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71.
The reaction rate of adiabatic proton/hydrogen/hydride (H) transfers in condensed phase is examined by combining the semiquantal time-dependent Hartree theory and the multidimensional transition state theory, which takes into account the zero-point effect and the dynamical modulation of the wavepacket width in the adiabatic transfer regime. By applying the theory to a model potential consisting of a quartic double well coupled linearly and quadratically (symmetrically) to external degrees of freedom, a set of compact analytical formulas was derived for the adiabatic H transfer rate. The analysis suggests that the kinetic isotope effect on the H transfer rate may exhibit a maximum as a function of the coupling strength to the external degrees of freedom measured by the reorganization energy. 相似文献
72.
73.
Lipid rafts are considered as specialized microdomains within the plasma membrane with unique lipid compositions different from surrounding membranes. Following T-cell receptor (TCR) stimulation, lipid rafts assemble in T-cell/antigen-presenting cell (APC) contact site known as the immunological synapse, inner leaflets of which serve as activation or docking sites for downstream signaling components. To understand the signaling events occurring in lipid rafts, we globally analyzed dynamic changes in lipid raft proteins during TCR/CD28 costimulation using 2-D fluorescence difference gel electrophoresis. We detected multiple spots whose intensities were enhanced after costimulation, and identified proteins in these spots by PMF. Identified proteins include Src family tyrosine kinases, tyrosine phosphatase, phosphatidylinositol 3-kinase (PI3-kinase), actin-binding proteins, and regulators for small GTPases. Of particular interest, a number of pleckstrin homology (PH) domain-containing proteins were identified. Biochemical and histochemical analyses confirmed the translocation of these proteins from cytosol to lipid rafts. We also demonstrated that these proteins assembled at the T-cell/APC interface. These results indicate the efficacy of our system to systematically analyze dynamics of lipid raft proteins during extracellular stimulation. 相似文献
74.
Abe I Morita H Oguro S Noma H Wanibuchi K Kawahara N Goda Y Noguchi H Kohno T 《Journal of the American Chemical Society》2007,129(18):5976-5980
Pentaketide chromone synthase (PCS) from Aloe arborescens is a novel plant-specific type III polyketide synthase (PKS) that produces 5,7-dihydroxy-2-methylchromone from five molecules of malonyl-CoA. On the basis of the crystal structures of wild-type and M207G mutant PCS, the F80A/Y82A/M207G triple mutant was constructed and shown to produce an unnatural novel nonaketide naphthopyrone by sequential condensations of nine molecules of malonyl-CoA. This is the first demonstration of the formation of a nonaketide by the structurally simple type III PKS. A homology model predicted that the active-site cavity volume of the triple mutant is increased to 4 times that of the wild-type PCS. 相似文献
75.
Yamada K Mukaihata N Kawahara T Tada H 《Langmuir : the ACS journal of surfaces and colloids》2007,23(16):8593-8596
The synergy of an anodic-biased alpha-Fe2O3 film and a cationic surfactant molecular assembly leads to a high visible light induced activity for 2-naphthol oxidation and high stability. An abrupt increase in the photocatalytic activity at a surfactant concentration of ca. 0.2 mmol dm(-3) results from the adsolubilization of 2-naphthol into the hydrophobic nanospace of the surfactant bilayer formed on the alpha-Fe2O3 surface. Also, the surfactant bilayer provides sustainable photocurrent during the reaction. 相似文献
76.
