Reactions of silicon-, germanium- and tin-containing carbene complexes of tungsten Ph3E-CW(OBu)3 (E=Si, Ge, Sn) with hydrogen chloride: crystal structures of carbene complexes Ph3E-CHWCl2(OBu)2 (E=Si, Ge)

The novel organosilicon, -germanium and -tin-containing carbene complexes of tungsten of the type Ph₃E-CHWCl₂(OBu^t)₂ (E=Si, Ge, Sn) have been prepared by the reaction of heteroelement-containing carbene complexes of tungsten Ph₃E-CW(OBu^t)₃ (E=Si, Ge, Sn) with hydrogen chloride. The tin-containing carbene complex was identified in solution by ¹H NMR spectroscopy. Silicon- and germanium-containing carbene complexes were isolated in high yields as crystalline solids and characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and ²⁹Si NMR spectroscopy and X-ray diffraction studies. The geometry of the W atoms in the compounds can be described as a distorted square pyramid.     

Relativistic calculation of autoionization widths of 1s2s2pjJ, 1s2s2 2S1/2, and 1s2pJ 2pj′J levels

The autoionization widths of levels 1s 2s 2p_jJ, 1s2s^{2 2}S_1/2, and 1s2p_j2p_j′ J have been calculated for ions with Z = 6–30. The calculation has been carried out in intermediate coupling. The decay amplitudes have been calculated in a relativistic approximation.     

Determination of glycine,alanine, and leucine at different solution ph with the aid of donnan potential sensors based on hybrid membranes

The cross sensitive sensors whose analytical signal is the Donnan potential (PD-sensors) were developed for the determination of the amino acids glycine, alanine, and leucine in acidic and alkaline solutions. Hybrid materials based on perfluorinated sulfo cation-exchange membranes Nafion and MF-4SC with incorporated zirconium dioxide and silicon dioxide nanoparticles, including those with modified surfaces containing proton-acceptor groups, were used in the PD-sensors. The sensitivity of the PD-sensors to hydronium ions, which interfere with the determination of amino acids at pH < 7, was considerably decreased due to the use of the membranes obtained by an in situ method that contained silicon dioxide nanoparticles with amine-containing groups. The greatest sensitivity of the PD-sensors to the anions of amino acids at pH > 7 and the smallest sensitivity to the cations K⁺ were observed in hybrid membranes, which combined an increased rate of anion transfer and a low moisture capacity. The use of the PD-sensors based on hybrid membranes makes it possible to determine the cations, anions, and zwitterions of amino acids over a wide range of pH with a sufficiently high accuracy.     

Application of capillary electrophoresis technique for the enantioseparation of bioactive ferrocene-based compounds versus DFT calculated data

Herein, a series of bioactive ferrocene-modified N-heterocycles with alkyl linkers was prepared in good to quantitative yields starting from easy accessible ferrocene alcohols and heterocycles under acidic or neutral (for imidazole) conditions in racemic forms. The analytical resolution of a number of bioactive racemic ferrocene azoles 1 – 6 (where azole = imidazole, pyrazole, and benzotriazole derivatives) into enantiomers was first carried out by CE using sulfobuthylether-β-CD (captisol) as a chiral selector. The analytical approaches to highly enantiomeric-enriched ferrocene derivatives are based on the formation of their inclusion complexes. The best chiral separation was achieved using zone CE in a quartz capillary. The ACE was used to evaluate the stability constants of captisol complexes with enantiomeric forms of two ferrocene derivatives 1 , FcCHMe-imidazole, and 6 , FcCHMe-benzotriazole. The optimal conditions for the resolution of the studied (R, S)-ferrocene compounds 1 , 2 , and 6 were predicted on the basis of the performed quantum chemical calculations and then implemented by the electrophoretic method. A high correlation between density functional theory calculation results and experimental electrophoresis data were obtained. Successful enantioseparation of racemic mixtures is of great importance for the characterization and further applications of drug candidates in enantiopure forms and in the development of clinical treatment. The advantages of the CE procedure make it possible to have important practical value and significance for determining the purity and enantiomeric excess of other ferrocene-containing compounds.     

