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41.
Gillespie KM Sanders CJ O'Shaughnessy P Westmoreland I Thickitt CP Scott P 《The Journal of organic chemistry》2002,67(10):3450-3458
Racemic 2,2'-diamino-6,6'-dimethylbiphenyl is resolved using simulated moving bed chromatography, and the absolute configuration of the enantiomers is confirmed via the X-ray crystal structure of a derivative. The diamine is condensed with a range of aldehydes to give bidentate aldimine proligands L. Molecular structures of the complexes formed between L and Cu(I) fall into two classes; bimetallic double helices ([Cu(2)L(2)](2+)) and monometallic ([CuL](+)). The latter are strikingly more efficient in the aziridination of alkenes than are the former in terms of rate, turnover, and enantioselection. In particular, the imine ligand formed from the diamine and 2,6-dichlorobenzaldehyde gives, in combination with Cu(I) or Cu(II), up to 99% ee in the aziridination of 6-acyl-2,2-dimethylchromene and 88-98% ee for a range of cinnamate esters. Styrenic and other alkenes are converted with lower selectivities (5-54%). The catalytic system shows a linear response in product ee to catalyst ee, and the product ee does not vary significantly during the reaction. UV spectrophotometric investigations indicate that conversion of Cu(I) to Cu(II) is not essential for catalysis but that Cu(II) is probably also a competent system. 相似文献
42.
Long-time-scale molecular dynamics simulations are presented of the spontaneous formation of methane hydrate at a methane/liquid water interface. The water film was prepared at 300 K, 30 bar and showed no significant hydrate order. On crash cooling to 250 K, 300 bar (about 20 K subcooling), the system showed a rapid growth of hydrate clusters. Contrary to popular models for hydrate nucleation, the clusters formed first as two-dimensional arrangements and only later into three-dimensional cage structures; the results are, however, consistent with the local order model proposed recently. The hydrate clusters showed clear signatures of the type II hydrate structure even though the type I structure is the thermodynamically stable form for methane hydrate; this is in accord with the results of recent diffraction experiments. 相似文献
43.
《Journal of Pure and Applied Algebra》2022,226(12):107137
We prove that a (lax) bilimit of a 2-functor is characterized by the existence of a limiting contraction in the 2-category of (lax) cones over the diagram. We also investigate the notion of bifinal object and prove that a (lax) bilimit is a limiting bifinal object in the 2-category of (lax) cones. Everything is developed in the context of marked 2-categories, so that the machinery can be applied to different levels of laxity, including pseudo-limits. 相似文献
44.
Algebraic decay and variable speeds in wavefront solutions of a scalar reaction-diffusion equation 总被引:1,自引:0,他引:1
Wavefront solutions of scalar reaction-diffusion equations havebeen intensively studied for many years. There are two basiccases, typified by quadratic and cubic kinetics. An intermediatecase is considered in this paper, namely, ul = uxx + u2(1 u). It is shown that there is a unique travelling-wave solution,with a speed 1/2, for which the decay to zero ahead of the waveis exponential with x. Moreover, numerical evidence is presentedwhich suggests that initial conditions with such exponentialdecay evolve to this travelling-wave solution, independentlyof the half-life of the initial decay. It is then shown thatfor all speeds greater than 1/2 there is also a travelling-wavesolution, but that these faster waves decay to zero algebraically,in proportion to 1/x. The numerical evidence suggests that initialconditions with such a decay rate evolve to one of these fasterwaves; the particular speed depends in a simple way on the detailsof the initial condition. Finally, initial conditions decayingalgebraically for a power law other than 1/x are considered.It is shown numerically that such initial conditions evolveeither to an algebraically decaying travelling wave, or in somecases to a wavefront whose shape and speed vary as a functionof time. This variation is monotonic and can be quite pronounced,and the speed is a function of u as well as of time. Using asimple linearization argument, an approximate formula is derivedfor the wave speed which compares extremely well with the numericalresults. Finally, the extension of the results to the more generalcase of ul = uxx + um(1 u), with m > 1, is discussed. 相似文献
45.
Francisco J. Castro-Jimé nez Luis Narvá ez-Macarro David Mond 《Transactions of the American Mathematical Society》1996,348(8):3037-3049
We prove that if is a ``strongly quasihomogeneous" free divisor in the Stein manifold , and is its complement, then the de Rham cohomology of can be computed as the cohomology of the complex of meromorphic differential forms on with logarithmic poles along , with exterior derivative. The class of strongly quasihomogeneous free divisors, introduced here, includes free hyperplane arrangements and the discriminants of stable mappings in Mather's nice dimensions (and in particular the discriminants of Coxeter groups).
