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991.
NMR J-couplings across hydrogen bonds reflect the static and dynamic character of hydrogen bonding. They are affected by thermal and solvent effects and can therefore be used to probe such effects. We have applied density functional theory (DFT) to compute the NMR (n)J(N,H) scalar couplings of a prototypical Chagas disease drug (metronidazole). The calculations were done for the molecule in vacuo, in microsolvated cluster models with one or few water molecules, in snapshots obtained from molecular dynamics simulations with explicit water solvent, and in a polarizable dielectric continuum. Hyperconjugative and electrostatic effects on spin-spin coupling constants were assessed through DFT calculations using natural bond orbital (NBO) analysis and atoms in molecules (AIM) theory. In the calculations with explicit solvent molecules, special attention was given to the nature of the hydrogen bonds formed with the solvent molecules. The results highlight the importance of properly incorporating thermal and solvent effects into NMR calculations in the condensed phase. 相似文献
992.
Olson IA Bacon WA Baez Sosa YY Delaney KM Forte SA Guglielmo MA Hill AN Kiesow KH Langenbacher RE Xun Y Young RO Bowyer WJ 《The journal of physical chemistry. A》2011,115(40):11001-11007
We describe three new strategies for determining heterogeneous reaction rates using photomicroscopy to measure the rate of retreat of metal surfaces: (i) spheres in a stirred solution, (ii) microscopic powder in an unstirred solution, and (iii) spheres on a rotating shaft. The strategies are applied to indium-mediated allylation (IMA), which is a powerful tool for synthetic chemists because of its stereoselectivity, broad applicability, and high yields. The rate-limiting step of IMA, reaction of allyl halides at indium metal surfaces, is shown to be fast, with a minimum value of the heterogeneous rate constant of 1 × 10(-2) cm/s, an order of magnitude faster than the previously determined minimum value. The strategies described here can be applied to any reaction in which the surface is retreating or advancing, thereby broadening the applicability of photomicroscopy to measuring heterogeneous reaction kinetics. 相似文献
993.
Li H Zhao YL Fahrenbach AC Kim SY Paxton WF Stoddart JF 《Organic & biomolecular chemistry》2011,9(7):2240-2250
A synthetic approach to the preparation of [2]rotaxanes (1-5·6PF(6)) incorporating bispyridinium derivatives and two 1,5-dioxynaphthalene (DNP) units situated in the rod portions of their dumbbell components that are encircled by a single cyclobis(paraquat-p-phenylene) tetracationic (CBPQT(4+)) ring has been developed. Since the π-electron-deficient bispyridinium units are introduced into the dumbbell components of the [2]rotaxanes 1-5·6PF(6), there are Coulombic charge-charge repulsions between these dicationic units and the CBPQT(4+) ring in the [2]rotaxanes. Thus, the CBPQT(4+) rings in the degenerate [2]rotaxanes exhibit slow shuttling between two DNP recognition sites on the (1)H NMR time-scale on account of the electrostatic barrier posed by the bispyridinium units, as demonstrated by variable-temperature (1)H NMR spectroscopy. Electrochemical experiments carried out on the [2]rotaxanes 1·6PF(6) and 2·6PF(6) indicate that the one-electron reduced bipyridinium radical cation in the dumbbell components of the [2]rotaxanes serves as an additional recognition site for the two-electron reduced CBPQT(2(˙+)) diradical cationic ring. Under appropriate conditions, the ring components in the degenerate rotaxanes 1·6PF(6) and 2·6PF(6) can shuttle along the recognition sites--two DNP units and one-electron reduced bipyridinium radical cation--under redox control. 相似文献
994.
Chiral separation by enantioselective liquid-liquid extraction 总被引:1,自引:0,他引:1
Schuur B Verkuijl BJ Minnaard AJ de Vries JG Heeres HJ Feringa BL 《Organic & biomolecular chemistry》2011,9(1):36-51
The literature on enantioselective liquid-liquid extraction (ELLE) spans more than half a century of research. Nonetheless, a comprehensive overview has not appeared during the past few decades. Enantioselective liquid-liquid extraction is a technology of interest for a wide range of chemists and chemical engineers in the fields of fine chemicals, pharmaceuticals, agrochemicals, fragrances and foods. In this review the principles and advances of resolution through enantioselective liquid-liquid extraction are discussed, starting with an introduction on the principles of enantioselective liquid-liquid extraction including host-guest chemistry, extraction and phase transfer mechanisms, and multistage liquid-liquid extraction processing. Then the literature on enantioselective liquid-liquid extraction systems is reviewed, structured on extractant classes. The following extractant classes are considered: crown ether based extractants, metal complexes and metalloids, extractants based on tartrates, and a final section with all other types of chiral extractants. 相似文献
995.
