Consecutive recovery of uranium oxides from uranyl-containing molten alkali metal sulfate electrolytes

The oxygen coefficient (atomic ratio O/U) of a cathode product and the cathode current yield in consecutive recovery of uranium oxides from molten salt mixtures (nLi₂SO₄ + (1 ? n)Cs₂SO₄) + UO₂SO₄ and (Li,Na,K)₂SO₄ + UO₂SO₄ in air were analyzed as dependent on the electrolyte and the mean solvent-salt cation radius. The increasing mean solvent-salt cation radius and decreasing UO₂SO₄ concentration in the electrolyte during long-term electrolysis suppress the solvolysis of uranyl ions and decrease the oxygen coefficient in the cathode product. The cathode current yield decreases systematically during electrolysis and drops to zero long before the uranium is completely recovered from the melt. The ultimate uranium recovery increases as the mean solvent-salt cation radius increases.     

Direct Phosphorylation of N-Protected Imidazoles and Benzoimidazoles-A Route to 1H-Imidazol(benzoimidazol)-2-yl Phosphonic and Phosphinic Acids and Their Derivatives

Synthetic approaches to 1H-imidazol-2-yl and 1H-benzoimidazol-2-yl phosphinic and phosphonic acids and their derivatives are reported, based on phosphorylation of N-protected heterocylcles by PhPOCl₂ or MePOCl₂. Reaction of N-alkylbenzoimidazoles with POCl₃ did not lead to C-phosphorylated products in a reasonable yield, [2,2′]-bis-benzoimidazolyles being formed instead.     

Pros and Cons of the Cannabinoid System in Cancer: Focus on Hematological Malignancies

The endocannabinoid system (ECS) is a composite cell-signaling system that allows endogenous cannabinoid ligands to control cell functions through the interaction with cannabinoid receptors. Modifications of the ECS might contribute to the pathogenesis of different diseases, including cancers. However, the use of these compounds as antitumor agents remains debatable. Pre-clinical experimental studies have shown that cannabinoids (CBs) might be effective for the treatment of hematological malignancies, such as leukemia and lymphoma. Specifically, CBs may activate programmed cell death mechanisms, thus blocking cancer cell growth, and may modulate both autophagy and angiogenesis. Therefore, CBs may have significant anti-tumor effects in hematologic diseases and may synergistically act with chemotherapeutic agents, possibly also reducing chemoresistance. Moreover, targeting ECS might be considered as a novel approach for the management of graft versus host disease, thus reducing some symptoms such as anorexia, cachexia, fatigue, anxiety, depression, and neuropathic pain. The aim of the present review is to collect the state of the art of CBs effects on hematological tumors, thus focusing on the essential topics that might be useful before moving into the clinical practice.     

Epoxy-amine composites with ultralow concentrations of single-layer carbon nanotubes

The physical and mechanical properties of composite materials based on epoxy-amine systems—diglycidyl ether of diphenylolpropane-eutectic mixture of aromatic amines (40 wt % m-phenylenediamine-60 wt % 4,4′-diaminodiphenylmethane) and epoxy-diane resin ED-20-eutectic mixture of aromatic diamines with ultralow contents (≤0.1 wt %) of single-layer carbon nanotubes—are studied. It is shown that, for the concentration dependence of the modulus of elasticity during tension, the additivity rule is obeyed only at the lowest concentrations of carbon nanotubes. In this case, the presence of near-surface layers of a matrix with an increased elastic modulus should be considered.     

Conversion reaction mechanisms in lithium ion batteries: study of the binary metal fluoride electrodes

Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF(2): M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF(2)) while others are not (e.g., CuF(2)). In this study, we investigated the conversion reaction of binary metal fluorides, FeF(2) and CuF(2), using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF(2) and CuF(2) react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li(+) with FeF(2), small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF(2). In contrast to FeF(2), no continuous Cu network was observed in the lithiated CuF(2); rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF(2) electrode.     

Iodo-alkynyl- and iodo-butadiynyl-ruthenium complexes

Addition of [I(py)₂]BF₄ to Ru(CCH)(dppe)Cp∗ gave the iodovinylidene [Ru(CCHI)(dppe)Cp∗]BF₄1, which could be deprotonated to Ru(CCI)(dppe)Cp∗ 2. The attempted preparation of Ru(CCCCI)(dppe)Cp∗, followed by derivatisation with tcne, gave the dienynyl Ru{CCC[C(CN)₂]CIC(CN)₂}(dppe)Cp∗ 3. The Pd(0)/Cu(I)-catalysed reaction of 3 with Ru{CCCCAu(PPh₃)}(dppe)Cp∗ afforded Ru{CCCC(CN)₂CC(CN)₂Au(PPh₃)}(dppe)Cp∗ 4 by formal replacement of I⁺ by [Au(PPh₃)]⁺. XRD structures of 1-4 are reported.     

Molecular Recognition by Zn(II)-Capped Dynamic Foldamers

Two α-aminoisobutyric acid (Aib) foldamers bearing Zn(II)-chelating N-termini have been synthesized and compared with a reported Aib foldamer that has a bis(quinolinyl)/mono(pyridyl) cap (BQPA group). Replacement of the quinolinyl arms of the BQPA-capped foldamer with pyridyl gave a BPPA-capped foldamer, then further replacement of the linking pyridyl with a 1,2,3-triazole gave a BPTA-capped foldamer. Their ability to relay chiral information from carboxylate bound to Zn(II) at the N-terminus to a glycinamide-based NMR reporter of conformational preference at the C-terminus was measured. The importance of the quinolinyl arms became readily apparent, as the foldamers with pyridyl arms were unable to report on the presence of chiral carboxylate in acetonitrile. Low solubility, X-ray crystallography and ¹H NMR spectroscopy suggested that interfoldamer interactions inhibited carboxylate binding. However changing solvent to methanol revealed that the end-to-end relay of chiral information could be observed for the Zn(II) complex of the BPTA-capped foldamer at low temperature.     

Mesoscopic simulation of an ionomeric membrane based on sulfonated aromatic poly(ether ether ketone)

Mesoscopic simulation in the framework of the mesoscopic dynamics method (a version of the dynamic density functional method) was performed for a proton conducting membrane based on sulfonated aromatic poly(ether ether ketone) in a wide range of water content in the system. For the selected parametric field, the model demonstrates microphase separation of hydrophilic and hydrophobic segments of the polymer. In the bulk of the membrane, a spatial network of water channels forms, whose walls consist of polar (sulfonated) units of the macromolecule. Independent molecular dynamics simulation for one set of parameters gives close values of the structural characteristics of the membrane, which confirms the correctness of the mesoscopic model.     

Reaction of α-(trialkylstannyl) acetylenes with metallic sodium

-Trialkylstannylacetylenes react under mild conditions with metallic sodium at the Sn-C(sp) bond to give hexaalkyldistannanes and sodium acetylalkynides inca. 65–85 % yields.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1109–1110, June, 1994.