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Dr. Zhenghai Yang Dr. Srinivas Doddipatla Dr. Chao He Vladislav S. Krasnoukhov Prof. Dr. Valeriy N. Azyazov Prof. Dr. Alexander M. Mebel Prof. Dr. Ralf I. Kaiser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13584-13589
The silene molecule (H2SiCH2; X1A1) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH4). Exploiting crossed molecular beams experiments augmented by high-level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon-hydrogen bond forming the silylmethyl (CH2SiH3; X2A′) complex followed by hydrogen migration to the methylsilyl radical (SiH2CH3; X2A′). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H2SiCH2; X1A1). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon–silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level. 相似文献
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24.
Novel types of hydrazinopeptide-like units containing five elements of diversity have been prepared in two steps using sequential
Ugi reactions. 相似文献
25.
Konrad Eichhorn Colombo Vladislav V. Kharton Alexandre P. Viskup Andrei V. Kovalevsky Aliaksandr L. Shaula Olav Bolland 《Journal of Solid State Electrochemistry》2011,15(2):329-347
A gas turbine power plant for CO2 capture, based on oxygen-permeable membranes with mixed ionic-electronic conductivity, was analysed with respect to long-term
stability by means of numerical simulation. Due to the attractive transport and physicochemical properties of mixed-conducting
La2NiO4+δ, this nickelate was selected as a prototype membrane material for this application. Experiments showed very slow degradation
of La2NiO4+δ membranes at oxygen chemical potentials close to atmospheric conditions, which are associated with kinetic demixing and other
microstructure-related factors. Interaction with CO2 in the intermediate temperature range also leads to lower oxygen permeation, whilst increasing oxygen pressure may cause
partial phase decomposition and microstructural changes, thus again limiting the range of possible operation conditions. The
relevant operational constraints were included in a detailed membrane-based gas turbine power plant model. The membrane performance
degradation with time was approximated by a linear function with average rate of 3.3% per 1,000 operation hours. Furthermore,
performance deterioration of the gas turbine compressor and turbine were also considered. Simulations revealed that the power
plant is substantially affected by degradation of the ceramic membranes and turbomachinery components. The already rather
small operating window was further narrowed when compared with a conventional gas turbine power plant. Two different designs
of the membrane-based power plant were analysed: (1) with and (2) without additional combustors (afterburners) between the
membrane reactor and the gas turbine. Afterburners increase thermal efficiency as well as power output, but also lead to non-negligible
CO2 emissions. In order to have a frame of comparison, results for a conventional gas turbine power plant with degradation of
turbomachinery components are also presented. Simulations representing changes in ambient temperature and fuel composition
as well as failure incidents were executed to analyse the susceptibility of the gas turbine power plant to external and internal
changes. 相似文献
26.
Nives Galić Nataša Burić Renato Tomaš Leo Frkanec Vladislav Tomišić 《Supramolecular chemistry》2013,25(5):389-397
The fluorescent peptidocalixarenes, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,27-di(O-methyl)-26,28-bis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (2), were prepared by introducing tryptophan subunits at a lower calixarene rim. Coordination abilities of 1 and 2 towards Eu(III) and alkali metal cations were studied by spectrophotometric, spectrofluorimetric, conductometric and potentiometric titrations in acetonitrile at 25°C. Rather strong complexation was observed for smaller alkali metal cations Li+ and Na+ (log K Li1 >6, log K Li2 >6, log K Na1 = 8.25, log K Na2 = 6.94), and moderate for K+ (log K K1 = 5.09, log K K2 = 4.09). Larger Rb+ and Cs+ cations did not fit in the ion binding site of 1 so no complexation was detected, whereas the more flexible ligand 2 accommodated Rb+ cation (log K Rb2 = 3.44). The fluorescence of 1 (λex = 280 nm, λem = 340 nm) was remarkably quenched by Eu(III). Stability constant of 1:1 (Eu3+:1) complex determined spectrofluorimetrically amounted to log K Eu1 = 6.16. 相似文献
27.
