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排序方式: 共有63条查询结果,搜索用时 25 毫秒
1.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
2.
Terada Y Misoi R Watanabe N Hornberger M Kreis W 《Chemical & pharmaceutical bulletin》2000,48(3):349-352
Cardenolide glucohydrolase II (CGH II) is a cardenolide-specific glucohydrolase obtained from Digitalis lanata leaves. We investigated the structure-specificity relationship of several cardenolide disaccharides as a substrate for CGH II. Conformation analysis of the substrates was performed using molecular mechanics calculations. The sugar chain conformation of two inert glycosides was significantly different from that of the other glycosides. The other two glycosides, which were weak substrates of CGH II, were suggested to have an intramolecular hydrogen bond between the sugar groups. It was deduced that this hydrogen bond restricts the conformational change of the sugar chain and prevents the glycosides from enzymatic recognition. 相似文献
3.
4.
Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
5.
Jost Klawitter Stephan Bek Marjorie Zakaria Chenhui Zeng Andrea Hornberger Richard Gilbert Touraj Shokati Jelena Klawitter Uwe Christians K. Olaf Boernsen 《Analytical and bioanalytical chemistry》2014,406(25):6399-6408
Stearoyl-CoA desaturase 1 (SCD1) plays a role in the development of obesity and related conditions, such as insulin resistance, and potentially also in neurological and heart diseases. The activity of SCD1 can be monitored using the desaturation index (DI), the ratio of product (16:1n-7 and 18:1n-9) to precursor (16:0 and 18:0) fatty acids. Here, different analytical strategies were applied to identify the method which best supports SCD1 biology. A novel effective approach was the use of the SCD1-independent fatty acid (16:1n-10) as a negative control. The first approach was based on a simple extraction followed by neutral loss triglyceride fatty acid analysis. The second approach was based on the saponification of triglycerides followed by fatty acid analysis (specific for the position of the double bond within monounsaturated fatty acids (MUFAs)). In addition to the analytical LC-MS assays, different matrices (plasma total triglyceride fraction and the very low-density lipoprotein (VLDL) fraction) were investigated to identify the best for studying changes in SCD1 activity. Samples from volunteers on a high-carbohydrate diet were analyzed. Both ultra HPLC (UHPLC)-MS-based assays showed acceptable accuracies (75–125 % of nominal) and precisions (<20 %) for the analysis of DI-specific fatty acids in VLDL and plasma. The most specific assay for the analysis of the liver SCD activity was then validated for specificity and selectivity, intra- and interday accuracy and precision, matrix effects, dilution effects, and analyte stability. After 3 days of high-carbohydrate diet, only the specific fatty acids in human plasma VLDL showed a significant increase in DI and associated SCD1 activity. 相似文献
6.
The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton. 相似文献
7.
Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results. 相似文献
8.
L. Hackermüller K. Hornberger S. Gerlich M. Gring H. Ulbricht M. Arndt 《Applied physics. B, Lasers and optics》2007,89(4):469-473
We discuss a novel application of matter wave interferometry to characterize the scalar optical polarizability of molecules
at 532 nm. The interferometer presented here consists of two material absorptive gratings and one central optical phase grating.
The interaction of the molecules with the standing light wave is determined by the optical dipole force and is therefore directly
dependent on the molecular polarizability at the wavelength of the diffracting laser light. By comparing the observed matter-wave
interference contrast with a theoretical model for several intensities of the standing light wave and molecular velocities,
we can infer the polarizability in this first proof-of-principle experiment for the fullerenes C60 and C70, and we find a good agreement with literature values.
PACS 03.75.Dg; 03.65.-w; 33.15.Kr 相似文献
9.
We show how the quantum analog of the Fokker-Planck equation for describing
Brownian motion can be obtained as the diffusive limit of the quantum linear
Boltzmann equation. The latter describes the quantum dynamics of a tracer
particle in a dilute, ideal gas by means of a translation-covariant master
equation. We discuss the type of approximations required to obtain the
generalized form of the Caldeira-Leggett master equation, along with their
physical justification. Microscopic expressions for the diffusion and
relaxation coefficients are obtained by analyzing the limiting form of the
equation in both the Schr?dinger and the Heisenberg picture. 相似文献
10.
Different mean field homogenization methods are applied to a short glass fiber reinforced polybutylene terephthalate. The different models' predictions for the anisotropic effective elastic properties are assessed and compared to experimental data from tensile tests. Additionally, the estimation of fiber stresses and the influence of the fiber length distribution is studied. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献