietveld method. The synthesized carbonates exhibited distinct structural features and decomposition behaviors, as demonstrated through thermogravimetry analysis, which revealed the presence of crystalline hydrate water in sodium neptunium(V) carbonate. Furthermore, calcium-containing neptunium(V) carbonates were synthesized and characterized. Samples with the general composition Ca 0.5 NpO 2 CO 3 were obtained using the ion exchange method and chemical precipitation from solutions containing competing cations (Ca 2+ , Na + , K + , and Mg 2+ ). The synthesis conditions notably affected the diffraction patterns of the obtained calcium neptunium(V) carbonates. This investigation enhances our understanding of the structural properties and thermodynamic stability of neptunium(V) carbonates in the presence of diverse cations commonly found under radioactive waste disposal conditions.

In this study, pyridine and phenanthroline diphosphonate ligands were investigated for the first time from the context of solvent extraction and potentiometric sensing of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) cations. The extraction efficiency under the same conditions for phenanthroline-diphosphonates is considerably higher than that for pyridine ligands. At the same time, the pyridine-diphosphonates show pronounced selectivity towards lead in this metal series. The extraction systems with phenanthroline diphosphonates provided the most efficient extraction of Cd(II) and Pb(II) cations ( D > 90). The newly developed pyridine and phenanthroline diphosphonate ligands have proven to be highly effective components in plasticized polymeric membranes. These ligands can be utilized to construct potentiometric ion sensors that exhibit a notable response specifically towards Pb(II) cations. Among the previously reported tetradentate ligands, the phenanthroline diphosphonate ligand, when incorporated into plasticized polymeric membranes, demonstrated the highest sensitivity towards d-metals and Pb(II). The structure of the single crystal complex of Pb(II) and Cd(II) with pyridine-diphosphonates was studied by X-ray diffraction analysis (XRD). The geometry of Cu(II), Zn(II), Cd(II) and Pb(II) complexes and the energy effect of the complex formation, including pseudo-oligomerization reactions, were determined by DFT calculations. The high sensing and extraction efficiency of diphosphonates with respect to Pb(II) is consistent with the minimum values of complex formation energies. The variation in sensory and extraction properties observed among the studied diphosphonate ligands is influenced by the ability to form polynuclear complexes with Pb(II) cations, whereas such properties are absent in the case of Cd(II) cations.

Porous carbons are not favorable for sorption of heavy metals and radionuclides due to absence of suitable binding sites. In this study we explored the limits for surface oxidation of "activated graphene" (AG), porous carbon material with the specific surface area of ∼2700 m 2 /g produced by activation of reduced graphene oxide (GO). Set of "Super-Oxidized Activated Graphene" (SOAG) materials with high abundance of carboxylic groups on the surface were produced using "soft" oxidation. High degree of oxidation comparable to standard GO (C/O=2.3) was achieved while keeping 3D porous structure with specific surface area of ∼700-800 m 2 /. The decrease in surface area is related to the oxidation-driven collapse of mesopores while micropores showed higher stability. The increase in the oxidation degree of SOAG is found to result in progressively higher sorption of U(VI), mostly related to the increase in abundance of carboxylic groups. The SOAG demonstrated extraordinarily high sorption of U(VI) with the maximal capacity up to 5400 μmol/g, that is 8.4 - fold increase compared to non-oxidized precursor AG, ∼50 -fold increase compared to standard graphene oxide and twice higher than extremely defect-rich graphene oxide. The trends revealed here show a way to further increase sorption if similar oxidation degree is achieved with smaller sacrifice of surface area., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Conflicts of interest The authors declare no financial or commercial conflict of interest., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

In the current research, we conducted a comparative study of the Ac 3+ complex with H 4 DOTA and H 4 BATA. The stability constants of the [AcBATA] - and [AcDOTA] - complexes were studied directly by extraction methods. We discovered that the thermodynamic properties of the [AcBATA] - complex are superior to those of [AcDOTA] - . Moreover, the fast kinetics of H 4 BATA complexation with Ac 3+ during the radiolabeling experiment was observed already at room temperature. Ac 3+ was placed inside the macrocyclic cavity of the [AcBATA] - complex, preventing the release of the cation. According to DFT studies, two possible conformations were found, where two pendant arms coordinate with the metal cation on one side of the azacrown cavity and two on the other side, or three pendant arms are located on one side and one on the other. Finally, high inertness in vitro and in vivo of [AcBATA] - was discovered, making the H 4 BATA ligand highly preferable for application as a component of actinium-based radiopharmaceuticals.

