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171.
Andrea Olmos Aurélien Alix Jean Sommer Prof. Dr. Patrick Pale Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(42):11229-11234
ScIII‐doped solids based on zeolite materials have been investigated for the first time as catalysts in organic synthesis. ScIII–USY zeolite proved to be a novel and very efficient heterogeneous catalyst for the Mukaiyama aldol reaction. This easy‐to‐prepare catalyst exhibited wide scope and compatibility with functional groups and is very simple to use, easy to remove (by simple filtration), and is recyclable (up to three times without loss of activity). 相似文献
172.
173.
Andrei Hutanu Steffen Kiessig Andrea Bathke Rolf Ketterer Sonja Riner Jan Olaf Stracke Markus Wild Bernd Moritz 《Electrophoresis》2019,40(22):3014-3022
Charge heterogeneity profiling is important for the quality control (QC) of biopharmaceuticals. Because of the increasing complexity of these therapeutic entities [1], the development of alternative analytical techniques is needed. In this work, flow‐through partial‐filling affinity capillary electrophoresis (FTPFACE) has been established as a method for the analysis of a mixture of two similar monoclonal antibodies (mAbs). The addition of a specific ligand results in the complexation of one mAb in the co‐formulation, thus changing its migration time in the electric field. This allows the characterization of the charged variants of the non‐shifted mAb without interferences. Adsorption of proteins to the inner capillary wall has been circumvented by rinsing with guanidine hydrochloride before each injection. The presented FTPFACE approach requires only very small amounts of ligands and provides complete comparability with a standard CZE of a single mAb. 相似文献
174.
Influence of external electric field as well as base substitution effects on the reduction/oxidation free energies of single stranded DNA suggest that base sequencing via measuring redox properties might be feasible under the conditions that (i) a difference of ~ 230 kJ mol(-1) in the oxidation potentials is enough to discriminate between nucleobases conductance signals and (ii) the strand is long enough to reduce end effects. 相似文献
175.
A dirhodium(II) complex with N-perfluorooctylsulfonylprolinate ligands is found to catalyze the cyclopropanation of olefins with simple aryl diazomethanes. In contrast to previously reported dirhodium(II) catalysts, the present complex works well not only with very electron-rich olefins such as enol ethers, but also with styrenes. Consequently, the present catalyst allows to prepare functionalized diarylcyclopropanes in moderate yields with good diastereoselectivity for the cis product, whereas the enantioselectivity of the reaction appears negligible. 相似文献
176.
Attila Takács Andrea Czompa Gábor Krajsovszky Péter Mátyus László Kollár 《Tetrahedron》2012,68(38):7855-7860
5-Iodo- and 4,5-dibromo-2-methylpyridazin-3(2H)-ones were aminocarbonylated in the presence of various amines including amino acid methyl esters in a palladium-catalysed reaction. The iodo derivative afforded the corresponding amides with complete conversion and high isolated yields. The dibromo derivative has shown unexpectedly high reactivity in this reaction, resulting in 4,5-dicarboxamides using primary amines as N-nucleophiles. Monoaminocarbonylation has not been observed, i.e., neither 4-bromo-5-carboxamide nor 4-carboxamido-5-bromo derivatives have been formed. However, the use of secondary amines such as piperidine and morpholine resulted in the formations of mixtures of amino-substituted bromopyridazinones. That is, no carbon monoxide insertion took place in these cases. Some mechanistic details of the formation of aminocarbonylation and amination products are also discussed. 相似文献
177.
178.
Andrea D. Beck David G. Flad Claudia Tonhäuser Gregor Gassner Claus-Dieter Munz 《Flow, Turbulence and Combustion》2016,97(2):475-511
In this work we investigate the interplay of polynomial de-aliasing and sub-grid scale models for large eddy simulations based on discontinuous Galerkin discretizations. It is known that stability is a major concern when simulating underresolved turbulent flows with high order nodal collocation type discretizations. By changing the interpolatory character of the nodal collocation type discretization to a projection based discretization by increasing the number of quadrature points (polynomial de-aliasing), one is able to remove the aliasing induced stability problems. We focus on this effect and on the consequence for large eddy simulations with explicit subgrid scale models. Often, subgrid scale models have to achieve two possibly conflicting tasks in a single simulation: firstly stabilizing the numerics and secondly modeling the physical effect of the missing scales. Within a discontinuous Galerkin approach, it is possible to use either a fast (but potentially aliasing afflicted) nodal collocation discretization or a projection-based (but computationally costly) variant in combination with an explicit subgrid scale model. We use this framework to investigate the effect on the appropriate model parameter of a standard Smagorinsky subgrid scale model and of a Variational Multiscale Smagorinsky formulation. For this we first consider the 3-D viscous Taylor-Green vortex example to investigate the impact on the stability of the method and second the turbulent flow past a circular cylinder to investigate and compare the accuracy of the results. We show that the aliasing instabilities of collocative discretizations severely limit the choice of the model constant, in particular for high order schemes, while for de-aliased DG schemes, the closure model parameters can be chosen independently from the numerical scheme. For the cylinder flow, we also find that for the same model settings, the projection-based results are in better agreement with the reference DNS than those of the collocative scheme. 相似文献
179.
180.
The reaction of [Cp2MoH2] and AgBF4 with the dithio ligands Na(S2CPh) and K(S2COiPr) afforded the complexes [(Cp2MoH2AgS2CPh)2] (1) and [(Cp2MoH2AgS2COiPr)2] (2). Using the monothio ligands Na(SC(O)Ph), K(SC(O)CH3) and Na(S(NHPh)C=C(CN)2) the complexes [(Cp2MoH2AgSC(O)Ph)2] (3), [((Cp2MoH2)2(AgSC(O)CH3)3)n] (4) and [(Cp2MoH2)2AgS(NHPh)C=C(CN)2] (6) were formed. The reaction of thiobenzamide and [(Cp2MoH2)2AgCl] gave the complex [(Cp2MoH2Ag(Cl)S(NH2)CPh)2] (5). Complexes 1 and 2 have a dimeric structure with the two dithio ligands bridging the two silver atoms. Complex 3 is also a dimer, however, the monothio ligands are coordinated with their single sulphur atoms to the silver atoms. In the polymer 4 the thioacetate ligand has the same bonding mode as in 3. The three-dimensional structure of 4 is built-up of parallel strings. In the dimer 5 the thiobenzamide ligands bind with the sulphur atom to a silver atom each. Complex 6 has a monomeric structure in which the silver atom is coordinated to two [Cp2MoH2] ligands and to the sulphur atom of the S(NHPh)C=C(CN)2 ligand. Compounds 1–6 were characterised analytically and spectroscopically and the structures were determined by single crystal X-ray analyses. 相似文献