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191.
Andrzej Chmura Sven Rustler Monica Paravidino Fred van Rantwijk Andreas Stolz Roger A. Sheldon 《Tetrahedron: Asymmetry》2013,24(19):1225-1232
Enantiomerically pure (S)-mandelic acid was synthesised from benzaldehyde by sequential hydrocyanation and hydrolysis in a bienzymatic cascade at starting concentrations up to 0.25 M. A cross-linked enzyme aggregate (CLEA) composed of the (S)-selective oxynitrilase from Manihot esculenta and the non-selective nitrilase from Pseudomonas fluorescens EBC 191 was employed as the biocatalyst. The nitrilase produces approx. equal amounts of (S)-mandelic acid and (S)-mandelic amide from (S)-mandelonitrile under standard conditions, but we surprisingly found that high (up to 0.5 M) concentrations of HCN induced a marked drift towards amide production. By including the amidase from Rhodococcus erythopolis in the CLEA we obtained (S)-mandelic acid as the sole product in 90% yield and >99% enantiomeric purity. 相似文献
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Véronique Pignon Roger Jeannot Emmanuel Sauvard 《International journal of environmental analytical chemistry》2013,93(4):345-366
Abstract The coupling between liquid chromatography and mass spectrometry with an APCI or ESI interface (in positive or negative mode) is used here for multi-residue analyses in natural waters, covering basic and neutral pesticides as well as acid pesticides. The methods developed are applied to drinking and, river waters after the samples are concentrated by liquid-liquid extraction or solid phase extraction on C18 cartridges. Comparisons are made between UV detection and mass spectrometry and between two chromatographic methods for acid substances. The quantitation limits range from 0.01 to 0.1 μg/l according to the substance. 相似文献
194.
The morphological evolution of pyramids, developed on bombarded copper surfaces, as a function of consecutive doses of 12 keV Kr—ions from 2.4 × 1016 up to 3 × 1016 ions/cm2, has been studied. In disagreement with many previous studies, apparently based on a limited choice of doses which were sometimes not in sequence, we found that the pyramids disappeared at high enough doses. Pyramids are therefore not an equilibrium structure. 相似文献
195.
Highly Chemoselective Synthesis of Indolizidine Lactams by SmI2‐Induced Umpolung of the Amide Bond via Aminoketyl Radicals: Efficient Entry to Alkaloid Scaffolds
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Shicheng Shi Prof. Dr. Roger Lalancette D.Sc. Roman Szostak Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):11949-11953
Samarium(II) iodide enables a wide range of highly chemoselective umpolung radical transformations proceeding by electron transfer to carbonyl groups; however, cyclizations of important nitrogen‐containing precursors have proven limited due to their prohibitive redox potential. Herein, we report the first reductive cyclizations of unactivated cyclic imides onto N‐tethered olefins using SmI2/H2O. This new umpolung protocol leads to the rapid synthesis of nitrogen‐containing heterocycles that are of particular significance as precursors to pharmaceutical pharmacophores and numerous classes of alkaloids. The reaction conditions tolerate a wide range of functional groups. Excellent chemoselectivity is observed in the cyclization over amide and ester functional groups. Such unconventional reactivity has important implications for the design and optimization of new bond‐forming reactions by umpolung radical processes. The reaction advances the SmI2 cyclization platform to the challenging unactivated N‐tethered acyl‐type radical precursors to access nitrogen‐containing architectures. 相似文献
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A comparison among three weakly nonlinear approaches for thermo‐gravitational instability in a Newtonian fluid layer heated from below is presented. First, the dynamical systems describing the time evolution of the problem from different weakly nonlinear approaches, namely, the Lorenz model, the amplitude equations and the perturbation expansion approaches are obtained. Next, the steady states and their stability, as well as the transient behaviour are obtained from each dynamical system. The similarity and difference among the three models are emphasized. The role of each of the nondimensional groups, the Rayleigh number and the Prandtl number is compared for the three models. The different approaches lead to similar behaviours when the Rayleigh number is just above its critical value and Prandtl number is high. However, only the dynamical system obtained from the amplitude equations is able to reflect the role of the Prandtl number. On the other hand, the amplitude equations and perturbation expansion techniques are not suitable for predicting the uniform oscillatory behaviour observed frequently in Rayleigh–Bénard convection. The novelty of the current work lies in studying the critical differences in the findings of the three popular approaches to investigate weakly nonlinear thermal convection for the first time. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
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199.
Natasha Flyer Zhen Qin Roger Temam 《Numerical Methods for Partial Differential Equations》2012,28(6):1996-2009
This article is the numerical counterpart of a theoretical work in progress Qin and Teman, Applicable Anal (2011), 1–19, related to the approximation of evolution hyperbolic equations with incompatible data. The Korteweg‐de Vries and Schrödinger equations with incompatible initial and boundary data are considered here. For hyperbolic equations, the lack of regularity (compatibility) is known to produce large numerical errors which propagate throughout the spatial domain, destroying convergence. In this article, we numerically test the effectiveness of the penalty‐based method proposed in Qin and Teman, Applicable Anal (2011), 1–19, which replaces the hyperbolic equations with incompatible data by a system with compatible data. We observe that convergence is increased. As explained in the text, in the case of the Schrödinger equation, the impact of incompatible (nonregular) data is most severe, and the authors are not aware of any other method that can handle such severe incompatible data. © 2011 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2011 相似文献
200.
Jeffrey J. Lombardo Roger A. Ristau William M. Harris Wilson K. S. Chiu 《Journal of synchrotron radiation》2012,19(5):789-796
The preparation of hard material samples with the necessary size and shape is critical to successful material analysis. X‐ray nanotomography requires that samples are sufficiently thin for X‐rays to pass through the sample during rotation for tomography. One method for producing samples that fit the criteria for X‐ray nanotomography is focused ion beam/scanning electron microscopy (FIB/SEM) which uses a focused beam of ions to selectively mill around a region of interest and then utilizes a micromanipulator to remove the milled‐out sample from the bulk material and mount it on a sample holder. In this article the process for preparing X‐ray nanotomography samples in multiple shapes and sizes is discussed. Additionally, solid‐oxide fuel cell anode samples prepared through the FIB/SEM technique underwent volume‐independence studies for multiple properties such as volume fraction, average particle size, tortuosity and contiguity to observe the characteristics of FIB/SEM samples in X‐ray nanotomography. 相似文献