Zinc Complexes of Fluorosubstituted N-[2-(Phenyliminomethyl)phenyl]-4-methylbenzenesulfamides: Synthesis, Structure, Luminescent Properties, and Biological Activity.

Mono-, di-, and trifluorophenyl substituted in different positions of amine fragments bis [2-[[(E)-((fluorophenyl)iminomethyl]-N-(p-tolylsulfonyl)anilino]zinc(II) complexes were synthesized. Their crystal structure, photo- and electroluminescent properties, and protistocidal, fungistatic, and antibacterial activities were studied. It has been shown that the introduction of fluorine atoms and an increase in their number in the ligand structure of the resulting metal complexes promote the luminescence quantum yields and values of performance and brightness in EL cells compared to their previously studied chlorine-substituted analogs.

Formation of Neptunium(V) Carbonates: Examining the Forceful Influence of Alkali and Alkaline Earth Cations.

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 NaNpO2CO3·3H2O (P1, a = 4.3420(2) Å, b = 4.8962(2) Å, c = 10.0933(11) Å, α = 91.014(7)°, ß = 77.834(11)°, and γ = 90.004(10)°) and KNpO2CO3 (P63/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 Ca0.5NpO2CO3 were obtained using the ion exchange method and chemical precipitation from solutions containing competing cations (Ca2+, Na+, K+, and Mg2+). 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.

Laboratory-based X-ray spectrometer for actinide science.

X-ray absorption and emission spectroscopies nowadays are advanced characterization methods for fundamental and applied actinide research. One of the advantages of these methods is to reveal slight changes in the structural and electronic properties of radionuclides. The experiments are generally carried out at synchrotrons. However, considerable progress has been made to construct laboratory-based X-ray spectrometers for X-ray absorption and emission spectroscopies. Laboratory spectrometers are reliable, effective and accessible alternatives to synchrotrons, especially for actinide research, which allow dispensing with high costs of the radioactive sample transport and synchrotron time. Moreover, data from laboratory spectrometers, obtained within a reasonable time, are comparable with synchrotron results. Thereby, laboratory spectrometers can complement synchrotrons or can be used for preliminary experiments to find perspective samples for synchrotron experiments with better resolution. Here, the construction and implementation of an X-ray spectrometer (LomonosovXAS) in Johann-geometry at a radiochemistry laboratory is reported. Examples are given of the application of LomonosovXAS to actinide systems relevant to the chemistry of f-elements, the physical chemistry of nuclear power engineering and the long-term disposal of spent nuclear fuel.

Oxidation and Nanoparticle Formation during Ce(III) Sorption onto Minerals.

The sorption of Ce(III) on three abundant environmental minerals (goethite, anatase, and birnessite) was investigated. Batch sorption experiments using a radioactive 139Ce 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 CeO2 nanoparticles on the mineral surface, which depended on the initial cerium concentration and pH value.

Uranium oxides structural transformation in human body liquids.

Uranium oxide microparticles ingestion is one of the potential sources of internal radiation doses to the humans at accidental or undesirable releases of radioactive materials. It is important to predict the obtained dose and possible biological effect of these microparticles by studying uranium oxides transformations in case of their ingestion or inhalation. Using a combination of methods, a complex examination of structural changes of uranium oxides in the range from UO2 to U4O9, U3O8 and UO3 as well as before and after exposure of uranium oxides in simulated biological fluids: gastro-intestinal and lung-was carried out. Oxides were thoroughly characterized by Raman and XAFS spectroscopy. It was determined that the duration of expose has more influence on all oxides transformations. The greatest changes occurred in U4O9, that transformed into U4O9-y. UO2.05 and U3O8 structures became more ordered and UO3 did not undergo significant transformation.

Biotinylated Pt(IV) prodrugs with elevated lipophilicity and cytotoxicity.