The production possibility of 161 Tb and 155 Tb by irradiating of natural dysprosium with gamma rays obtained by decelerating an electron beam with an energy of 55 MeV has been demonstrated experimentally. The yield of 161 Tb was 14.4 × 10 3 Bq × μA -1  × h -1  × cm 2 × g Dy2O3 -1 . Simultaneously, upon irradiation, 155 Dy is formed with the yield of 25 × 10 3 Bq × μA -1  × h -1  × cm 2 × g Dy2O3 -1 , which leads to the formation of 1.6 × 10 3 Bq × μA -1  × h -1  × cm 2 × g Dy2O3 -1 of 155 Tb. It has been shown that the isolation of terbium radioisotopes from tens of mg of dysprosium target can be achieved by extraction chromatography, and final separation yield was 39%. The impurity of 160 Tb is 7.3% of the 161 Tb activity at EOB., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In this work, we synthesized two new benzo-18-azacrown-6 ethers bearing picolinate and pyridine pendant arms and studied the copper complexes of these ligands, as well as those of an acetate analog. All considered ligands were capable of forming mono- and dinuclear complexes due to their large size and large number of donor sites. Among all forms of complexes, the coordination of cations inside the macrocycle has only been shown for the mononuclear form of the acetate complex, while out-cage coordination has been observed for other forms. Electrochemical studies have shown the instability of the mononuclear form of the complex with the pyridine ligand to the reduction in the range of redox potentials of bioreductants. The stabilities of labeled acetate complexes with "in-cage" coordination of the cation and picolinate with "out-cage" coordination were compared in an excess of serum and superoxide dismutase; while the former turned out to be unstable to transchelation, the latter was stable throughout the experiment. Additional studies in biologically relevant media were performed for the picolinate complex and demonstrated its stability in vitro . The biodistribution of this complex in mice after 6 hours post-injection demonstrates a slow excretion from the body; however, the accumulation is noticeably lower than that of free copper cations.

The sorption of Ce(III) on three abundant environmental minerals (goethite, anatase, and birnessite) was investigated. Batch sorption experiments using a radioactive 139 Ce tracer were performed to investigate the key features of the sorption process. Differences in sorption kinetics and changes in oxidation states were found in the case of the sorption of Ce(III) on birnessite compared to that on other minerals. Speciation of cerium onto all of the studied minerals was investigated using spectral and microscopic methods: high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and X-ray absorption spectroscopy (XAS) in conjunction with theoretical calculations. It was found that during the sorption process onto birnessite, Ce(III) was oxidized to Ce(IV), while the Ce(III) on goethite and anatase surfaces remained unchanged. Oxidation of Ce(III) by sorption on birnessite was also accompanied by the formation of CeO 2 nanoparticles on the mineral surface, which depended on the initial cerium concentration and pH value.

Phenanthroline diamides ( L ) demonstrated a unique ability to extract uranium from nitric acid solutions into a polar organic solvent forming complexes of 1:2 stoichiometry as tight ion pairs {[UO 2 L NO 3 ] + [UO 2 (NO 3 ) 3 ] - } by a novel extraction mechanism, which is a combination of two already well-known mechanisms: solvation and ion-pair anion exchange. A UV-vis study was used to confirm the formation of such complexes directly in the organic phase. Moreover, chemical synthesis and single crystal growth were performed to confirm unambiguously the structure of the complexes in the solid state.

The fractionation of high-level radioactive waste from nuclear power plants simplifies the handling of its components, and facilitates the reduction of radiotoxic effects on the environment. The search and study of new ligands for solvent extraction, as one of the methods in fractionation, remains a complex and important research task. In this work, four pyridine diphosphonate ligands were synthesized. These ligands are part of the class of the N,O-donor extractants, which are selective towards Am(III). The separation factor SF(Am/Eu) for the best extractant reached values up to 10. The influence of the substituents on the efficiency of extraction and complexation of trivalent f-elements, the kinetics of extraction, and the behavior of the ligand at the interface were described. The effect of nitric acid concentration on the extraction was shown. The stoichiometry of the complexes was determined by slope analysis in solvent extraction experiment and verified by spectrophotometric titration in acetonitrile. Liquid tension experiments with a pendant drop method revealed the interfacial properties of the ligands in "F-3 solvent/H 2 O" and "F-3 solvent/HNO 3 " systems. The relationship between the surface activity and the ligand structure was shown. Studies of the extraction kinetics were performed in a modified Lewis cell. The effect of the ligand structure on the extraction rate was shown. The DFT calculation with the B3LYP density functional was used to explain the extraction properties of the ligands, including selectivity. The calculation of the pre-organization energy of the ligands explained the kinetics and extraction patterns for the studied series.

The first examples of 1,10-phenanthroline-2,9-diamides bearing CF 3 -groups on the side amide substituents were synthesized. Due to stereoisomerism and amide rotation, such complexes have complicated behavior in solutions. Using advanced NMR techniques and X-ray analysis, their structures were completely elucidated. The possibility of the formation of complex compounds with lanthanoids nitrates was shown, and the constants of their stability are quantified. The results obtained are explained in terms of quantum-chemical calculations.

