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21.
Low-temperature specific heat measurements on the heavy-fermion antiferromagnet CePb3 have been performed under pressures up to 1.3 GPa. From the shift of the anomaly atT
N
the magnetic phase diagram is constructed. The change of the shape of the anomaly, when the pressure exceeds 0.7 GPa, clearly indicates the crossover from one magnetic structure to another as had already been concluded from formern-scattering results. The Kondo temperature does not show a peculiar variation with pressure. 相似文献
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Appropriate oxygen-18 labeling experiments demonstrate that N,O-diarylhydroxylamines do not undergo solvolysis the reversible formation of ion pairs. This is in total conflict with the conclusions from previous indirect kinetic studies of these ultimate carcinogen models. 相似文献
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Asymptotics of the Interband Light Absorption Coefficient near the Band Edge for an Alloy-Type Model
We find the asymptotics of the interband light absorption coefficient of an alloy-type model in the case when the ground-state energies of the electron and the hole Hamiltonians are finite. 相似文献
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Cannon JS Kirsch SF Overman LE Sneddon HF 《Journal of the American Chemical Society》2010,132(43):15192-15203
The catalytic enantioselective S(N)2' displacement of (Z)-allylic trichloroacetimidates catalyzed by the palladium(II) complex [COP-OAc](2) is a broadly useful method for the asymmetric synthesis of chiral branched allylic esters. A variety of experiments aimed at elucidating the nature of the catalytic mechanism and its rate- and enantiodetermining steps are reported. Key findings include the following: (a) the demonstration that a variety of bridged-dipalladium complexes are present and constitute resting states of the COP catalyst (however, monomeric palladium(II) complexes are likely involved in the catalytic cycle); (b) labeling experiments establishing that the reaction proceeds in an overall antarafacial fashion; (c) secondary deuterium kinetic isotope effects that suggest substantial rehybridization at both C1 and C3 in the rate-limiting step; and (d) DFT computational studies (B3-LYP/def2-TZVP) that provide evidence for bidentate substrate-bound intermediates and an anti-oxypalladation/syn-deoxypalladation pathway. These results are consistent with a novel mechanism in which chelation of the imidate nitrogen to form a cationic palladium(II) intermediate activates the alkene for attack by external carboxylate in the enantiodetermining step. Computational modeling of the transition-state structure for the acyloxy palladation step provides a model for enantioinduction. 相似文献
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Regina Schmitt Patrick Mayer Benjamin Kirsch Jan Aurich Charlotte Kuhn Ralf Müller Kaushik Bhattacharya 《PAMM》2014,14(1):383-384
This work is motivated by cryogenic turning which allows end shape machining and simultaneously attaining a hardened surface due to deformation induced martensitic transformations. To study the process on the microscale, a multivariant phase field model for martensitic transformations in conjunction with a crystal plastic material model is introduced. The evolution of microstructure is assumed to follow a time-dependent Ginzburg-Landau equation. To solve the field equations the finite element method is used. Time integration is performed with Euler backward schemes, on the global level for the evolution equation of the phase field, and on the element level for the crystal plastic material law. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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Jamal Souady Denis Dadimov Stephan Kirsch Laura Bindila Jasna Peter‐Katalinić Sergey Y. Vakhrushev 《Rapid communications in mass spectrometry : RCM》2010,24(7):1039-1048
Glycosphingolipids (GSLs) are major components of the outer leaflet of the cell membrane. These lipids are involved in many cell surface events and show disease‐related expression changes. GSLs could thus serve as useful targets for biomarker discovery. The GSL structure is characterized by two entities: a hydrophilic glycan and a hydrophobic ceramide moiety. Both components exhibit numerous structural variations, the combination of which results in a large diversity of GSL structures that can potentially exist. Mass spectrometry (MS) is a powerful tool for high‐throughput analysis of GSL expression analysis and structural elucidation. Yet, the assignment of GSL structures using MS data is tedious and demands highly specialized expertise. SysBioWare, a software platform developed for MS data evaluation in glycomics, was here applied for the MS analysis of human serum GSLs. The program was tuned to provide automated compositional assignment, supporting a variety of glycan and ceramide structures. Upon in silico fragmentation, the masses of predicted ions arising from cleavages in the glycan as well as the ceramide moiety were calculated, thus enabling structural characterization of both entities. Validation of proposed structures was achieved by matching in silico calculated fragment ions with those of experimental MS/MS data. These results indicate that SysBioWare can facilitate data interpretation and, furthermore, help the user to deal with large sets of data by supporting management of MS and non‐MS data. SysBioWare has the potential to be a powerful tool for high‐throughput glycosphingolipidomics in clinical applications. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献