A review of new wire arrays with open and closed magnetic configurations at the 1.6 MA Zebra generator for radiative properties and opacity effects

The studies emphasize investigation of plasma formation, implosion, and radiation features as a function of two load configurations: compact multi-planar and cylindrical wire arrays. Experiments with different Z-pinch loads were performed on 1.6 MA, 100 ns, Zebra generator at University of Nevada, Reno. The multi-planar wire arrays (PWAs) were studied in open and closed configurations with Al, Cu, brass, Mo and W wires. In the open magnetic configurations (single, double, triple PWAs) magnetic fields are present inside the arrays from the beginning of discharge, while in closed configurations (prism-like PWA) the global magnetic field is excluded inside before plasma flow occurs. The new prism-like PWA allows high flexibility in control of implosion dynamics and precursor formation. The spectral modeling, magneto-hydrodynamic (MHD) and wire ablation dynamic model (WADM) codes were used to describe the plasma evolution and plasma parameters. Experimentally observed electron temperature and density in multiple bright spots reached 1.4 keV and 5 × 10²¹ cm^?3, respectively. Two types of bright spots were observed. With peak currents up to 1.3 MA opacity effects became more pronounced and led to a limiting of the X-ray yields from compact cylindrical arrays. Despite different magnetic energy to plasma coupling mechanisms early in the implosion a comparison of compact double PWA and cylindrical WA results indicates that during the stagnation stage the same plasma heating mechanism may occur. The double PWA was found to be the best radiator tested at University scale 1 MA generator. It is characterized by a combination of larger yield and power, mm-scale size, and provides the possibility of radiation pulse shaping. Further, the newer configuration, the double PWA with skewed wires, was tested and showed the possibility of a more effective X-ray generation.     

Efficient tandem synthesis of 3-alkylaminoprop-2-enamides from 3-trimethylsilylprop-2-ynamides

A tandem synthetic approach to previously unknown 3-aminoprop-2-enamides has been developed. It is based on Si-C _sp desilylation of 3-trimethylsilylprop-2-ynamides and subsequent addition of an amine to the triple bond of intermediate terminal propynamides. The effects of the reaction conditions and amine nature on the efficiency of the process have been studied.     

Oxygen and Carbon Isotope Variations of Carbonates and Silicates from the Carbonatite Massif Tiksheozero (Northern Karelia)

Abstract

Carbon and oxygen isotope compositions have been determined for carbonate minerals from different types of carbonatites (large carbonatite bodies, veins, eruptive breccia), as well as from different temperature classes of carbonatites (according to Samoilov [1]). It could be shown, that only high temperature carbonatites exhibit small variations of δ¹⁸O and δ¹³C falling in the range of “high temperature mantle carbonates”, whereas low temperature calcites and dolomites show wide variations in δ¹⁸O. These changes in both isotope and mineral compositions of low temperature carbonatites are interpreted as a result of repeated interaction with fluids. The oxygen isotope ratios in most of the eruptive breccia have been changed by secondary processes. The primary deep-seated isotope record has been preserved only in samples, in which carbonate occurs as fine-grained calcite groundmass.

Preliminary results on oxygen isotope composition of different silicate minerals (amphibole, magnetite, biotite, albite, apatite) indicate isotope equilibrium for the mineral pair calcite-amphibole with isotope temperatures representing superimposed processes.     

The Search for Variation of Fundamental Constants with Clocks

In many theories beyond the Standard Model the quantities that we call “fundamental constants” become space‐time dependent, leading to corresponding variation of atomic and molecular spectra and clock frequencies. The extraordinary improvement of the atomic clock precision in the past fifteen years enabled testing the constancy of the fundamental constant at a very high level of precision. Herein, searches for the variation of fundamental constants with clocks are discussed, focusing on recent key results and future proposals, including highly charged ion, molecular, and nuclear clocks. The relevance of the recent searches for oscillatory and transient variation of fundamental constants to the major unexplained phenomena of our Universe, the nature of dark matter, is discussed.