A synthetic procedure for the synthesis of azacrown ethers with a combination of pendant arms has been developed and the synthesized ligand, characterized by various techniques, was studied. The prepared benzoazacrown ether with hybrid pendant arms and its complexes with copper and lead cations were studied in terms of biomedical applications. Similarly to a fully acetate analog, the new one binds both cations with close stability constants, despite the decrease in both constants. The calculated geometry of the complexes correlate with the data from X-ray absorption and NMR spectroscopy. Coordination of both cations differs due to the difference between the ionic radii. However, these chelation modes provide effective shielding of cations in both cases, that was shown by the stability of their complexes in the biologically relevant media towards transchelation and transmetallation.

The aim of this study is to synthesize PuO 2 nanoparticles (NPs) at low pH values and characterize the materials using laboratory and synchrotron-based methods. Properties of the PuO 2 NPs formed under acidic conditions (pH 1-4) are explored here at the atomic scale. High-resolution transmission electron microscopy (HRTEM) is applied to characterize the crystallinity, morphology and size of the particles. It is found that 2 nm crystalline NPs are formed with a PuO 2 crystal structure. High energy resolution fluorescence detected (HERFD) X-ray absorption spectroscopy at the Pu M 4 edge has been used to identify the Pu oxidation states and recorded data are analysed using the theory based on the Anderson impurity model (AIM). The experimental data obtained on NPs show that the Pu(iv) oxidation state dominates in all NPs formed at pH 1-4. However, the suspension at pH 1 demonstrates the presence of Pu(iii) and Pu(vi) in addition to the Pu(iv), which is associated with redox dissolution of PuO 2 NPs under acidic conditions. We discuss in detail the mechanism that affects the PuO 2 NPs synthesis under acidic conditions and compare it with one in neutral and alkaline conditions. Hence, the results shown here, together with the first Pu M 4 HERFD data on PuF 3 and PuF 4 compounds, are significant for the colloid facilitated transport governing the migration of plutonium in a subsurface environment., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Reprocessing of spent nuclear fuel (SNF) is an important task in a frame of ecology and rational use of natural resources. Uranium, as the main component of SNF (>95%), can be recovered for further use as fresh nuclear fuel. To minimize an amount of solid radioactive waste generated during SNF reprocessing, new extractants are under investigation. Diamides of 1,10-phenanthroline-2,9-dicarboxylic acid are perspective tetradentate N-donor ligands that form strong complexes with f -elements, which are soluble in polar organic solvents. As an example of three ligands of this class, we conducted a comparative study and showed how the substituent in the amide functional group affects the extraction ability toward uranyl nitrate from nitric acid media. We have performed a careful study (NMR, FT-IR, XRD, RMC-EXAFS) of the structures of synthesized complexes of new ligands with uranyl nitrate and used quantum mechanical calculations to explain the discovered regularities through.

Somatostatin analogues play an important role in the therapy of neuroendocrine tumors by binding to somatostatin receptors on the surface of cancer cells. In this work, we analyze the receptor-binding affinity and in vitro stability of a novel ultra-short somatostatin analogue Thz-Phe-D-Trp-Lys-Thr-DOTA (DOTA-P4). This conjugate is successfully radiolabeled with 44 Sc, 90 Y, 152 Eu, and 207 Bi, characterized and validated by thin layer and high-performance liquid chromatography. The optimum conditions for M-DOTA-P4 labeling are found. In vitro stability studies are performed in saline, in the presence of serum proteins, and with biologically relevant metal cations. All complexes demonstrate no cation release in vitro within 4-24 h. The conformations of DOTA-conjugates are studied by circular dichroism spectroscopy. The circular dichroism spectra of DOTA-P4 conjugates show a negative peak at 225 nm, which may correspond to the required β-sheet conformation. The binding to somatostatin receptors of types 2 and 5 is performed with the IMR-32 cells at 4°C, with non-specific binding representing 26% of the total binding. A two-line approximation of the Scatchard plot results in the apparent dissociation constants of 0.10 and 2.25 nM. It is shown that the chelator position with respect to the amino acid sequence significantly affects the labeling conditions with cations of different ionic radii. For the first time, the binding of a linear type ultra-short peptide conjugate with DOTA to somatostatin receptors is demonstrated. The obtained results are promising for experiments with DOTA-P4 in vivo in mice with inoculated tumors., (© 2021 European Peptide Society and John Wiley & Sons, Ltd.)

