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排序方式: 共有177条查询结果,搜索用时 15 毫秒
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Mercury photosensitized hydrogen abstraction from alkanes is studied theoretically. A simple model based on the energy transfer to an electronic state of the alkane is shown to yield satisfactory agreement with the available experimental data. 相似文献
23.
Model calculations are reported which elucidate the effect of pyramidalization vibrations on sudden polarization in a symmetrically substituted ethylene. 相似文献
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Enantioselective Organocatalytic Reduction of β‐Trifluoromethyl Nitroalkenes: An Efficient Strategy for the Synthesis of Chiral β‐Trifluoromethyl Amines
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Elisabetta Massolo Prof. Maurizio Benaglia Manuel Orlandi Dr. Sergio Rossi Giuseppe Celentano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3589-3595
An efficient organocatalytic stereoselective reduction of β‐trifluoromethyl‐substituted nitroalkenes, mediated by 3,5‐dicarboxylic ester‐dihydropyridines (Hantzsch ester type), has been successfully developed. A multifunctional thiourea‐based (S)‐valine derivative was found to be the catalyst of choice, promoting the reaction in up to 97 % ee. The methodology has been applied to a wide variety of substrates, leading to the formation of differently substituted precursors of enantiomerically enriched β‐trifluoromethyl amines. The mechanism of the reaction and the mode of action of the metal‐free catalytic species were computationally investigated; on the basis of DFT transition‐state (TS) analysis, a model of stereoselection was also proposed. 相似文献
26.
Enantiopure chiral amidic derivatives of sinapic acid were oxidised with hydrogen peroxide using horseradish peroxidase (HRP) as the catalyst to give the aryltetraline dilignol thomasidioic acid. Trans-diastereoselectivity and enantioselectivity in the formation of thomasidioic acid was observed. Computational methods show that the enantioselectivity is controlled by the beta-beta oxidative coupling step, while the diastereoselectivity is controlled by the stability of the reactive conformation of the intermediate quinomethide. 相似文献
27.
Total order ranking methods are multicriteria decision making techniques used for the ranking of various alternatives on the basis of more than one criterion. The criteria, which are the standards by which the elements of the system are judged are not always in agreement, they can be conflicting, motivating the need to find an overall optimum that can deviate from the optima of one or more of the single criteria. Total order ranking methods are based on an aggregation of the criteria in a scalar function, i.e. an order or ranking index, which allow to sort elements according to its numerical value. Several evaluation methods which define a ranking parameter generating a total order ranking have been proposed in the literature. Four total order ranking methods are here described: Desirability functions, Utility functions, Dominance functions and Absolute Reference method. These methods have been compared to each other by applying them to a decision making problem in the paper industry. Various bleaching processes have been analysed and compared on the basis of multiple criteria, the aim being to find out best bleaching process among the ones proposed in the last years as alternative to chlorine bleaching process which is of high environmental impact due to the potential for chlorinated dioxin production. 相似文献
28.
Colombo F Benaglia M Orlandi S Usuelli F Celentano G 《The Journal of organic chemistry》2006,71(5):2064-2070
The stereoselective addition of aryl- and alkylacetylene derivatives to imines was studied. The reaction is catalyzed by copper complexes of enantiomerically pure bisimines, readily prepared in very high yields from the commercially available binaphthyl diamine. A very simple experimental procedure allowed to obtain at room temperature optically active propargylamines in high yields and enantioselectivity. Interestingly, bisimine/copper(I) complexes were able to promote the direct, enantioselective, catalytic addition to imines of alkylacetylenes. The effects of catalyst loading and other reaction parameters on the stereochemical outcome of the transformation were investigated. The extremely convenient methodology, the mild reaction conditions, and the possibility of a modular approach for developing new and more efficient bisimine-based chiral ligands make the present methodology very attractive. 相似文献
29.
Direct Numerical Simulation of a linearly accelerating channel flow starting from an initially statistically steady turbulent flow has been performed. It is shown that the response of the accelerating flow is fundamentally the same as that of the step-change transient flow described in He and Seddighi (J Fluid Mech 715:60–102, 2013). The flow structure again behaves like a boundary layer bypass transition undergoing three distinct phases, namely, (i) initially (pre-transition), the flow is laminar-like and the pre-existing turbulent structures are modulated resulting in elongated streaks leading to a strong and continuous increase in the streamwise fluctuating velocity but little changes in the other two components; (ii) it then undergoes transition when isolated turbulent spots are generated which spread and merge with each other, and (iii) they eventually cover the entire surface of the wall when the flow is fully turbulent. The similarity between the turbulence responses in the two flows is significant noting the contrasting features of the two types of mean flow unsteadiness: in the step-change flow, a sharp boundary layer is resulted in nearly instantly on the wall which closely resembles the spatially developing boundary layer, whereas the linear flow acceleration causes a continuing change of velocity gradient adjacent to the wall which propagates into the flow field with time, resulting in a gradually-developing boundary layer. There are, however, quantitative differences in the detailed behavior of the two flows and especially the transition is much delayed in the accelerating flow. It is also shown that the late pre-transition and early transition stages in both flows are characterised by significantly increased inwards sweep events in the wall region and ejection events in the outer layer. The flatness of the wall-normal velocity increases markedly near the wall around the time of onset of transition as a consequence of the huge intermittency of the velocity fluctuations. That is, there are long periods of quiescent flow coupled with occasional turbulent bursts. 相似文献
30.
P Orlandi C Ferrari M John Strain A Canciamilla F Morichetti M Sorel P Bassi A Melloni 《Optics letters》2012,37(17):3669-3671
We present the design and the fabrication of compact tunable silicon-on-insulator bandpass filters based on the integration of a Mach-Zehnder interferometer with ring resonators and activated via thermo-optic phase shifters. The proposed architecture provides wide filter bandwidth tunability from 10% to 90% of the free spectral range preserving the filter off-band rejection. Possible applications are channel subset selection in wavelength division multiplexing optical systems, adaptive filtering to signal bandwidth, and reconfigurable filters for gridless networking. 相似文献