Maxim A. Mironov Iliya D. Shulepov Vladislav S. Ponomarev Vasily A. Bakulev 《Colloid and polymer science》2013,291(7):1683-1691
A novel method for obtaining cross-linked microgels of apple pectin has been introduced. This method is based on the Ugi four-component condensation in colloidal suspensions of pectinic acid and amines. Using various processing parameters (the polysaccharide concentration, the type and density of crosslink, and the optimal pH range), particles with controlled colloidal properties have been obtained. Lightly cross-linked polysaccharide chains acquire anionic character due to deprotonation of the carboxyl groups at pH?9–10. Increasing the degree of cross-linking leads to a polyampholyte microgel, which can be protonated in acidic medium or deprotonated in basic medium. Polyampholyte microgels derived from apple pectin have proved to be an effective Pickering emulsifier at low concentrations and pH?2–3, forming stable oil-in-water emulsions. These Pickering emulsions exhibited pH-responsive behavior: raising the solution pH to 10 resulted in immediate demulsification due to the destabilization of microgel network at the oil–water interface. 相似文献
28.
Selberg-type integrals that can be turned into constant term identities for Laurent polynomials arise naturally in conjunction with random matrix models in statistical mechanics. Built on a recent idea of Karasev and Petrov we develop a general interpolation based method that is powerful enough to establish many such identities in a simple manner. The main consequence is the proof of a conjecture of Forrester related to the Calogero–Sutherland model. In fact we prove a more general theorem, which includes Aomoto's constant term identity at the same time. We also demonstrate the relevance of the method in additive combinatorics. 相似文献
29.
Vladislav S. Krasnoukhov Prof. Dr. Valeriy N. Azyazov Prof. Dr. Alexander M. Mebel Dr. Srinivas Doddipatla Dr. Zhenghai Yang Shane Goettl Prof. Dr. Ralf I. Kaiser 《Chemphyschem》2021,22(14):1497-1504
The chemical dynamics of the elementary reaction of ground state atomic silicon (Si; 3P) with germane (GeH4; X1A1) were unraveled in the gas phase under single collision condition at a collision energy of 11.8±0.3 kJ mol−1 exploiting the crossed molecular beams technique contemplated with electronic structure calculations. The reaction follows indirect scattering dynamics and is initiated through an initial barrierless insertion of the silicon atom into one of the four chemically equivalent germanium-hydrogen bonds forming a triplet collision complex (HSiGeH3; 3 i1 ). This intermediate underwent facile intersystem crossing (ISC) to the singlet surface (HSiGeH3; 1 i1 ). The latter isomerized via at least three hydrogen atom migrations involving exotic, hydrogen bridged reaction intermediates eventually leading to the H3SiGeH isomer i5 . This intermediate could undergo unimolecular decomposition yielding the dibridged butterfly-structured isomer 1 p1 (Si(μ-H2)Ge) plus molecular hydrogen through a tight exit transition state. Alternatively, up to two subsequent hydrogen shifts to i6 and i7 , followed by fragmentation of each of these intermediates, could also form 1 p1 (Si(μ-H2)Ge) along with molecular hydrogen. The overall non-adiabatic reaction dynamics provide evidence on the existence of exotic dinuclear hydrides of main group XIV elements, whose carbon analog structures do not exist. 相似文献
30.
In this study, new biodegradable and biocompatible amphiphilic polymers were obtained by modifying the peripheral hydroxyl groups of branched polyethers and polyesters with organosilicon substituents. The structures of the synthesized polymers were confirmed by NMR and GPC. Organosilicon moieties of the polymers were formed by silatranes and trimethylsilyl blocks and displayed hydrophilic and hydrophobic properties, respectively. The effect of the ratio of hydrophilic to hydrophobic organosilicon structures on the surface activity and biological activity of macromolecules was studied, together with the effect on these activities of the macromolecules’ molecular weight and chemical structure. In particular, the critical micelle concentrations were determined, the effect of the structure of the polymers on their wetting with aqueous solutions on glass and parafilm was described, and the aggregation stability of emulsions was studied. Finally, the effect of the polymer structures on their antifungal activity and seed germination stimulation was examined. 相似文献