Hybrid donor extractants are a promising class of compounds for the separation of trivalent actinides and lanthanides. Here, we investigated a series of sterically loaded diphosphonate ligands based on bipyridine (BiPy-PO-iPr and BiPy-PO-cHex) and phenanthroline (Phen-PO-iPr and Phen-PO-cHex). We studied their complex formation with nitrates of trivalent f-elements in solvent extraction systems (Am and Eu) and homogeneous acetonitrile solutions (Nd, Eu, and Lu). Phenanthroline extractants demonstrated the highest efficiency and selectivity [ SF (Am/Eu) up to 14] toward Am(III) extraction from nitric acid solutions among all of the studied diphosphonates of N-heterocycles. The binding constants established by UV-vis titration also indicated stronger binding of sterically impaired diphosphonates compared to the primary substituted diphosphonates. NMR titration and slope analysis during solvent extraction showed the formation of 2:1 complexes at high concentrations (>10 -3 mol/L) for phenanthroline-based ligands. According to UV-vis titrations at low concentrations (10 -5 -10 -6 mol/L), the phenanthroline-based ligands formed 1:1 complexes. Bipyridine-based ligands formed 1:1 complexes regardless of the ligand concentration. Luminescence titrations revealed that the quantum yields of the complexes with Eu(III) were 81 ± 8% (BiPy-PO-iPr) and 93 ± 9% (Phen-PO-iPr). Single crystals of the structures [Lu(μ 2 ,κ 4 -(iPrO) 2 P(O)Phen(O) 2 (OiPr))(NO 3 ) 2 ] 2 and Eu(Phen-PO-iPr)(NO 3 ) 3 were obtained by chemical synthesis with the Phen-PO-iPr ligand. X-ray diffraction studies revealed a closer contact of the f -element with the aromatic N atoms in the case of sterically loaded P═O ligands compared with sterically deficient ligands. Density functional theory calculations allowed us to rationalize the observed selectivity trends in terms of the bond length, Mayer bond order, and preorganization energy.

About ten years have passed since the last published report in Russian on the speciation and distribution features of radionuclides in the bottom sediment of Production Association (PA) "Mayak" (further mentioned as Mayak) artificial reservoirs. Herein, the desorption parameters of 137 Cs, 90 Sr, 241 Am, and 238,239+240 Pu and their association with bottom sediment components were investigated in two Mayak reservoirs (R-17 (decommissioned) and R-4 (still in use) with big differences in size, activity and water regime). It was established that 137 Cs and 90 Sr desorption from the R-17 bottom sediment reach constant values after 24 h, and the desorption degree is not dependant on pH but on ionic strength. Sequential extraction indicated that the main accumulation mechanism of 137 Cs is incorporation into the clay minerals. The maximum plutonium content was detected in the residual fraction of the R-17 bottom sediment, which could be associated with the effects of precipitation aging. In R-4, plutonium is equally distributed between residual and bound to organic matter fractions. The 241 Am is associated with carbonates in the R-17 bottom sediment and with organic matter in the R-4 bottom sediment and to lesser extent with iron-manganese oxides. The radionuclides are becoming less environmentally available with time since deposition., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Modern structure-property models are widely used in chemistry; however, in many cases, they are still a kind of a "black box" where there is no clear path from molecule structure to target property. Here we present an example of deep learning usage not only to build a model but also to determine key structural fragments of ligands influencing metal complexation. We have a series of chemically similar lanthanide ions, and we have collected data on complexes' stability, built models, predicting stability constants and decoded the models to obtain key fragments responsible for complexation efficiency. The results are in good correlation with the experimental ones, as well as modern theories of complexation. It was shown that the main influence on the constants had a mutual location of the binding centers.

Sequential extraction tests were used to study partitioning of U in the bottom sediments of two reservoirs that have been used for the temporary storage of nuclear waste at the "Mining and Chemical Combine" (Zheleznogorsk, Krasnoyarsk region, Russia). Various sequential extraction protocols were applied to the bottom sediment samples and the results compared with those obtained for laboratory-prepared simulated samples with different speciation and partitioning, e.g., U(VI) sorbed onto various inorganic minerals and organic matter, as well as uranium oxides. The distributions of uranium in fractions extracted from simulated and actual contaminated samples were compared to shed light on the speciation of U in the bottom sediments. X-ray absorption spectroscopy, X-ray diffraction, and scanning electron microscopy were also used to analyze the partitioning of U in contaminated sediments. We also compared the results obtained using the spectroscopic and microscopic techniques, as well as sequential extraction., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The structural characterisation of actinide nanoparticles (NPs) is of primary importance and hard to achieve, especially for non-homogeneous samples with NPs less than 3 nm. By combining high-energy X-ray scattering (HEXS) and high-energy-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD XANES) analysis, we have characterised for the first time both the short- and medium-range order of ThO 2 NPs obtained by chemical precipitation. By using this methodology, a novel insight into the structures of NPs at different stages of their formation has been achieved. The pair distribution function revealed a high concentration of ThO 2 small units similar to thorium hexamer clusters mixed with 1 nm ThO 2 NPs in the initial steps of formation. Drying the precipitates at around 150 °C promoted the recrystallisation of the smallest units into more thermodynamically stable ThO 2 NPs. HERFD XANES analysis at the thorium M 4 edge, a direct probe for f states, showed variations that we have correlated with the breakdown of the local symmetry around the thorium atoms, which most likely concerns surface atoms. Together, HEXS and HERFD XANES are a powerful methodology for investigating actinide NPs and their formation mechanism., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