A novel consecutive three-component coupling-enamine addition synthesis gives access to three types of diene merocyanines in a selective fashion and in good yields. Moreover, all these push-pull systems are intensely red or yellow emissive in the solid state and display large Stokes shifts. 相似文献
996.
Using TMPZnCl·LiCl as a kinetically highly active base, nitriles and esters undergo a Pd-catalyzed α-arylation under mild conditions. Remarkably, in the case of α,β- or β,γ-unsaturated nitriles, a regioselective γ-arylation or a γ-alkenylation is observed. 相似文献
997.
Walter D. van Suijlekom 《Journal of Functional Analysis》2011,260(8):2483-2496
We study the spectral functional for a suitable function f, a self-adjoint operator D having compact resolvent, and a certain class of bounded self-adjoint operators A. Such functionals were introduce by Chamseddine and Connes in the context of noncommutative geometry. Motivated by the physical applications of these functionals, we derive a Taylor expansion of them in terms of Gâteaux derivatives. This involves divided differences of f evaluated on the spectrum of D, as well as the matrix coefficients of A in an eigenbasis of D. This generalizes earlier results to infinite dimensions and to any number of derivatives. 相似文献
998.
Martin Keller-Ressel Walter Schachermayer Josef Teichmann 《Probability Theory and Related Fields》2011,151(3-4):591-611
We show that stochastically continuous, time-homogeneous affine processes on the canonical state space ${\mathbb{R}_{\geq 0}^m \times \mathbb{R}^n}$ are always regular. In the paper of Duffie et?al. (Ann Appl Probab 13(3):984?C1053, 2003) regularity was used as a crucial basic assumption. It was left open whether this regularity condition is automatically satisfied for stochastically continuous affine processes. We now show that the regularity assumption is indeed superfluous, since regularity follows from stochastic continuity and the exponentially affine form of the characteristic function. For the proof we combine classic results on the differentiability of transformation semigroups with the method of the moving frame which has been recently found to be useful in the theory of SPDEs. 相似文献
999.
Huidong Yang Walter Zulehner 《Journal of Computational and Applied Mathematics》2011,235(18):5367-5379
Fluid-structure interaction problems arise in many fields of application such as flows around elastic structures and blood flow in arteries. The method presented in this paper for solving such a problem is based on a reduction to an equation at the interface, involving the so-called Steklov-Poincaré operators. This interface equation is solved by a Newton iteration, for which directional derivatives involving shape derivatives with respect to the interface perturbation have to be evaluated appropriately. One step of the Newton iteration requires the solution of several decoupled linear sub-problems in the structure and the fluid domains. These sub-problems are spatially discretized by a finite element method on hybrid meshes. For the time discretization, implicit first-order methods are used for both sub-problems. The discretized equations are solved by algebraic multigrid methods. 相似文献
1000.
A critical discussion is presented on the properties and prerequisites of adsorbed polyelectrolytes that have to function as substrates for further layer-by-layer deposition. The central theme is discriminating between the roles of electrostatic and non-electrostatic interactions. In order to emphasize this feature we refrain from discussing practical problems sometimes incurred in polyelectrolyte adsorption like freezing-in of non-equilibrium situations, patchwise attachment, unclear chemistry and only consider solid substrates. Although it is in principle ambiguous to discriminate between coulombic and non-coulombic or "chemical" interactions, it will be shown that, as a rule, non-coulombic contributions to the interactions cannot be neglected. They are responsible for the familiar overcharging. For obtaining more insight, it is recommended to consider electrometric techniques such as electrokinetics, conductometry and potentiometry, in combination with other analytical techniques applied to well-defined systems, for which various parameters can be modulated in a systematic way. 相似文献