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121.
122.
William F. Sokol Dennis H. Evans Katsumi Niki Tatsuhiko Yagi 《Journal of Electroanalytical Chemistry》1980,108(1):107-115
The cyclic voltammetric and differential pulse polarographic behavior of cytochrome c3 of Desulfovibrio vulgaris, strain Miyazaki, has been evaluated in terms of a model employing four reversible redox centers. Both types of experiments can be fit by digital simulations using the four standard potentials: E10=?0.467, E20=?0.519, E30=?0.539 and E40=?0.580 V vs. SCE. The results are interpreted to mean that the four redox centers are chemically different and only weakly interacting. The relationships between the observed macroscopic standard potentials and the microscopic standard potentials for reduction of individual sites are discussed. 相似文献
123.
Yuan DQ Tahara T Chen WH Okabe Y Yang C Yagi Y Nogami Y Fukudome M Fujita K 《The Journal of organic chemistry》2003,68(24):9456-9466
Three types of reactions of 2,3-anhydro-beta-cyclodextrins, namely nucleophilic ring-opening, reduction to 2-enopyranose, and reduction to 3-deoxypyranose, have been investigated to regio- and stereoselectively functionalize the secondary face of beta-cyclodextrin. Upon treatment with various nucleophiles, both 2,3-mannoepoxy and 2,3-alloepoxy-beta-cyclodextrins are found to undergo nucleophilic ring-opening reaction generating 3- and 2-modified cyclodextrin derivatives. In each case, the 3-position is more easily accessible than the 2-position. By using these ring-opening reactions, imidazolyl, iodo, azido, and benzylmercapto groups are selectively introduced to the secondary face of beta-cyclodextrin in place of the 2- or 3-hydroxyl groups. The functionalized cyclodextrins have either modified glucosidic subunits or modified altrosidic subunits that make the hydrophobic cavity slightly distorted from that of native beta-cyclodextrin. Thiourea also reacts with the cyclodextrin epoxides. In this case, thiirane and olefin species are generated instead of any ring-opening products. By ameliorating the reaction condition, cyclodextrin olefin, diene, and triene derivatives are prepared in moderate to good yields. Reduction of per[6-(tert-butyldimethyl)silyl]-beta-cyclodextrin permannoepoxide with lithium aluminum hydride produces the per(3-deoxy)-beta-cyclomannin. All these chemically modified cyclodextrins are structurally well characterized and most of them are expected to serve as versatile scaffolds for diverse purposes such as the construction of catalysts and development of synthetic receptors and molecular containers. 相似文献
124.
The effect of nonadiabatic transitions through the spin-orbit couplings has been investigated on the fast neutral reaction, O((3)P)+CH(3)-->CH(3)O. Adiabatic potential energies and the spin-orbit coupling terms have been evaluated for the four electronic states of CH(3)O ((2)E, (2)A(2), (4)E, and (4)A(2)) that correlate with the O((3)P)+CH(3) asymptote, as a function of CO distance and OCH angle under the C(3v) symmetry, by ab initio electronic structure calculations using multireference internally contracted single and double excitation configuration interaction method with the 6-311G(2df,2pd) basis sets. Multistate quantum reactive scattering calculations have been carried out with the use of thus obtained potential energies and spin-orbit coupling matrices, based on the generalized R-matrix propagation method. The calculated thermal rate constants show a slight positive dependence on temperature in a range between 50 and 2000 K, supporting the previous experimental results. It is shown that the spin-orbit coupled excited states give rise to reflections over the centrifugal barrier due to the quantum interference. Classical capture calculations yield larger rate constants due to the neglect of quantum reflections. It is concluded that the effect of nonadiabatic transitions is of minor importance on the overall reactivity in this reaction. 相似文献
125.
T. Omori R. Kimizuka K. Yoshihara M. Yagi 《Journal of Radioanalytical and Nuclear Chemistry》1984,82(2):269-273
The kinetics of reaction of indium(III)ion with EDTA (H4 edta) has been studied in aqueous acidic solutions using carrier-free111In and low concentrations of EDTA. The reaction takes place predominatly between indium(III) and H3 edta. The rate constant k3 is determined to be k3=(1.3±0.1)·105 dm3 mol–1 s–1 (25 °C). 相似文献
126.
