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31.
Inside Cover: Solvent‐Driven Reductive Activation of CO2 by Bismuth: Switching from Metalloformate Complexes to Oxalate Products (Angew. Chem. Int. Ed. 48/2016) 下载免费PDF全文
32.
He J Fu Q Lindsay S Ciszek JW Tour JM 《Journal of the American Chemical Society》2006,128(46):14828-14835
We have studied electron transport in bipyridyl-dinitro oligophenylene-ethynelene dithiol (BPDN) molecules both in an inert environment and in aqueous electrolyte under potential control, using scanning tunneling microscopy. Current-voltage (IV) data obtained in an inert environment were similar to previously reported results showing conductance switching near 1.6 V. Similar measurements taken in electrolyte under potential control showed a linear dependence of the bias for switching on the electrochemical potential. Extrapolation of the potentials to zero switching bias coincided with the potentials of redox processes on these molecules. Thus switching is caused by a change in the oxidation state of the molecules. 相似文献
33.
Naka Seidel Klaus Jacob Piero Zanello Marco Fontani 《Journal of organometallic chemistry》2001,620(1-2)
The reaction of {C,N-[Fe(η5-C5H5)(η5-C5H3(CH2NMe2)-2)]}Li, (FcN)Li, with zinc chloride affords the diorganozinc complex (FcN)2Zn (1). In solution, 1 appears as a mixture of rac and meso diastereomers, whereas in the solid state it crystallizes solely as a rac diastereomer. The ratio of rac/meso diastereomers in solution is solvent-, temperature- and concentration-dependent, consistent with an intermolecular exchange between diastereomers. An intramolecular dynamic phenomenon involving dissociation and recoordination of Zn---N bonds was also observed. The reaction of 1 with zinc chloride yields the monoorganozinc compound (FcN)ZnCl (2) as a slightly soluble yellow microcrystalline powder. 相似文献
34.
Yu. A. Ryndin Yu. N. Nogin V. I. Zaikovskii K. Jacob K. -H. Thiele Yu. I. Yermakov 《Reaction Kinetics and Catalysis Letters》1985,29(2):395-402
(Pd+Ce)/SiO2 catalysts prepared by decomposition of organometallic complexes of Ce and Pd have higher activity, dispersity and selectivity in methanol synthesis than Pd/SiO2 catalysts.
, (Pd+Ce)/SiO2 , Ce Pd, Pd/SiO2.相似文献
35.
Tyrsted C Pauw BR Jensen KM Becker J Christensen M Iversen BB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(18):5759-5766
Understanding nanoparticle-formation reactions requires multi-technique in situ characterisation, since no single characterisation technique provides adequate information. Here, the first combined small-angle X-ray scattering (SAXS)/wide-angle X-ray scattering (WAXS)/total-scattering study of nanoparticle formation is presented. We report on the formation and growth of yttria-stabilised zirconia (YSZ) under the extreme conditions of supercritical methanol for particles with Y(2)O(3) equivalent molar fractions of 0, 4, 8, 12 and 25 %. Simultaneous in situ SAXS and WAXS reveals a quick formation (seconds) of sub-nanometre amorphous material forming larger agglomerates with subsequent slow crystallisation (minutes) into nanocrystallites. The amount of yttria dopant is shown to strongly affect the crystallite size and unit-cell dimensions. At yttria-doping levels larger than 8 %, which is known to be the stoichiometry with maximum ionic conductivity, the strain on the crystal lattice is significantly increased. Time-resolved nanoparticle size distributions are calculated based on whole-powder-pattern modelling of the WAXS data, which reveals that concurrent with increasing average particle sizes, a broadening of the particle-size distributions occur. In situ total scattering provides structural insight into the sub-nanometre amorphous phase prior to crystallite growth, and the data reveal an atomic rearrangement from six-coordinated zirconium atoms in the initial amorphous clusters to eight-coordinated zirconia atoms in stable crystallites. Representative samples prepared ex situ and investigated by transmission electron microscopy confirm a transformation from an amorphous material to crystalline nanoparticles upon increased synthesis duration. 相似文献
36.
