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121.
Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl 下载免费PDF全文
Christoph Schnegelsberg Sebastian Bachmann Marlene Kolter Thomas Auth Dr. Michael John Prof. Dr. Dietmar Stalke Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7752-7762
Grignard reagents RMgCl and their so‐called turbo variant, the highly reactive RMgCl?LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity‐enhancing effect. A combination of electrospray‐ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion‐ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl?LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron‐rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents. 相似文献
122.
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
123.
124.
Michal Achmatowicz Agnieszka Szczepańska Daniel T. Gryko Piotr Salański Janusz Jurczak 《Supramolecular chemistry》2013,25(1):93-95
Abstract Bisamidation of oxaloyl chloride using L-amino acid methyl ester hydrochlorides afforded chiral diesters. The following reactions of diesters with 2,2-(ethylene-dioxy)diethylamine, afforded tetramides possessing C2 symmetry. Coupling of N-hydroxysuccinimide ester of N-benzyloxycarbonyl-L-alanine with 1,5-diamino-3-oxapentane, followed by cleavage of protecting groups, afforded an optically active diamine, which was transformed consequently into tetramide via the reaction with diglycolic acid dimethyl ester under high pressure conditions. 相似文献
125.
Ying Su Christos S. Karamitros Julian Nomme Theresa McSorley Manfred Konrad Arnon Lavie 《Chemistry & biology》2013,20(4):533-540
Highlights? Increased expression of hASNase3 was observed in several tumors, but the relevance is unclear ? Cancer cells have increased glycolytic flux and thus have more glycine but less aspartate ? Glycine activates the asparaginase activity of hASNase3 by promoting self-cleavage ? Thus, glycine may act as a sensor that regulates cellular aspartate concentrations 相似文献
126.
Agata Górniak Bożena Karolewicz Ewa Żurawska-Płaksej Janusz Pluta 《Journal of Thermal Analysis and Calorimetry》2013,111(3):2125-2132
The objective of the present investigation was to study the effect of eutectic formation on in vitro dissolution of simvastatin (SIM) released from mixtures with acetylsalicylic acid (ASA) prepared by a grinding method. SIM–ASA mixtures were characterized by means of differential scanning calorimetry (DSC), infrared spectroscopy (IR), X-ray powder diffractometry (XRPD), and in vitro dissolution tests. IR spectroscopy and XRPD studies indicated no interaction between SIM and ASA in the solid state. The DSC investigation has revealed that SIM and ASA form a simple eutectic system containing 66.6 % w/w of SIM at the eutectic point. In vitro dissolution studies of SIM and its mixtures with ASA were carried out. The eutectic mixture shows an appreciable increase in the dissolution rate in comparison with other ratios and SIM in 0.5 % w/v sodium lauryl sulfate. The dissolution enhancement of SIM was related to the effective wetting of the drug particles with a significantly reduced size released from eutectic composition. In conclusion, dissolution of SIM can be enhanced through eutectic formation with ASA by means of simple mechanical activation (a grinding method). 相似文献
127.
Dr. Christian Kulp Konrad Gillmeister Prof. Dr. Wolf Widdra Prof. Michael Bron 《Chemphyschem》2013,14(6):1205-1210
The synthesis of Cu(core)Pt(shell) model catalysts by the direct electrochemical deposition of Pt on Cu particles is presented. Cu particles with an average diameter of 200 nm have been deposited on glassy‐carbon electrodes by double pulse electrodeposition from a copper sulfate solution. Subsequent deposition from a platinum nitrate solution under potential control allows for a high selectivity of the Pt deposition towards Cu. Using a combination of cyclic voltammetry, XPS and sputtering, the structure of the generated particles has been analyzed and their core–shell configuration proven. It is shown that the electrocatalytic activity for the oxygen reduction is similar to that of other PtCu catalyst systems. The synthesized structures could allow for the analysis of structure–activity relations of core–shell catalysts on the way to the simple and controlled synthesis of supported Cu(core)Pt(shell) nanoparticles as oxygen reduction catalysts. 相似文献
128.
Niko Guskos Janusz Typek Aleksander Guskos Grzegorz Zolnierkiewicz Pawel Berczynski Diana Dolat Barbara Grzmil Antoni Morawski 《Central European Journal of Chemistry》2013,11(12):1996-2004
Nanoparticles of nitrogen-modified TiO2 (N-doped TiO2) calcined at 300°C and 350°C, have been prepared with and without water rinsing. Samples were characterized by x-ray diffractrometry (XRD) and optical spectroscopy. The electron paramagnetic resonance (EPR) spectra from centers involving oxygen vacancies were recorded for all samples. These could be attributed to paramagnetic surface centers of the hole type, for example to paramagnetic oxygen radicals O?, O2 ? etc. The concentration of these centers increased after water rising and it further increased for samples annealed at higher temperature. Additionally, for samples calcined at 300°C, and calcined at 350°C and rinsed, the EPR spectra evidenced the presence of magnetic clusters of Ti3+ ions. The photocatalytic activity of samples was studied towards phenol decomposition under unltraviolet-visible (UV-Vis) irradiation. It was found that, in comparison to the starting materials, the rinsed materials showed increased photocatalytic activity towards phenol oxidation. The light absorption (UV-Vis/DRS) as well as surface Fourier transform infrared/diffuse reflectance spectroscopy (FTIR/DR) studies confirmed a significantly enhanced light absorption and the presence of nitrogen groups on the photocatalysts surfaces, respectively. A significant increase of concentration of paramagnetic centers connected with oxygen vacancies after water rising has had an essential influence on increasing their photocatalytic activity. 相似文献
129.
Barbara Bojko Krzysztof Gorynski German Augusto Gomez-Rios Jan Matthias Knaak Tiago Machuca Vinzent Nikolaus Spetzler Erasmus Cudjoe Michael Hsin Marcelo Cypel Markus Selzner Mingyao Liu Shaf Keshavjee Janusz Pawliszyn 《Analytica chimica acta》2013
Metabolomics and biomarkers discovery are an integral part of bioanalysis. However, untargeted tissue analysis remains as the bottleneck of such studies due to the invasiveness of sample collection, as well as the laborious and time-consuming sample preparation protocols. In the current study, technology integrating in vivo sampling, sample preparation and global extraction of metabolites – solid phase microextraction was presented and evaluated during liver and lung transplantation in pig model. Sampling approaches, including selection of the probe, transportation, storage conditions and analyte coverage were discussed. The applicability of the method for metabolomics studies was demonstrated during lung transplantation experiments. 相似文献
130.
Jerzy Jabłoński Władysław Janusz Marta Szymula Jerzy Szczypa 《Journal of Dispersion Science and Technology》2013,34(6):663-681
The adsorption of metal ions at the stearic acid/electrolyte and nnonadccane-stearic acid mixture/electrolyte interface was investigated by means of the potentiometric titration, zeta potential and adsorption measurements. It was found that the studied colloidal suspensions exhibited an adsorption affinity towards multivalent metal ions. The adsorption of Ca2+, Cd2+ and Al3+ ions caused a strong decrease of surface charge density and zeta potential values in this systems. The adsorption reactions occur by way of cation exchange with protons from two surface carboxyl groups. Al high metal concentrations, in adsorption reactions there are involved also carboxyl groups from the subsurface layer. On the basis of the adsorption data, the cation surface complexation constants were calculated by Shindler's method. 相似文献