This paper reports the developed non-destructive methods for the plutonium isotopes and strontium-90 content determination in hot particles and other samples. The proposed methods are based on the measurement of the characteristic X-rays accompanying the decay of these radionuclides. For hot particles of NPP accident origin, the proposed method's error limits are 10-15% for hot particles (samples) with activity above 100 Bq and 15-20% for hot particles (samples) with activity less than 100 Bq. For explosive particles, the determination accuracy is 10-15% for activity more than 5 Bq and 20-30% for 0.1-5 Bq activity. The accuracy of the proposed method for determining 90 Sr in samples with its specific content of more than 10 4 Bq/sample is 5%, with ~10 2 Bq/sample its content is 15-20%. The cost of one sample measurement and the processing time of these methods are significantly reduced compared to traditional studies. The proposed methods are reasonably simple measurement methods and can be carried out even in the field condition. They open up new possibilities for the quick search and study of hot particles and environmental samples., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Extremely defect graphene oxide (dGO) is proposed as an advanced sorbent for treatment of radioactive waste and contaminated natural waters. dGO prepared using a modified Hummers oxidation procedure, starting from reduced graphene oxide (rGO) as a precursor, shows significantly higher sorption of U(VI), Am(III), and Eu(III) than standard graphene oxides (GOs). Earlier studies revealed the mechanism of radionuclide sorption related to defects in GO sheets. Therefore, explosive thermal exfoliation of graphite oxide was used to prepare rGO with a large number of defects and holes. Defects and holes are additionally introduced by Hummers oxidation of rGO, thus providing an extremely defect-rich material. Analysis of characterization by XPS, TGA, and FTIR shows that dGO oxygen functionalization is predominantly related to defects, such as flake edges and edge atoms of holes, whereas standard GO exhibits oxygen functional groups mostly on the planar surface. The high abundance of defects in dGO results in a 15-fold increase in sorption capacity of U(VI) compared to that in standard Hummers GO. The improved sorption capacity of dGO is related to abundant carboxylic group attached hole edge atoms of GO flakes as revealed by synchrotron-based extended X-ray absorption fine structure (EXAFS) and high-energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy.

The nanoscience field often produces results more mystifying than any other discipline. It has been argued that changes in the plutonium dioxide (PuO 2 ) particle size from bulk to nano can have a drastic effect on PuO 2 properties. Here we report a full characterization of PuO 2 nanoparticles (NPs) at the atomic level and probe their local and electronic structures by a variety of methods available at the synchrotron, including extended X-ray absorption fine structure (EXAFS) at the Pu L 3 edge, X-ray absorption near edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode at the Pu L 3 and M 4 edges, high energy X-ray scattering (HEXS) and X-ray diffraction (XRD). The particles were synthesized from precursors with different oxidation states of plutonium (III, IV, and V) under various environmentally and waste storage relevant conditions (pH 8 and pH > 10). Our experimental results analyzed with state-of-the-art theoretical approaches demonstrate that well dispersed, crystalline NPs with a size of ∼2.5 nm in diameter are always formed in spite of diverse chemical conditions. Identical crystal structures and the presence of only the Pu(iv) oxidation state in all NPs, reported here for the first time, indicate that the structure of PuO 2 NPs is very similar to that of the bulk PuO 2 . All methods give complementary information and show that investigated fundamental properties of PuO 2 NPs, rather than being exotic, are very similar to those of the bulk PuO 2 .

The row of 15 chemical elements from Ac to Lr with atomic numbers from 89 to 103 are known as the actinides, which are all radioactive. Among them, uranium and plutonium are the most important as they are used in the nuclear fuel cycle and nuclear weapon production. Since the beginning of national nuclear programs and nuclear tests, many radioactively contaminated nuclear legacy sites, have been formed. This mini review covers the latest experimental, modeling, and case studies of plutonium and uranium migration in the environment, including the speciation of these elements and the chemical reactions that control their migration pathways., (Copyright © 2020 Romanchuk, Vlasova and Kalmykov.)

