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121.
122.
S Matsuo N Sakaguchi E Obuchi K Nakano R C Perera T Watanabe T Matsuo H Wakita 《Analytical sciences》2001,17(1):149-153
Ni L- and Ti L-edge as well as Ti K-edge X-ray absorption experiments for TiO2 thin films and Ni-doped TiO2 thin films coated on glass plates were performed using synchrotron radiation to investigate the structures around Ni and Ti ions in the films. The obtained spectra were compared with the results of theoretical calculations. It has consequently been found that the spectral features were affected by a change in the oxidizing form of Ni ions due to hydrogen reduction, by the charge variation and/or slight orbital splitting of Ti ions, and by the magnitude of the interaction between the center Ti ion and neighboring Ti ions. 相似文献
123.
Phosphorylimidates reacted with N-Boc imines in the presence of a catalytic amount of potassium hexamethyldisilazide, to afford the corresponding Mannich-type adducts in high yields. It was shown that, like sulfonylimidates, phosphorylimidates can function as ester equivalents. In contrast to sulfonylimidates however, phosphorylimidates exhibited high anti-selectivity even in low polar solvents. An explanation for the anti-selectivity is given. 相似文献
124.
Hidemi Nagao Masayoshi Nakano Kiyoshi Nishikawa Kizashi Yamaguchi 《International journal of quantum chemistry》2001,84(4):401-408
We investigate the quantum dynamics of two‐boson and two‐level systems interacting with a one‐mode photon field. The time evolution of the population for each state is calculated in terms of the Jaynes–Cummings model. We find the collapses and revivals of the order parameter for the Bose–Einstein condensation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 401–408, 2001 相似文献
125.
Taichi Nakano Takashi Miyamoto Takanori Endoh Makoto Shimotani Naoki Ashida Toshishige Morioka Yutaka Takahashi 《应用有机金属化学》2004,18(2):65-67
The palladium‐catalyzed silastannation of acetylenes with tributyl(trimethylsilyl)stannane in the presence of triethylphosphite is reported for the first time. The reaction occurs at room temperature to give (Z)‐silyl(stannyl)ethenes in high yields. The protodemetallation of the resulting adducts with HCl–tetraethylammonium chloride is described first, which demonstrates that the reaction is governed only by the stability of a carbonium ion arising from the protonation to (Z)‐silyl(stannyl)ethenes rather than the hard and soft acid and base principle, i.e. the β‐cation stabilization effect (σ–π stabilization one) of a stannyl group in the carbonium ion is rather significant. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
126.
A. Kotani T. Jo K. Okada T. Nakano M. Okada A. Bianconi A. Marcelli J.C. Parlebas 《Journal of magnetism and magnetic materials》1987,70(1-3):28-32
X-ray photoemission, X-ray photoabsorption and bremmstrahlung isochromat spectroscopy in Ce and La compounds are theoretically analyzed by using the single-site Anderson model incorporated with various final state interactions. Discussions are given on the physical information derived from the analysis and also on similarities and differences in spectral features between metallic and insulating systems. 相似文献
127.
The directional energy transport, i.e. exciton migration, in nanostar dendritic systems composed of two-state monomer units is studied using a quantum master equation approach. We examine the effects of the variation in the excitation energy of the monomer in the core region (core monomer) on the multistep exciton migration from the periphery to the core based on the relaxation factors among exciton states originating in weak exciton-phonon coupling. It turns out that when the core monomer possesses both an excitation energy slightly lower than that of the first generation and a partial exciton overlap with the first generation, more efficient and rapid exciton migration to the core is expected as compared with other core monomer cases with the energy level closer to or much lower than that of the first generation. 相似文献
128.
We applied a time-resolved small-angle neutron scattering technique to the vesicle system of dimyristoylphosphatidylcholine for the first time to determine lipid kinetics. The observed kinetics could be explicitly represented by a simple model that includes two independent kinetic parameters, i.e., the rates of transbilayer and interbilayer exchange. This technique is perfectly suited for the determination of lipid exchange kinetics in equilibrium and applicable to evaluation of the activity of the factors relevant to lipid migration, such as translocase and lipid transfer proteins. 相似文献
129.
The mechanism of the gold nanocluster‐catalyzed aerobic homocoupling of arylboronic acids has been elucidated by means of DFT calculations with Au20? as a model cluster for the Au:[poly(N‐vinylpyrrolidin‐2‐one)] catalyst. We found that oxygen affects the adsorption of phenylboronic acid and, by lowering the energy barrier, a water molecule enhances dissociation of the C?B bond, which is probably the rate‐determining step. The key role of oxygen is in activating the surface of the gold cluster by generating Lewis acidic sites for adsorption and activation of the phenylboronic acid, leading to the formation of biphenyl through a superoxo‐like species. Moreover, the oxygen adsorbed on the Au nanocluster can act as an oxidant for phenylboronic acid, giving phenol as a byproduct. As shown by NBO analysis, the basic aqueous reaction medium facilitates the reductive elimination process by weakening the Au?C bond, thereby enhancing the formation of biphenyl. The coupling of phenyl and reductive elimination of biphenyl occur at the top or facet site with low‐energy‐barrier through spillover of phenyl group on Au NC. The present findings are useful for the interpretation or design of other coupling reactions with Au NC. 相似文献
130.
Gold/Palladium Alloy for Carbon–Halogen Bond Activation: An Unprecedented Halide Dependence
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Dr. Raghu Nath Dhital Dr. Karan Bobuatong Prof. Dr. Masahiro Ehara Prof. Dr. Hidehiro Sakurai 《化学:亚洲杂志》2015,10(12):2669-2676
New catalytic activity of gold/palladium alloy nanoclusters (NCs) for carbon–halogen bond activation is demonstrated. In the case of an aryl chloride, the inclusion of gold in a bimetallic catalyst is indispensable to achieve the coupling reactions. Gold has the unique effect of stabilizing palladium, such that Pd2+ leached from clusters by means of spillover of chloride during oxidative addition. The thus‐formed spillover intermediate further reacts heterogeneously in both Ullmann and Suzuki‐type coupling reactions through a new type of mechanism. In the case of an aryl bromide, Ullmann coupling occurs through the spillover of bromide, similar to that of aryl chloride. However, a significant fraction of palladium also leached, which diminished the Ullmann coupling activity of the aryl bromide and, as a result, the order of reactivity was ArCl>ArBr. With regard to the activation of the C?Br bond towards a Suzuki‐type reaction, the inclusion of a higher gold content in gold/palladium clusters stabilized palladium to prevent the leaching of Pd2+ from the clusters by means of spillover of bromide. The spillover intermediate reacts heterogeneously with PhB(OH)2, palladium‐rich gold/palladium, or pure palladium clusters; the oxidative addition of ArBr favors the extraction of palladium from the clusters, yielding Pd2+ intermediates. The extracted intermediates react homogenously (Pd2+/Pd0 catalysis) with PhB(OH)2, which results in the higher selectivity of the cross‐coupling product. An initial step to observe such unprecedented halide dependency, together with the dynamic behavior of palladium on the surface of gold is the oxidative addition of Ar?X. A detailed insight into the first oxidative addition process was also examined by quantum chemical calculations. 相似文献