ESR and phosphorescence of phosphorescent triplet states of 4-phenylpyridine, 4,4′-bipyridine and their singly pretonated cations have been studied in methanol-water (4: 1 by volume) and in stretched poly(vinyl alcohol) films at 77 K. The stretched-film method is useful for ESR assignments of aromatic bases whose triplet states are influenced by pH. 相似文献
127.
A. A. Kaminskii K. Ueda A. F. Konstantinova H. Yagi T. Yanagitani A. V. Butashin V. P. Orekhova J. Lu K. Takaichi T. Uematsu M. Musha A. Shirokava 《Crystallography Reports》2003,48(6):1041-1043
A continuous-wave lasing at 1 μm was excited by the radiation of semiconductor laser diodes at room temperature in nanocrystalline ceramics Y2O3 doped with Nd3+ and Yb3+ ions. The refractive indices of the undoped nanocrystalline Y2O3 ceramics were measured in the wavelength range 0.4–9 μm. 相似文献
128.
The effects of protonation on the excited states oftrans-3-styrylpyridine (StP) andtrans-4,4′-dipyridylethylene (DPE) have been studied through measurements of the time-resolved electron paramagnetic resonance (EPR), ultraviolet absorption, and fluorescence spectra in methanol-water mixtures at 77 K. The assignment of the transient EPR signals was carried out with the aid of the stretched poly(vinyl alcohol) films method. From the analysis of these spectra it is concluded that the single protonation appears to have little effect on the zero-field splitting parameters and the anisotropy in the sublevel populating rates of the lowest excited triplet (T1) states of StP and DPE. However, the decay rate constants of the fluorescent states decrease and fluorescence quantum yields increase on single protonation. These experimental results suggest that the single protonation causes a decrease in the intersystem crossing (ISC) rates for the three T1 sublevels. These results are explained in terms of the vibronic mixing between the1nπ* and1ππ* states in the lowest excited singlet state. The assignment of StP to the specified conformer was carried out through the analysis of the anisotropic ISC processes. 相似文献
129.
Rhodium nanoparticles were synthesized by the reduction of Rh3+ ion in ethanol solvent with use of the polyvinylpyrrolidone (PVP) of various molecular weights and the solvent of different volume ratios of water to ethanol. The formed Rh(PVP) nanoparticles have been characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) techniques. The TEM and AFM results show that the Rh(PVP) nanoparticles are monodispersed and do not agglomerate with each other. The particle size can be controlled by the molecular weight of PVP and/or the water/ethanol ratio of the solvent. The XPS and NEXAFS results indicate that the chlorine derived from RhCl3(3H2O) remains in the obtained nanoparticles but can be removed by heating. 相似文献
130.
Optical properties of Cr,Yb:YAG, Cr,Nd:YAG crystals, and composite Yb:YAG/Cr:YAG ceramics self-Q-switched solid-state laser
materials are presented. The merits of these self-Q-switched laser materials are given and the potentials of such lasers can
be chosen by the applications. Cr,Yb:YAG and composite Yb:YAG/Cr:YAG ceramics self-Q-switched laser are conducted. Although
several tens of kW peak power can be obtained with a monolithic microchip Cr,Yb:YAG laser, the experimental results show that
the performance of this laser is limited by the absorption of Cr4+ ions at a pump wavelength of 940 nm and strong fluorescence quenching at high Cr concentration. Composite Yb:YAG/Cr:YAG ceramics
are more suitable to realize high pulse energy and peak power (up to MW level) with optimized lasing and Q-switching parts.
In addition, the instabilities induced by the multi-longitudinal mode competition in Cr,Nd:YAG and Cr,Yb:YAG microchip lasers
are addressed. The different gain bandwidths of Yb:YAG and Nd:YAG play an important role in the instability of the output
laser pulse trains. Stable laser pulses from the Cr,Yb:YAG microchip laser were obtained due to the antiphase dynamics. For
the Cr,Nd:YAG microchip laser, the instability caused by the multi-longitudinal mode competition is an intrinsic property.
Different transverse patterns were observed in Cr,Nd:YAG microchip lasers when a pump beam with larger diameter was used.
Saturated inversion population distribution inside the gain medium plays an important role in the transverse pattern formation.
Different transverse patterns were reconstructed by combining different sets of the Hermite-Gaussian modes. 相似文献