A design of Pt(IV) prodrugs with tumor cell targeting moieties leading to increased selectivity is of interest. Herein, we designed a novel Pt(IV) prodrugs with COX-inhibitor naproxen, long-chain hydrophobic stearic acid moiety and biotin as axial ligands. We have established that for Pt(IV) prodrugs with biotin and naproxen or stearate in axial position, the lipophilicity rather than biotin receptors expression is the main factor of cytotoxicity. We also monitored the reduction speed of Pt(IV) prodrug 3 with naproxen and biotin in axial positions in A549 cells using XANES and demonstrated that the prodrug gradually releases cisplatin within 20 hours of incubation.

Synthesis, Structure, Spectral-Luminescent Properties, and Biological Activity of Chlorine-Substituted N-[2-(Phenyliminomethyl)phenyl]-4-methylbenzenesulfamide and Their Zinc(II) Complexes.

New azomethine compounds of 2-(N-tosylamino)benzaldehyde or 5-chloro-2-(N-tosylamino)benzaldehyde and the corresponding chlorine-substituted anilines, zinc(II) complexes based on them have been synthesized. The structures of azomethines and their complexes were determined by elemental analysis, IR, 1H NMR, X-ray spectroscopy, and X-ray diffraction. It is found that all ZnL2 complexes have a tetrahedral structure according to XAFS and X-ray diffraction data. The photoluminescent properties of azomethines and zinc complexes in methylene chloride solution and in solid form have been studied. It is shown that the photoluminescence quantum yields of solid samples of the complexes are an order of magnitude higher compared to the solutions and range from 11.34% to 48.3%. The thermal properties of Zn(II) complexes were determined by thermal gravimetric analysis (TGA) and differential scanning calorimetry. The TGA curves of all the compounds suggest their high thermal stability up to temperatures higher than 290 °C. The electrochemical properties of all complexes were investigated by the cyclic voltammetry method. The multilayered devices ITO/PEDOT:PSS/NPD/Zn complex/ TPBI/LiF/Al with wide electroluminescence (EL) color range spanning the range from bluish-green (494 nm) to green (533 nm) and the high values of brightness, current and power efficiency were fabricated. The biological activity of azomethines and zinc complexes has been studied. In the case of complexes, the protistocidal activity of the zinc complex with azomethine of 5-chloro-2-(N-tosylamino)benzaldehyde with 4-chloroaniline was two times higher than the activity of the reference drug toltrazuril.

Electrochemical Detection of a Novel Pt(IV) Prodrug with the Metronidazole Axial Ligand in the Hypoxic Area.

We report herein a Pt(IV) prodrug with metronidazole in axial positions Pt-Mnz. The nitroaromatic axial ligand was conjugated with a cisplatin scaffold to irreversibly reduce under hypoxic conditions, thereby retaining the Pt(IV) prodrug in the area of hypoxia. X-ray near-edge adsorption spectroscopy (XANES) on dried drug-preincubated tumor cell samples revealed a gradual release of cisplatin from the Pt-Mnz prodrug instead of rapid intracellular degradation. The ability of the prodrug to penetrate into three-dimensional (3D) spheroid cellular cultures was evaluated by a novel electrochemical assay via a platinum-coated carbon nanoelectrode, capable of single-cell measurements. Using a unique technique of electrochemical measurements in single tumor spheroids, we were able to both detect the real-time response of the axial ligand to hypoxia and establish the depth of penetration of the drug into the tumor model.

Novel Hybrid Benzoazacrown Ligand as a Chelator for Copper and Lead Cations: What Difference Does Pyridine Make.

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.

Effective coordination numbers from EXAFS: general approaches for lanthanide and actinide dioxides.

Extended X-ray absorption fine structure (EXAFS) is a comprehensive and usable method for characterizing the structures of various materials, including radioactive and nuclear materials. Unceasing discussions about the interpretation of EXAFS results for actinide nanoparticles (NPs) or colloids were still present during the last decade. In this study, new experimental data for PuO2 and CeO2 NPs with different average sizes were compared with published data on AnO2 NPs that highlight the best fit and interpretation of the structural data. In terms of the structure, PuO2, CeO2, ThO2, and UO2 NPs exhibit similar behaviors. Only ThO2 NPs have a more disordered and even partly amorphous structure, which results in EXAFS characteristics. The proposed new core-shell model for NPs with calculated effective coordination number perfectly fits the results of the variations in a metal-metal shell with a decrease in NP size.