Yusuke Himei Tomohiro Nagakane Naoyuki Kitamura Akihiko Sakamoto 《Journal of Non》2008,354(27):3113-3119
Reduction in the temperature coefficient of the optical path length, dS/dT of Li2O-Al2O3-SiO2 glass-ceramics with near-zero thermal expansion coefficient was attempted using control of the temperature coefficient of electronic polarizability, ?, and the thermal expansion coefficient, α. The dS/dT value of 2.6 mol% B2O3-doped glass-ceramic was 12.5 × 10−6/°C, which was 0.9 × 10−6/°C smaller than that of B2O3-free glass-ceramic. On the other hand, reduction in dS/dT through B2O3 doping was not confirmed in precursor glasses. Results showed that reduction in dS/dT of the glass-ceramic through B2O3 doping is caused by the reduction in ?. The reduction in ? from B2O3 doping was probably attributable to numerical reduction in non-bridging oxide ions with larger ? value by the concentration of boron ions in the residual glass phase. In addition, application of hydrostatic pressure during crystallization was effective to inhibit precipitation of β-spodumene solid solution, which thereby decreases dS/dT. The dS/dT value of B2O3-doped glass-ceramic crystallized under 196 MPa was 11.7 × 10−6/°C. That value was slightly larger than that of silica glass. The α value of this glass-ceramic was smaller than that of silica glass. 相似文献
77.
Ryuichi Wada Tomoki Nakayama Tetsuya Hiyama Yasushi Fujiyoshi Naoyuki Kurita 《Isotopes in environmental and health studies》2017,53(6):646-659
Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO2 and water vapour were observed. The isotope ratios of both CO2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ13C–CO2 and δ18O–CO2 increased, while δ2H–H2Ov and δ18O–H2Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO2 and H2Ov could be used as a tracer of meteorological information. 相似文献
78.
Yoshiumi Kohno Yuuki Tamura Ryoka Matsushima 《Journal of photochemistry and photobiology. A, Chemistry》2009,201(2-3):98-101
A trial full-color rewritable film has been prepared by mixing fulgide derivatives as three primary-coloring dyes in a polymer, giving practically colorless or black form upon irradiation with white light or UV light. A good color image was obtained by a simple, one-shot irradiation with white light above the positive-color mask attached on the black film. The image could be erased and rewritten with another positive mask though degraded after many erase–write cycles. 相似文献
79.
Arc-disjoint in-trees in directed graphs 总被引:2,自引:0,他引:2
Given a directed graph D = (V,A) with a set of d specified vertices S = {s
1,…, s
d
} ⊆ V and a function f: S → ℕ where ℕ denotes the set of natural numbers, we present a necessary and sufficient condition such that there exist Σ
i=1
d
f(s
i
) arc-disjoint in-trees denoted by T
i,1,T
i,2,…, for every i = 1,…,d such that T
i,1,…, are rooted at s
i
and each T
i,j
spans the vertices from which s
i
is reachable. This generalizes the result of Edmonds [2], i.e., the necessary and sufficient condition that for a directed
graph D=(V,A) with a specified vertex s∈V, there are k arc-disjoint in-trees rooted at s each of which spans V. Furthermore, we extend another characterization of packing in-trees of Edmonds [1] to the one in our case.
Supported by JSPS Research Fellowships for Young Scientists.
Supported by the project New Horizons in Computing, Grand-in-Aid for Scientific Research on Priority Areas, MEXT Japan. 相似文献
80.
Naoyuki Hoshiya 《Tetrahedron》2006,62(24):5808-5820
Five bicyclic dioxetanes bearing a 2-hydroxynaphthyl group, 1aA-1eA, were synthesized and their chemiluminescent decomposition was examined by the use of tetrabutylammonium fluoride (TBAF) as a base in DMSO. It was found that these dioxetanes hold completely the ‘odd/even’ relationship between the substitution pattern of hydroxy as a trigger on the naphthalene ring and their chemiluminescent efficiency, and that dioxetane 1aA exhibited chemiluminescence with the highest efficiency among those for the oxynaphthyl-substituted dioxetanes hitherto known. The significant change in chemiluminescent efficiency depending on the substitution pattern was clarified to be attributed to the marked change in singlet-chemiexcitation efficiency for charge-transfer-induced chemiluminescence (CTICL) of 1aA-1eA. In respect of the rate of CTICL-decomposition, ‘odd/even’ relationship was observed for 1aA-1dA. 相似文献