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171.
Long-range electrostatic fields deform the surface profile of a conductive liquid in the vicinity of the contact line. We have investigated the equilibrium profiles by balancing electrostatic and capillary forces locally at the liquid vapor interface. Numerical results show that the contact angle at the contact line approaches Young's angle. Simultaneously, the local curvature displays a weak algebraic divergence. Furthermore, we present an asymptotic analytical model, which confirms these results and elucidates the scaling behavior of the profile close to the contact line. 相似文献
172.
Al-free Zr-zeolite beta catalyzes the transfer reduction of ketones to the corresponding alcohols in high yield and with exceptional stereocontrol. Notably, the catalyst is very robust and gives good results even with 10% water content in the reaction mixture. 相似文献
173.
Studer A Amrein S Matsubara H Schiesser CH Doi T Kawamura T Fukuyama T Ryu I 《Chemical communications (Cambridge, England)》2003,(10):1190-1191
4-[(Trimethylstannyl)diphenylsilyl]butanoyl radical, arising from the corresponding 3-(stannylsilyl)propyl radical and CO, undergoes an SHi reaction at Si with extrusion of trimethyltin radical to give silacyclopentanone. The parent 3-(stannylsilyl)propyl radical was also found to isomerize to (3-stannylpropyl)silyl radical via a 1,4-Sn shift from Si to C with a rate constant of 9.3 x 10(4) s-1 at 80 degrees C. Ab initio and DFT MO calculations support a front-side attack mechanism. 相似文献
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Lowe LB Brewer SH Krämer S Fuierer RR Qian G Agbasi-Porter CO Moses S Franzen S Feldheim DL 《Journal of the American Chemical Society》2003,125(47):14258-14259
Laser-induced temperature jumps (LITJs) at gold nanoparticle-coated indium tin oxide (ITO) electrodes in contact with electrolyte solutions have been measured using temperature-sensitive redox probes and an infrared charge-coupled device. Upon irradiation with 532 nm light, interfacial temperature changes of ca. 20 degrees C were recorded for particle coverages of ca. 1 x 1010 cm-2. In the presence of a redox molecule, LITJ yields open-circuit photovoltages and photocurrents that are proportional to the number of particles on the surface. When ssDNA was used to chemisorb nanoparticles to the ITO surface, solution concentrations as low as 100 fM of target ssDNA-modified nanoparticles could be detected at the electrode surface. 相似文献
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Stephan Klaus Maximilian W. Lehenmeier Carly E. Anderson Bernhard Rieger 《Coordination chemistry reviews》2011,255(13-14):1460-1479
The catalytic copolymerization of CO2 with epoxides has been known for over 40 years. Even though many heterogeneous and homogeneous catalyst systems have been developed, catalyst activity and selectivity still remain too low for large scale industrial application.Recent investigations have identified new copolymerization pathways with strong evidence for cooperative (bifunctional) mechanisms. At high dilutions, traditional discrete mononuclear single-site catalyst systems generally show a loss in activity. This effect can be overcome with the help of recently developed dinuclear and binary linked systems that involve cooperative mechanisms and thus permit high catalyst efficiency.This review gives an overview on the most recent advances in CO2/epoxide copolymerization, new mechanistic studies and strategies for future catalyst developments. 相似文献
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Teobald Kupka Michał Stachów Jakub Kaminsky Stephan P. A. Sauer 《Magnetic resonance in chemistry : MRC》2013,51(8):482-489
A linear correlation between isotropic nuclear magnetic shielding constants for seven model molecules (CH2O, H2O, HF, F2, HCN, SiH4 and H2S) calculated with 37 methods (34 density functionals, RHF, MP2 and CCSD(T)), with affordable pcS‐2 basis set and corresponding complete basis set results, estimated from calculations with the family of polarization‐consistent pcS‐n basis sets is reported. This dependence was also supported by inspection of profiles of deviation between CBS estimated nuclear shieldings and shieldings obtained with the significantly smaller basis sets pcS‐2 and aug‐cc‐pVTZ‐J for the selected set of 37 calculation methods. It was possible to formulate a practical approach of estimating the values of isotropic nuclear magnetic shielding constants at the CCSD(T)/CBS and MP2/CBS levels from affordable CCSD(T)/pcS‐2, MP2/pcS‐2 and DFT/CBS calculations with pcS‐n basis sets. The proposed method leads to a fairly accurate estimation of nuclear magnetic shieldings and considerable saving of computational efforts. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献