Development of efficient extractants for the separation of actinides and lanthanides in the technologies of nuclear fuel cycle is one of the most urgent and complex tasks in modern nuclear energetics. New family of 4,7-dichloro-1,10-phenanthroline-2,9-dicarboxylic acid diamides based on cyclic amines was synthesized and shown to exhibit high selectivity in the La/Am pair separation (SF (Am/La ≈ 10)) and in the Am/Eu pair separation (SF (Am/Eu ≈ 12)). It was shown that pyrrolidine derived diamide is more efficient extractant for americium, curium and lanthanides from highly acidic HNO 3 solution than its non-cyclic N , N , N ', N '-tetraalkyl analogues. The structures of synthesized compounds were studied in details by IR, NMR spectroscopy, and single crystal X-ray diffraction. According to spectroscopy data, incorporation of aromatic rings to the amide fragment of ligand leads to complex dynamic behavior in solutions what is believed to strongly affect the extraction ability of synthesized ligands., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Herein, a multi-technique study was performed to reveal the elemental speciation and microphase composition in altered granitic rock collected from the Krunkelbach Valley uranium (U) deposit area near an abandoned U mine, Black Forest, Southern Germany. The former Krunkelbach U mine with 1-2 km surrounding area represents a unique natural analogue site with the rich accumulation of secondary U minerals suitable for radionuclide migration studies from a spent nuclear fuel (SNF) repository. Based on a micro-technique analysis using several synchrotron-based techniques such as X-ray fluorescence analysis, X-ray absorption spectroscopy, powder X-ray diffraction and laboratory-based scanning electron microscopy and Raman spectroscopy, the complex mineral assemblage was identified. While on the surface of granite, heavily altered metazeunerite-metatorbernite (Cu(UO 2 ) 2 (AsO 4 ) 2- x (PO 4 ) x ·8H 2 O) microcrystals were found together with diluted coatings similar to cuprosklodowskite (Cu(UO 2 ) 2 (SiO 3 OH) 2 ·6H 2 O), in the cavities of the rock predominantly well-preserved microcrystals close to metatorbernite (Cu(UO 2 ) 2 (PO 4 ) 2 ·8H 2 O) were identified. The Cu(UO 2 ) 2 (AsO 4 ) 2- x (PO 4 ) x ·8H 2 O species exhibit uneven morphology and varies in its elemental composition, depending on the microcrystal part ranging from well-preserved to heavily altered on a scale of ∼200 μm. The microcrystal phase alteration could be presumably attributed to the microcrystal morphology, variations in chemical composition, and geochemical conditions at the site. The occurrence of uranyl-arsenate-phosphate and uranyl-silicate mineralisation on the surface of the same rock indicates the signatures of different geochemical conditions that took place after the oxidative weathering of the primary U- and arsenic (As)-bearing ores. The relevance of uranyl minerals to SNF storage and the potential role of uranyl-arsenate mineral species in the mobilization of U and As into the environment is discussed., Competing Interests: Authors declare no conflict of interests., (This journal is © The Royal Society of Chemistry.)

Copper-based radiopharmaceuticals are of high interest these days owing to the decay properties of copper radioisotopes. In contrast, labeled zinc compounds have been less studied for applications in nuclear medicine. In this study, the stability of labeled zinc and copper complexes with two azacrown ether ligands was investigated and compared. Then, the in vitro and in vivo stability of the studied zinc complexes was demonstrated, with the complexes showing promise for biomedical applications. In contrast, analogous copper complexes quickly dissociated in the presence of serum proteins. Furthermore, a simple method for the production of radiochemically pure 65Zn was proposed, and the opportunity for its use as a surrogate radionuclide for research into potential zinc-containing radiopharmaceuticals was demonstrated.

Here we provide evidence that the formation of PuO 2 nanoparticles from oxidized Pu VI under alkaline conditions proceeds through the formation of an intermediate Pu V solid phase, similar to NH 4 PuO 2 CO 3 , which is stable over a period of several months. For the first time, state-of-the-art experiments at Pu M 4 and at L 3 absorption edges combined with theoretical calculations unambiguously allow to determine the oxidation state and the local structure of this intermediate phase., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Phosphonate based ligands are well known for the extraction of 'f' block elements. Three N,O-donor N-heterocyclic aromatic diphosphonate ligands were evaluated in the present work for the extraction/separation studies of Am 3+ and Eu 3+ . Complexation studies in aqueous medium using luminescence titration indicated the formation of anionic complexes in the case of Eu 3+ . Two phase liquid-liquid extraction studies were, therefore, carried out by employing Aliquat-336 as the liquid anion exchanger. The results indicated the formation of a species with a metal-ligand stoichiometry of 1 : 3 in the case of pyridine-2,6-diphosphonic acid (PyPOH). In the case of 2,2'-bipyridine-6,6'-diphosphonic acid (BipyPOH), however, a 1 : 2 complex was extracted and 1,10-phenanthroline-2,9-diphosphonic acid (PhenPOH) extracts the Am 3+ and Eu 3+ ions by forming both 1 : 2 and 1 : 3 complexes. Formation of these kinds of anionic complexes was further confirmed using electrospray ionization mass spectrometry (ESI-MS). DFT calculations predicted the structure of the anionic complexes. The non-selectivity of these kinds of ligands between Am 3+ and Eu 3+ was attributed to the presence of unfavorable covalent interactions in the metal-ligand bonds.