From EXAFS of reference compounds to U(VI) speciation in contaminated environments.

Understanding the speciation of technogenic uranium in natural systems is crucial for estimating U migration and bioavailability and for developing remediation strategies for contaminated territories. Reference EXAFS data of model laboratory-prepared uranium compounds (`standards') are necessary to analyze U-contaminated samples from nuclear legacy sites. To minimize errors associated with measurements on different synchrotrons, it is important not only to compare data obtained on environmentally contaminated samples with the literature but also with `standards' collected at the same beamline. Before recording the EXAFS spectra, all reference compounds were thoroughly characterized by Raman spectroscopy and powder X-ray diffraction. The U(VI) local molecular environments in the reference compounds, i.e. uranyl oxyhydroxides, phosphates, carbonates and uranates, were examined using XAFS. Based on the EXAFS fitting results obtained, including the nature of the bonding, interatomic distances and coordination numbers, parameters that are typical for a particular U compound were differentiated. Using data for `standards', U speciation in the sample of radioactively contaminated soil was determined to be a mixture of U oxyhydroxide and carbonate phases.

Behavior of implanted Xe, Kr and Ar in nanodiamonds and thin graphene stacks: experiment and modeling.

Implantation and subsequent behaviour of heavy noble gases (Ar, Kr, and Xe) in few-layer graphene sheets and in nanodiamonds are studied both using computational methods and experimentally using X-ray absorption spectroscopy. X-ray absorption spectroscopy provides substantial support for Xe-vacancy (Xe-V) defects as main sites for Xe in nanodiamonds. It is shown that noble gases in thin graphene stacks distort the layers, forming bulges. The energy of an ion placed in between flat graphene sheets is notably lower than that in domains with high curvature. However, if the ion is trapped in the curved domain, considerable additional energy is required to displace it. This phenomenon is likely responsible for strong binding of noble gases implanted into disordered carbonaceous phase in meteorites (the Q-component).

Alternative mechanism of action of the DNP PtIV prodrug: intracellular cisplatin release and the mitochondria-mediated apoptotic pathway.

In a recent research paper Dr. Suxing Jin et al. reported two multispecific PtIV complexes DNP and NP with non-steroidal anti-inflammatory drug naproxen (NPX) as the axial ligand(s). Herein, we clarify the mechanism of action of DNP, its therapeutic target and intracellular redox-status.

Partitioning of uranium in contaminated bottom sediments: The meaning of fractionation.

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.

Speciation of Zn and Cu in Technosol and evaluation of a sequential extraction procedure using XAS, XRD and SEM-EDX analyses.

Metal speciation, linked directly to bioaccessibility and lability, is a key to be considered when assessing associated human and environmental health risks originated from anthropogenic activities. To identify the Zn and Cu speciation in the highly contaminated, technogenically transformed soils (Technosol) from the impact zone near the industrial sludge reservoirs of chemical plant (Siverskyi Donets River floodplain, southern Russia), the validity of the BCR sequential extraction procedure using the X-ray absorption fine-structure and X-ray powder diffraction (XRD) analyses was examined after each of the three stages. After the removal of exchange and carbonate-bonded Zn and Cu compounds from Technosol (first stage of extraction), the resulting residual soil showed enrichment in a great diversity of metal compounds, primarily with Me-S and Me-O bonds. The number of compounds with a higher solubility decreased at the subsequent stages of extraction. In the residual soil left over after extracting the first and second fractions, the dominant Zn-S bond appeared as würtzite (hexagonal ZnS) that made up more than 50%, while the Cu-S bond was almost completely represented only by chalcocite (Cu2S). The XRD analysis revealed the authigenic minerals of metals with S: sphalerite (cubic ZnS), würtzite (hexagonal ZnS), covellite (CuS) and bornite (Cu5FeS4). The scanning electron microscopy data confirmed that würtzite was the dominant form of Me with sulfur-containing and carbonate-containing minerals. The Zn-S bond was the main component (57%), whereas the Cu-O bond was dominant in the residual fraction (the fraction after the third-stage extraction). The results revealed that the composition of the residual fractions might include some of the most stable and hard-to-recover metal compounds of technogenic origin. Thus, the application of the novel instrumental methods, coupled with the chemical fractionation, revealed the incomplete selectivity of the extractants in the extraction of Zn and Cu in long-term highly contaminated soils.