46.
Summary We prove that every mixing
d
by automorphisms of a compact, connected, abelian group is mixing of all orders.Oblatum 5-II-1992The second author gratefully acknowledges support from NSF grant DMS-91-03056 at the Ohio State University 相似文献
47.
Ruthenium(II) complexes of monodonor ligands: efficient reagents for asymmetric ketone hydrogenation
Xu YA Clarkson GC Docherty G North CL Woodward G Wills M 《The Journal of organic chemistry》2005,70(20):8079-8087
[Chemical reaction: See text] A series of BINOL-derived ligands have been prepared and incorporated into ruthenium(II) complexes containing a diamine ligand. The complexes have proven to be excellent catalysts for the asymmetric hydrogenation of ketones, giving reduction products with enantiomeric excesses of up to 99%. 相似文献
48.
Ruiz V Nicholson PG Jollands S Thomas PA Macpherson JV Unwin PR 《The journal of physical chemistry. B》2005,109(41):19335-19344
This paper reports the first comparison of the structure and electrical conductivity properties of spin cast (SC) and Langmuir-Schaeffer (LS) films of regioregular poly(3-hexylthiophene) (P3HT). In addition, the effect of incorporating highly monodisperse Au nanoparticles (NPs), with a core diameter of approximately 5 nm, into SC and LS P3HT films is described. A detailed picture of molecular organization in the films has been obtained using ultraviolet-visible absorption spectroscopy, atomic force microscopy, field-emission scanning electron microscopy, X-ray diffraction, and X-ray reflectivity. Film morphology was correlated with pseudo-two-dimensional conductivity measured using scanning electrochemical microscopy, with P3HT in the semiconducting regime. It was found that SC films, which were slightly thicker than those formed with the LS technique, exhibited greater organization. This resulted in an order of magnitude higher lateral conductivity for the SC films. Inclusion of Au NPs (50 wt %) into both SC and LS films resulted in the formation of uniform and relatively flat (rms roughness approximately 1 nm) composite films. Surprisingly, the addition of NPs did not disrupt the characteristic crystal structure found for the native P3HT films. The effect of Au NPs on film lateral conductivity was found to be determined by the distribution of Au NPs within the polymer, which varied significantly between SC and LS films. Whereas Au NPs aggregated into hexagonally packed clusters in SC films, NPs in LS films were predominantly uniformly distributed between the lamella bilayer. It was found that, while the inclusion of Au NPs caused the lateral conductivity to decrease in SC films, in LS films, the lateral conductivity increased by a factor of 2. 相似文献
49.
Targeted cellular delivery of drugs to specific tissues is an important goal in biomedical chemistry. Achieving this requires harnessing and applying molecular-level recognition events prevalent in (or specific to) the desired tissue type. Tissues rich in estrogen receptors (ERs), which include many types of breast cancer, accumulate molecules that have high binding affinities for these receptors. Therefore, molecules that (i) bind to the ER, (ii) have favorable cellular transport properties, and (iii) contain a second functionality (such as a center that may be used for diagnostic imaging or medical therapy) are exciting synthetic targets in the field of drug delivery. To this end, we have prepared a range of metallo-estrogens based on 17alpha-ethynylestradiol and examined their binding to the ER both as isolated receptor and in whole cell assays (ER positive MCF-7 cells). Estrogens functionalized with metal binding units are prepared by palladium-catalyzed cross-coupling reactions and a wide range of metal centers introduced readily. All the compounds prepared and tested exhibit effective binding to the estrogen receptor and are delivered across the cell membrane into MCF-7 cells. In the whole cell assays, despite their monocationic nature, the palladium and platinum complexes prepared exhibit similar (and even enhanced) receptor binding affinities compared to their corresponding neutral free ligands. It is unprecedented for a higher ER binding affinity to be observed for a cationic complex than for its metal-free ligand. 相似文献
50.
Anilinium is strongly adsorbed at monolayers of the phospholipid L-alpha-dimyristoylphosphatidic acid (DMPA) and hexadecanesulfonic acid (HDSA) at the air-water interface, and undergoes chemical polymerisation under conditions where bulk polymerisation does not occur. 相似文献