Understanding the complex chemistry of functional nanomaterials is of fundamental importance. Controlled synthesis and characterization at the atomic level is essential to gain deeper insight into the unique chemical reactivity exhibited by many nanomaterials. Cerium oxide nanoparticles have many industrial and commercial applications, resulting from very strong catalytic, pro- and anti-oxidant activity. However, the identity of the active species and the chemical mechanisms imparted by nanoceria remain elusive, impeding the further development of new applications. Here, we explore the behavior of cerium oxide nanoparticles of different sizes at different temperatures and trace the electronic structure changes by state-of-the-art soft and hard X-ray experiments combined with computational methods. We confirm the absence of the Ce(iii) oxidation state at the surface of CeO2 nanoparticles, even for particles as small as 2 nm. Synchrotron X-ray absorption experiments at Ce L3 and M5 edges, combined with X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and small angle X-ray scattering (SAXS) and theoretical calculations demonstrate that in addition to the nanoceria charge stability, the formation of hydroxyl groups at the surface profoundly affects the chemical performance of these nanomaterials.

A new benzoazacrown ligand H 4 BATA was synthesized and its complexation ability towards bismuth cations was evaluated. Binding of cation occurs at room temperature in a few minutes and formed complex exhibits the same level of inertness as highly stable complex with the well-known H 4 DOTA in biologically relevant and challenging media under in vivo conditions., (This journal is © The Royal Society of Chemistry 2019.)

Developing characterization techniques and analysis methods adapted to the investigation of nanoparticles (NPs) is of fundamental importance considering the role of these materials in many fields of research. The study of actinide based NPs, despite their environmental relevance, is still underdeveloped compared to that of NPs based on stable and lighter elements. We present here an investigation of ThO 2 NPs performed with High-Energy Resolution Fluorescence Detected (HERFD) X-ray Absorption Near-Edge Structure (XANES) and with ab initio XANES simulations. The first post-edge feature of Th L 3 edge HERFD XANES disappears in small NPs and simulations considering non-relaxed structural models reproduce the trends observed in experimental data. Inspection of the simulations of Th atoms in the core and on the surface of the NP indeed demonstrates that the first post-edge feature is very sensitive to the lowering of the number of coordinating atoms and therefore to the more exposed Th atoms at the surface of the NP. The sensitivity of the L 3 edge HERFD XANES to low coordinated atoms at the surface stems from the hybridization of the d-Density of States (DOS) of Th with both O and Th neighboring atoms. This may be a common feature to other oxide systems that can be exploited to investigate surface interactions.

A new phosphine oxide ligand demonstrates high selectivity for the Am-Cm pair with SF = 2.9-3.5 and the Am-Eu pair with SF = 7.3-8.5 in a range of 0.1-3 M nitric acid. Thermodynamic measurements show that the entropy factor is responsible for selectivity observed in the extraction experiment. The most prevalent complexes of all three metal ions were (Ph2PyPO)2M(NO3)3. According to their DFT modelling, the M-N distances for the Cm ion were larger than those for Am, so the last ion enters deeper into the pseudo-cavity of the ligand, which causes the observed selectivity.

Actinide binding to colloidal particles of different nature was studied under oxic and anoxic conditions of an underground nuclear waste disposal site using successive micro- and ultrafiltration techniques. According to the actinide redox speciation, under oxic conditions they were present in high oxidation states except for plutonium, for which a significant part was found in the tetravalent state. In case of the anoxic conditions, the share of An (IV) was proportional to the total U(IV) concentration. This indicated formation of intrinsic U(IV) hydroxocolloids, which bound other actinides. Formation of the intrinsic actinide colloids was proven by the secondary ion mass spectrometry (SIMS) with the submicron resolution. In contrast, under the oxic conditions uranium and plutonium were sorbed by natural colloids (amorphous hydrous ferric oxide and Mn oxides)., (Copyright © 2018. Published by Elsevier Ltd.)

Precipitates formed by the neutralisation of Pu(iii), Pu(iv), Pu(v), and Pu(vi) solutions were characterised by HRTEM, SAXS, and XRD in the suspensions. PuO2 nanoparticles uniform in size (typical diameter around 2.5 nm) and phase composition were observed in all cases under equilibrium conditions. For Pu(vi), the precipitation reactions proceed via an intermediate product.

