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71.
Geng J Ducati C Shephard DS Chhowalla M Johnson BF Robertson J 《Chemical communications (Cambridge, England)》2002,(10):1112-1113
A nanoscale ruthenium/gold bimetallic cluster of clusters has been used as a molecular precursor to produce pure ruthenium nanoparticles (seeds) as catalysts for the growth of carbon nanohorns (CNHs). 相似文献
72.
Supramolecular isomerism in coordination compounds: nanoscale molecular hexagons and chains 总被引:1,自引:0,他引:1
Abourahma H Moulton B Kravtsov V Zaworotko MJ 《Journal of the American Chemical Society》2002,124(34):9990-9991
A nanoscale supramolecular hexagon, 1, and its supramolecular isomeric chain structure, 2, have been prepared from self-assembly of 5-NO2-bdc and Cu(II) cations. The hexagon is neutral and soluble and has outer and inner diameters of 3.1 and 0.8 nm, respectively. 相似文献
73.
The results of (low energy) photoelectron spectroscopy render possible a better appreciation of the “Nature of the Chemical Bond”. The application of this new experimental method is demonstrated utilizing representative compounds of the nonmetal elements, and a close symbiosis delineated with molecular orbital models. In particular, general consequences are discussed concerning electron deficiency, σ- and π-interactions, electron pair delocalization, and substituent effects or geometric perturbations. Photoelectron spectroscopic ionization energies permit evaluation of parameters for specified molecular groups, allow correlation with numerous other experimental data, and are didactically valuable in the teaching of general chemistry. 相似文献
74.
Initially in this review the sodalite framework [T12O24]6– (T=Al, Si] is modeled with regular tetrahedra and disordered T atoms. Equations are given for calculating atomic coordinates from the unit cell parameter a and the T—O distancet; the expansion or contraction of the sodalite-cage is related quantitatively to changes ina through the cooperative twists of TO4 tetrahedra about 4 axes and changes in < TOT bridge angles. The fully expanded cage has=0° and the maximum value ofa. The equations are general for any framework formed by isomorphous substitution of T by atoms other than Al, Si and for any SiAl ratio. The model and equations are extended to the zeolite A framework, which can be built from fully expanded sodalite cages. With the cooperative tilt of the TO4 tetrahedra of zeolite A, described by Depmeier, the major variable features of the zeolite A framework are explained quantitatively. The faujasite framework has twisted-cages (>0), as in sodalite examples, and is quantitatively modeled most conveniently from sodalite examples with similar-cage contents. The review is extended to structures with T-ordering and distorted tetrahedra. Methods are given for estimating a for sodalites from a knowledge of the cavity contents, especially the sizes of cations and anions, and so on, present. Ways of predicting cavity sites in zeolite A as a function of cation size are presented, and the principal cavity sites in the faujasite-cage region are discussed. Finally the review considers isomorphous replacement of T atoms (Si or Al) by B, Be, Fe, Ga, Ge, and P; many of these substituted frameworks are stabilized by templates, or guest molecules, which reside in the cavities. Templates also stabilize Si, Al frameworks with high SiAl ratios. The modeling approach reviewed here is tested on a range of isomorphously substituted frameworks isotypic with sodalite; observed and calculated values of twist and 12O24]12– with distorted tetrahedra; these are structures with Al-O-Al bridges, which violate Loewenstein's Rule. 相似文献
75.
Tondi D Morandi F Bonnet R Costi MP Shoichet BK 《Journal of the American Chemical Society》2005,127(13):4632-4639
Bacterial expression of beta-lactamases is the most widespread resistance mechanism to beta-lactam antibiotics, such as penicillins and cephalosporins. There is a pressing need for novel, non-beta-lactam inhibitors of these enzymes. One previously discovered novel inhibitor of the beta-lactamase AmpC, compound 1, has several favorable properties: it is chemically dissimilar to beta-lactams and is a noncovalent, competitive inhibitor of the enzyme. However, at 26 microM its activity is modest. Using the X-ray structure of the AmpC/1 complex as a template, 14 analogues were designed and synthesized. The most active of these, compound 10, had a K(i) of 1 microM, 26-fold better than the lead. To understand the origins of this improved activity, the structures of AmpC in complex with compound 10 and an analogue, compound 11, were determined by X-ray crystallography to 1.97 and 1.96 A, respectively. Compound 10 was active in cell culture, reversing resistance to the third generation cephalosporin ceftazidime in bacterial pathogens expressing AmpC. In contrast to beta-lactam-based inhibitors clavulanate and cefoxitin, compound 10 did not up-regulate beta-lactamase expression in cell culture but simply inhibited the enzyme expressed by the resistant bacteria. Its escape from this resistance mechanism derives from its dissimilarity to beta-lactam antibiotics. 相似文献
76.
