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131.
It is shown that the process of resonant double electron capture in high energy He2++He collisions can be approximately described by a sum over products of one-electron CDW amplitudes. The summation coefficients are determined by stationary ground-state calculations with CI wavefunctions. Total and differential cross sections are calculated and compared with experimental values. 相似文献
132.
133.
[reaction: see text] The enzymatic degradation of starch can be monitored electronically using single-walled carbon nanotubes (SWNTs) as semiconducting probes in field-effect transistors (FETs). Incubation of these devices in aqueous buffer solutions of amyloglucosidase (AMG) results in the removal of the starch from both the silicon surfaces and the side walls of the SWNTs in the FETs, as evidenced by direct imaging and electronic measurements. 相似文献
134.
A simple and effective method of measuring diffusion rates of various acylating reagents in macro beads (in this work diameters greater than 570 microm) of amino-functionalized resins is presented. The extent of diffusion at various points of time was determined by treating beads with a staining reagent ("chloranil", 2,3,5,6-tetrachloro-1,4-benzoquinone) that colored the regions of the beads that had not yet been permeated by reagent (the central part of the beads). The volume of unstained resin (permeated part) was compared with the volume of the stained part, and diffusion rate constants were calculated. Factors influencing diffusion such as reagent concentration, solvent, temperature, resin type, and mechanical effects were investigated. The results showed that diffusion was promoted by increased temperature, good swelling of the resin, small reagents, and high concentrations but not by sonication or mechanical agitation. 相似文献
135.
An oxidation method (sulfone method) for the determination of polycyclic aromatic sulfur heterocycles (PASH) in diesel fuel is presented. The aromatic fraction of a diesel fuel, isolated by solid phase extraction, is oxidized under controlled conditions with hydrogen peroxide. The oxidation products, mainly methylated dibenzosulfone, are determined and quantified directly, without further clean-up, by HPLC with photodiode-array detection. 相似文献
136.
Wang Q Zakeeruddin SM Cremer J Bäuerle P Humphry-Baker R Grätzel M 《Journal of the American Chemical Society》2005,127(15):5706-5713
We report on cross surface ambipolar charge percolation within a monolayer of a molecular triad adsorbed on semiconducting or insulating mesoscopic metal oxide films. The triad consists of a triphenlyamine (TPA) donor and a perylenemonoimide (PMI) acceptor connected by a bithiophene (T2) bridge. The self-assembled PMI-T2-TPA monolayer exhibits p-type or n-type conduction depending on the potential that is applied to the conducting glass (FTO) electrode supporting the oxide films. Cross surface electron transfer is turned on at around -1.24 V (vs Fc+/Fc) where the PMI moiety is electroactive. The color of the film changes from red to blue during the reduction of the PMI. By contrast, lateral hole transfer is turned on at around 0.8 V (vs Fc+/Fc) where the TPA moiety becomes electroactive. The stepwise oxidation of the T2-TPA units at 0.79 and 1.28 V (vs Fc+/Fc) is associated with a color change of the film from red to black. Cyclic voltammetric as well as chronocoulometric and spectroelectrochemical measurements were applied to determine the percolation threshold for cross surface charge transfer and the diffusion coefficients for the electron and hole hopping process. The effect of oxide surface states on the lateral charge motion was also investigated. 相似文献
137.
The addition of C6H5? to the NN' ligand (NN' = Schiff base of pyridine carbaldehyde-(2) and (S)-(—)-α-phenylethylamine) in [C5H5 Mo(CO)2 NN'] PF6 occurs stereospecific from the side opposite to the C5H5-ring. 相似文献
138.
139.
NMR spectroscopy plays an important part in the determination of the structures of organic compounds. The parameters of importance here are the chemical shifts of the 1H and 13C nuclei and the spin-spin interactions both between 1H nuclei and between 1H and 13C nuclei. Couplings between 13C nuclei were almost completely neglected until a few years ago, since they were extremely difficult to observe because of the low natural abundance of 13C. However, it is these couplings which afford information directly on the carbon-carbon connectivities in the molecule. It is now possible to use a special NMR pulse sequence to make these couplings more readily visible: the result of using this sequence is a 13C-NMR spectrum from which the carbon skeleton concerned can be directly read off. Two-dimensional spectra in particular are very easy to evaluate. The pulse sequence involved, which bears the somewhat puzzling name INADEQUATE, produces double-quantum coherences from which the NMR signals of the coupled carbon nuclei can be obtained. In this article the principle of double-quantum coherence is described and a number of examples for the application of the INADEQUATE pulse sequences to problems in synthetic organic chemistry, biosynthesis and natural products chemistry are presented; in addition, the possibility of applying the INADEQUATE method to other nuclei is considered. 相似文献
140.
Miranda LP Lubell WD Halkes KM Groth T Grøtli M Rademann J Gotfredsen CH Meldal M 《Journal of combinatorial chemistry》2002,4(5):523-529
A novel polymer matrix for solid-phase synthesis, SPOCC(194) resin (1), was designed featuring a backbone of homogeneous tetraethylene glycol (TEG(194)) macromonomer linked by quaternary carbon junctions and terminating in primary alcohol functionality. Beaded SPOCC(194) resin was effectively prepared by suspension polymerization of oxetanylated TEG macromonomer 5 in stirred silicon oil. Mechanically stable and inert to a diverse range of reaction conditions, SPOCC(194) possessed a high hydroxyl group loading (0.9-1.2 mmol/g) for substrate attachment and swelled effectively ( approximately 2-4 mL/g) in a variety of organic and aqueous solvents. Developed for solid-phase synthesis at high reactant concentrations for driving organic and aqueous reactions to completion, SPOCC(194) exhibited high functional group density (mmol/mL) similar to that of low-loaded aminomethylated polystyrene-divinylbenzene copolymer (PS-1%DVB) yet significantly higher than that of PEGA(1900), SPOCC(1500), and TentaGel S. High-resolution MAS NMR spectra of Fmoc-derivatized SPOCC(194) indicate that monitoring of functional group transformation is possible. Moreover, by employment of a nonaromatic resin-linker combination, electrophilic chemistry, such as Lewis acid catalyzed glycosylation and Friedel-Crafts acylation, was selectively performed on substrate bound to SPOCC(194) resin. Such properties make SPOCC(194) resin a promising new polymer matrix for the support-bound construction of small organic molecules by parallel and combinatorial synthesis and the scavenging of solution-phase reactants or byproducts. 相似文献