XANES Measurements for Studies of Adsorbed Protein Layers at Liquid Interfaces.

X-ray absorption near edge structure (XANES) spectra for protein layers adsorbed at liquid interfaces in a Langmuir trough have been recorded for the first time. We studied the parkin protein (so-called E3 ubiquitin ligase), which plays an important role in pathogenesis of Parkinson disease. Parkin contains eight Zn binding sites, consisting of cysteine and histidine residues in a tetracoordinated geometry. Zn K-edge XANES spectra were collected in the following two series: under mild radiation condition of measurements (short exposition time) and with high X-ray radiation load. XANES fingerprint analysis was applied to obtain information on ligand environments around zinc ions. Two types of zinc coordination geometry were identified depending on X-ray radiation load. We found that, under mild conditions, local zinc environment in our parkin preparations was very similar to that identified in hemoglobin, treated with a solution of ZnCl2 salt. Under high X-ray radiation load, considerable changes in the zinc site structure were observed; local zinc environment appeared to be almost identical to that defined in Zn-containing enzyme alkaline phosphatase. The formation of a similar metal site in unrelated protein molecules, observed in our experiments, highlights the significance of metal binding templates as essential structural modules in protein macromolecules.

Enhanced Sorption of Radionuclides by Defect-Rich Graphene Oxide.

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.

Synthesis of ZnO Nanoparticles Doped with Cobalt Using Bimetallic ZIFs as Sacrificial Agents.

: We report here a simple two-stage synthesis of zinc-cobalt oxide nanoparticles. We used Zn/Co-zeolite imidazolate framework (ZIF)-8 materials as precursors for annealing and optional impregnation with a silicon source for the formation of a protective layer on the surface of oxide nanoparticles. Using bimetallic ZIFs allowed us to trace the phase transition of the obtained oxide nanoparticles from wurtzite ZnO to spinel Co3O4 structures. Using (X-Ray diffraction) XRD and (X-ray Absorption Near Edge Structure) XANES techniques, we confirmed the incorporation of cobalt ions into the ZnO structure up to 5 mol.% of Co. Simple annealing of Zn/Co-ZIF-8 materials in the air led to the formation of oxide nanoparticles of about 20-30 nm, while additional treatment of ZIFs with silicon source resulted in nanoparticles of about 5-10 nm covered with protective silica layer. We revealed the incorporation of oxygen vacancies in the obtained ZnO nanoparticles using FTIR analysis. All obtained samples were comprehensively characterized, including analysis with a synchrotron radiation source.

The missing pieces of the PuO2 nanoparticle puzzle.

The nanoscience field often produces results more mystifying than any other discipline. It has been argued that changes in the plutonium dioxide (PuO2) particle size from bulk to nano can have a drastic effect on PuO2 properties. Here we report a full characterization of PuO2 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 L3 edge, X-ray absorption near edge structure (XANES) in high energy resolution fluorescence detection (HERFD) mode at the Pu L3 and M4 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 PuO2 NPs is very similar to that of the bulk PuO2. All methods give complementary information and show that investigated fundamental properties of PuO2 NPs, rather than being exotic, are very similar to those of the bulk PuO2.

A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO2 Nanoparticles.

Here we provide evidence that the formation of PuO2 nanoparticles from oxidized PuVI under alkaline conditions proceeds through the formation of an intermediate PuV solid phase, similar to NH4 PuO2 CO3 , which is stable over a period of several months. For the first time, state-of-the-art experiments at Pu M4 and at L3 absorption edges combined with theoretical calculations unambiguously allow to determine the oxidation state and the local structure of this intermediate phase.