[reaction: see text] A palladium-catalyzed arylation of allylic acetates followed by beta-acetoxy elimination was shown to produce Heck-type coupling products. Optimal reaction conditions employed ligand-free palladium on carbon in the presence of tetrabutylammonium chloride, a trialkylamine base, and water. 相似文献
77.
SCF MO calculations at the 6-31G** level of approximation are reported for 2H and 14N electric field gradients in HCN?HCN, HCN?HF, and CH3CN?HF dimers, with emphasis on the configurational dependence of these quantities in (HCN)2. In comparison with available experimental nuclear quadrupolar coupling constants, the calculated values for the monomers and dimers exhibit an accuracy of ≈ 10%, which is comparable to that of other spectroscopic parameters. The implications of hydrogen bonding for quadrupolar spin-lattice relaxation rates are briefly discussed. 相似文献
78.
A mesoporous silica-supported uranyl material (U(aq)O(2)(2+)-silica) was prepared by a co-condensation method. Our approach involves an I(-)M(+)S(-) scheme, where the electrostatic interaction between the anionic inorganic precursor (I(-)), surfactant (S(-)), and cationic mediator (M(+)) provides the basis for the stability of the composite material. The synthesis was carried out under acidic conditions, where the anionic sodium dodecyl sulfate provided the template for the uranyl cation and silicate to condense. Excitation with visible or near-UV light of aqueous suspensions of U(aq)O(2)(2+)-silica generates an excited state that decays with k(0) = 1.5 x 10(4) s(-1). The reaction of the excited state with aliphatic alcohols exhibits kinetic saturation and concentration-dependent kinetic isotope effects. For 2-propanol, the value of k(C)3(H)7(OH)/k(C)()3(D)7(OH) decreases from 2.0 at low alcohol concentrations to 1.0 in the saturation regime at high alcohol concentrations. Taken together, the data describe a kinetic system controlled by chemical reaction at one extreme and diffusion at the other. At low [alcohol], the second-order rate constants for the reaction of silica-U(aq)O(2)(2+) with methanol, 2-propanol, 2-butanol, and 2-pentanol are comparable to the rate constants obtained for these alcohols in homogeneous aqueous solutions containing H(3)PO(4). Under slow steady-state photolysis in O(2)-saturated suspensions, U(aq)O(2)(2+)-silica acts as a photocatalyst for the oxidation of alcohols with O(2). 相似文献
79.
Brian K. Nicholson 《Journal of organometallic chemistry》1992,440(3):411-418
The specific additions of one, three or four Ph3PAu groups to [M(CO)5]− (M=Mn, Re) are described. Thus [M(CO)5] − in THF reacts with [(Ph3PAu)3O]BF4 to give [(Ph3PAu)4Mn(CO)4]BF4. An X-ray crystal structure of the M = Mn example shows the cation to have a trigonal bipyramidal Au4Mn core with the Mn in an equatorial site. The previously known neutral (Ph3PAu)3M(CO)4 clusters are formed by addition of two Ph3PAu groups, using the mixed reagent [(Ph3PAu) 3O]BF4/[ppn][Co(CO)4], to Ph3PAuM(CO)5, which itself is readily prepared from [M(CO)5]− and Ph3PAuCl. 相似文献
80.
Peter V. Broadhurst Brian F.G. Johnson Jack Lewis A.Guy Orpen Paul R. Raithby John R. Thornback 《Journal of organometallic chemistry》1980,187(1):141-145
Reaction of CS2 with H2Os3(CO)8(MeCN)S in cyclohexane yields a product H2Os3(CO)7(CS)S2. this has been characterised by NMR and mass spectroscopy, and by X-ray analysis, and has been shown to contain a terminal thiocarbonyl ligand. 相似文献