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51.
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Khan S  Michel R  Koley D  Roesky HW  Stalke D 《Inorganic chemistry》2011,50(21):10878-10883
In a previous contribution, we have reported on a convenient and high yield synthesis of the disilene trans-[(TMS)(2)N(η(1)-Me(5)C(5))Si═Si(η(1)-Me(5)C(5))N(TMS)(2)] (2). Herein, we show the reactions of 2 with N(2)O and S(8). The former reaction affords two isomeric (cis- and trans-) dioxadisiletane ring compounds. To the best of our knowledge, this is the first report where both cis-and trans-isomers are isolated from the same disilene precursor and characterized structurally by single-crystal X-ray diffraction (XRD) studies. The reaction of 2 with elemental sulfur yields only the trans-isomer. To investigate this dissimilar reaction pattern exhibited by 2, computational studies were performed. Density functional theory (DFT) calculations showed that the two dioxadisiletane ring isomers are isoenergetic, with the trans isomer being slightly more stable than the cis counterpart, by 3.3 kcal/mol, while that is not the case with sulfur. All the isolated compounds are characterized by single-crystal XRD studies, multinuclear NMR spectroscopy, and electron ionization-mass spectrometry (EI-MS).  相似文献   
53.
A simple and convenient method to prepare acid-responsive microcapsules by using functionalized single-walled carbon nanotubes and ytterbium triflate has been developed. Fluorescence active compounds were "pre-loaded" or "post-loaded" in the microcapsules and released later in acidic medium. An interesting "zip-unzip" phenomenon was observed while filming the action of acid on microcapsules under a microscope.  相似文献   
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In this study, we have considered a prey-predator model reflecting the predator interference with discrete time delay. This delay is regarded as the lag due to gestation. In absence of delay, the criteria for existence of interior equilibrium and its global stability are derived. By choosing the delay as a bifurcation parameter, we have shown that a Hopf bifurcation may occur when the delay passes its critical value. Finally, we have derived the criteria for stability switches and verified the results through computer simulation.  相似文献   
56.
In this paper certain correspondences have been shown among various formulations of coupled-cluster theories for many electron closed-shell systems. Specifically it is shown that (i) the energy functional using unitary ansatz of the form exp (TT +) is exactly sameorder by order inT with the size-consistent energy functional 〈ψ|H|ψ〉/〈ψ|ψ〉 recently obtained by us in coupled-cluster framework; (ii) in the framework of unitary ansatz of the form exp (TT +), both non-variational and variational approaches lead to identical equations upto any given order inT andT + inTT 2 approximation; (iii) variational procedure using our size-consistent energy functional or using the functional obtained in the framework of unitary ansatz (as envisaged by Kutzelnigg) leads to energy in both cases, inTT 2 approximation, for a total of quadratic powers inT andT +, same as Cizek’s linearised coupled pair many electron theory energy; (iv) in case of practical calculation of the energy through the variational procedures using our size-consistent energy functional and the functional in unitary ansatz framework, there is a loss of upper bound.  相似文献   
57.
Photoenolization of a ketone in its lowest triplet state was examined using the AM 1 semiempirical molecular orbital method with complete geometry optimization at the configuration interaction level in the restricted Hartree–Fock frame. The theoretical barrier fits with a polynomial given by Eq. (1) and the probability of tunneling of hydrogen was calculated by the WKB method. The density of states above the zero-point level was estimated by the Whitten–Rabinovitch approximation. Rate constants for the hydrogen and deuterium-abstraction processes via tunneling were then computed at different temperatures. © 1994 John Wiley & Sons, Inc.  相似文献   
58.
The mechanism of the cross-coupling of phenylboronic acid with acetic anhydride, a viable model of the widely used Suzuki reaction, has been studied by DFT calculations at the BP86/6-31G level of theory. Two alternative catalytic cycles have been investigated, one starting from a neutral Pd(0)L(2) complex, the other from an anionic "Jutand-type" [Pd(0)L(2)X](-) species. The reaction profiles are in good agreement with the experimental findings, as both pathways require only moderate activation energies. Both pathways are dominated by cis-configured square-planar palladium(II)diphosphine intermediates. Despite careful investigations, we did not find in this model reaction any evidence for five-coordinate palladium(II) intermediates, which are commonly believed to cause the profound effects of counterions in palladium-catalyzed transformations. Instead, our calculations suggest that the higher catalytic activity of anionic complexes, such as [Pd(PMe(3))(2)OAc](-), may arise from their stronger ability to coordinate to carbon electrophiles. The transmetalation sequence is the same for both catalytic cycles, involving the dissociation of one phosphine ligand from the palladium. In the decisive transition state, in which the phenyl group is transferred from boron to palladium, the acetate base is found to be in a bridging coordination between these two atoms.  相似文献   
59.
Due to the inherent difficulty in crystallizing membrane proteins, approaches based on fluorescence spectroscopy have proved useful in elucidating their conformational characteristics. The ion channel peptide gramicidin serves as an excellent prototype for monitoring membrane protein conformation and dynamics due to a number of reasons. We have analyzed conformational heterogeneity in membrane-bound gramicidin using fluorescence lifetime distribution analysis of tryptophan residues by the maximum entropy method (MEM). MEM represents a model-free and robust approach for analyzing fluorescence lifetime distribution. In this paper, we show for the first time, that fluorescence lifetime distribution analysis using MEM could be a convenient approach to monitor conformational heterogeneity in membrane-bound gramicidin in particular and membrane proteins in general. Lifetime distribution analysis by MEM therefore provides a novel window to monitor conformational transitions in membrane proteins.  相似文献   
60.
The design of a medium energy beam transport (MEBT) line comprising of a re-buncher and four quadrupoles, two upstream and the other two downstream of the re-buncher, has been presented. The design was done to ensure almost 100% transport of heavy-ion beams of about 99 keV/u energy from RFQ having a q/A not less than 1/14 through the re-buncher and then through IH Linac of about 0.6 m length in which beam would be accelerated to about 185 keV/u. The re-buncher has been designed to operate at 37.8 MHz, the resonating frequency of both the RFQ and the IH Linac. The entire beam line has been installed and recently O5+ beam from RFQ has been transported through the re-buncher and subsequently accelerated in the IH Linac successfully.  相似文献   
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