A novel original biosensing system for the simultaneous multiplex determination of general markers of catecholamine-producing diseases - catecholamines (dopamine, epinephrine, norepinephrine) and their metabolites (homovanillic and vanillylmandelic acids) in biological liquids without preliminary separation of analytes, in the absence of specific antibodies and receptors and with minimum pretreatment of a samples has been developed. This outstanding approach includes the unique combination of obtaining highly fluorescent derivatives of the analytes as a result of their interaction with two different amines ̶ benzylamine and 1,2-diphenylethylenediamine in the presence of peroxidase as a catalyst, with the application of first-order derivative fluorescence spectroscopy for the resolution of their spectra. Fluorescence is measured in 96-well microplates, which wells contain a bio-recognizing film consisted of horseradish peroxidase immobilized in the polymer chitosan. Spectra of the solutions are recorded in the range 400-500 nm (λ ex  ∼ 305-356 nm). The proposed procedures provide sensitive (in the range of 3-200 nM), selective, and reproducible (RSDs ≤ 1%, n = 6) multiplex determination of the catecholamines and their metabolites in biological liquids were successfully applied for the rapid simultaneous (20 samples per 15-30 min) screening of human urine and mice blood plasma. The validated results showed good linearity, precision, accuracy and selectivity of this method., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The X-ray photoelectron spectral structure of CeO2 valence electrons in the binding energy range of 0 to ∼50 eV was analyzed. The core-electron spectral structure parameters and the results of relativistic discrete-variational calculations of CeO8 and Ce63O216 clusters were taken into account. Comparison of the valence and the core-electron spectral structures showed that the formation of the inner (IVMO) and the outer (OVMO) valence molecular orbitals contributes to the spectral structure more than the many-body processes. The Ce 4f electrons were established to participate directly in chemical bond formation in CeO2 losing partially their f character. They were found to be localized mostly within the outer valence band. The Ce 5p atomic orbitals were shown to participate in the formation of both the inner and the outer valence molecular orbitals (MOs). A large part in the IVMO formation is taken by the filled Ce 5p1/2, 5p3/2 and O 2s atomic shells, while the Ce 5s electrons participate weakly in the chemical bond formation. The composition and the sequent order of the molecular orbitals in the binding energy range of 0 to ∼50 eV were established. A quantitative scheme for the molecular orbitals of CeO2 was built. This scheme is fundamental for understanding the nature of chemical bonding and also for the interpretation of other X-ray spectra of CeO2. Evaluations revealed that the IVMO electrons weaken the chemical bond formed by the OVMO electrons by 37%.

Zinc is one of the most important microelements necessary for normal body functioning. Zinc is marked in numerous diseases and, hence, its properties and behavior in the body have long been a subject of extensive study. This review considers trends in the assessment of the role of zinc and its compounds in the past decade. It becomes evident that redox-inactive zinc is the main supervisor in the conformation of the most important molecules in all body organs and tissues. We placed emphasis on the variety of zinc-binding sites and the role of zinc in the genesis and progress of different forms of leukemia. The importance of some families of transcription factors in the development and prognosis of treatment of various leukemia forms is examined; new directions of these studies are shown.

We have predicted earlier by DFT simulation that tridentate O,N,O-donor cyclic dilactams (B) belonging to the family of pyridine-2,6-dicarboxamides are much more selective and efficient extractants for the separation of lanthanides and actinides than open-structure pyridine-2,6-dicarboxamides due to the higher degree of "ligand preorganization". In the present work, three new ligands of type (B) were synthesized. Extraction experiments showed that, in line with the data from DFT simulation, these ligands have 5-6-fold higher selectivity for the separation of an Am 3+ /Eu 3+ pair and provide distribution coefficients D which are by three orders of magnitude higher than those for the related parent ligands with an open structure. Determination of the solvate numbers (SNs) for Eu 3+ and Am 3+ cations by slope analysis has shown that the stoichiometry of complexes, in the form of which these ions pass from the aqueous into the organic phase, depends to a considerable extent on the polarity of the organic solvent. Strongly polar solvents (ε > 20) extract these cations mainly in the form of 1 : 1 complexes LM(NO 3 ) 3 having according to the DFT simulation the largest dipole moments (μ = 18.6-19.7 D). The solvents of low polarity (ε ≤ 10) extract these cations mainly in the form of less polar 2 : 1 complexes L 2 M(NO 3 ) 3 (μ ≈ 1.6 D). For solvents of intermediate polarity fractional values of solvate numbers were obtained which indicates the coexistence of complexes LM(NO 3 ) 3 and L 2 M(NO 3 ) 3 in the organic phase.