Poehlsgaard J Harpsøe K Jørgensen FS Olsen L 《Journal of chemical information and modeling》2012,52(2):409-419
The binding affinity of a drug-like molecule depends among other things on the availability of the bioactive conformation. If the bioactive conformation has a significantly higher energy than the global minimum energy conformation, then the molecule is unlikely to bind to its target. Determination of the global minimum energy conformation and calculation of conformational penalties of binding is a prerequisite for prediction of reliable binding affinities. Here, we present a simple and computationally efficient procedure to estimate the global energy minimum for a wide variety of structurally diverse molecules, including polar and charged compounds. Identifying global energy minimum conformations of such compounds with force field methods is problematic due to the exaggeration of intramolecular electrostatic interactions. We demonstrate that the global energy minimum conformations of zwitterionic compounds generated by conformational analysis with modified electrostatics are good approximations of the conformational distributions predicted by experimental data and with molecular dynamics performed in explicit solvent. Finally the method is used to calculate conformational penalties for zwitterionic GluA2 agonists and to filter false positives from a docking study. 相似文献
37.
Rocha-Rinza T Sneskov K Christiansen O Ryde U Kongsted J 《Physical chemistry chemical physics : PCCP》2011,13(4):1585-1589
Using advanced QM/MM methods, the surprisingly negligible shift of the lowest-lying bright electronic excitation of the deprotonated p-coumaric acid (pCA(-)) within the photoactive yellow protein (PYP) is shown to stem from a subtle balance between hypsochromic and bathochromic effects. More specifically, it is found that the change in the excitation energy as a consequence of the disruption of the planarity of pCA(-) inside PYP is nearly canceled out by the shift induced by the intermolecular interactions of the chromophore and the protein as a whole. These results provide important insights about the primary absorption and the tuning of the chromophore by the protein environment in PYP. 相似文献
38.
Jacob J. Habeeb Farouq F. Said Dennis G. Tuck 《Journal of organometallic chemistry》1980,190(4):325-334
The electrochemical oxidation of indium metal in cells of the type
leads to the formation of RInX2 compounds; if 2,2′-bipyridine is also present, the products are the adducts RInX2·bipy (R = CH3, C2H5, C6H5, C6H5CH2, C6F5; X = Cl, Br, I (not all combinations)). When R′4NX is present instead of bipy, the products are the salts R′4N[RInX3]. The electrochemical oxidation apparently proceeds via the general mechanism discussed previously. Anomalous results with CH3I or C2H5I are discussed in the light of the known solution chemistry of organoindium(III) compounds. 相似文献
39.
Contributions to the Chemistry of Organo-Transition Metal Compounds. 47. Reactions of Hexachlorocerates(IV) with Organolithium Compounds Pyridinium hexachlorocerate(IV) reacts with lithium organyls RLi RLi (R = 1-Nor, (CH3)2NCH2CH2CH2, n-C4H9) in the molar ratio 1:2 with formation of Li2[CeCl6] · 2 NC5H5. A further mol RLi effects a reduction to Li3[CeCl6] · 2 NC5H5. With an excess of RLi amidocerium(III) complexes of the typ Li4 are formed. Li2[CeCl6] is formed also at reactions of quartery ammonium salts, e. g. [C6H5CH2N(C2H5)3]2[CeCl6], with RLi (R = 1-Nor, Me22NCH2CH2CH2) followed by an reduction to Li3[CeCl6]. An excess of the lithium organyl effects the formation Li4[RCeCl6] complexes. The yielded compounds were characterized by elementary analysis, the hydrolysis and deuterolysis products, magnetic moments, and IR-spectra. 相似文献
40.
Jacob Katriel 《International journal of quantum chemistry》1991,39(4):593-604
An expression for the product of a single-cycle class [(1)N - P(p)]N and an arbitrary class [(1)l1(2)l …? (N)lN]N of the symmetric group has recently been conjectured. This expression involves a sum over a relatively small number of reduced class sums, depending on p indices. A further conjecture is formulated and demonstrated, according to which reduced class coefficients (RCCS ) involving cycles whose length is expressed by means of a single index can be related to corresponding coefficients in the product of [(1)N - P+1(p - 1)]N with an arbitrary class sum. Consequently, the problem of evaluating the general class sum product reduces to that of obtaining a relatively small set of fundamental RCCS containing no single-index cycles. The conjectures mentioned can be used to evaluate the product [(1)N - p(p)]N · [(1)N - q(q)]N in terms of fundamental RCCS that can all be obtained from the product [(r)]r · [(r)]r, where r = min(p, q). For the latter product, we use a result due to Boccara. 相似文献