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191.
We measured quantitative spectra of firefly (Photinus pyralis) bioluminescence in the presence of Zn2+ and other bivalent metal ions to investigate the effects of these metal ions on luciferin‐luciferase reaction. We studied the dependence of the quantum yield and spectrum on quantity and kind of bivalent metal ions. Adding various amounts of Mg2+, Mn2+ and Ca2+ produced virtually no change in the quantum yields or the spectra of bioluminescence. In contrast, increasing amounts of ions such as Zn2+ and Cd2+ decreased quantum yields and changed the bioluminescence color from yellow‐green to red. Quantitative analysis showed that the sensitivities of the quantum yield and color to various metal ions were in the order of Hg2+>Zn2+, Cd2+>Ni2+, Co2+, Fe2+≫Mg2+, Mn2+, Ca2+. We propose that the changes in quantum yield and spectrum caused by the metal ions are due to their effect on luciferase that surrounds oxyluciferin during its radioactive decay. We also found that having more metal ions accelerated bioluminescence reactions. The sensitivity of the reaction rate had no correlation with those of the quantum yield and spectrum. 相似文献
192.
Tsukamoto D Ikeda M Shiraishi Y Hara T Ichikuni N Tanaka S Hirai T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9816-9824
Semiconductor TiO2 particles loaded with WO3 (WO3/TiO2), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO3/TiO2 catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO2. In particular, a catalyst loading 7.6 wt % WO3 led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO2 surface of the catalyst, which is active for oxidation, is partially coated by the WO3 layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO2 surface. This suppresses subsequent decomposition of the aldehyde on the TiO2 surface and results in high aldehyde selectivity. The WO3/TiO2 catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity. 相似文献
193.
Periodic density functional theory calculations revealed strong enhancement of chemical reactivity by defects located at the oxide-metal interface for water dissociation on ultrathin MgO films deposited on Ag(100) substrate. Accumulation of charge density at the oxide-metal interface due to irregular interface defects influences the chemical reactivity of MgO films by changing the charge distribution at the oxide surface. Our results reveal the importance of buried interface defects in controlling chemical reactions on an ultrathin oxide film supported by a metal substrate. 相似文献
194.
Taniguchi M Tsutsui M Mogi R Sugawara T Tsuji Y Yoshizawa K Kawai T 《Journal of the American Chemical Society》2011,133(30):11426-11429
The symmetry of a molecule junction has been shown to play a significant role in determining the conductance of the molecule, but the details of how conductance changes with symmetry have heretofore been unknown. Herein, we investigate a naphthalenedithiol single-molecule system in which sulfur atoms from the molecule are anchored to two facing gold electrodes. In the studied system, the highest single-molecule conductance, for a molecule junction of 1,4-symmetry, is 110 times larger than the lowest single-molecule conductance, for a molecule junction of 2,7-symmetry. We demonstrate clearly that the measured dependence of molecule junction symmetry for single-molecule junctions agrees with theoretical predictions. 相似文献
195.
Copper-mediated chemoselective trifluoromethylation at the benzylic position by the use of shelf-stable electrophilic trifluoromethylating reagents 3 in good to high yields under mild conditions is described for the first time. The generality of this trifluoromethylation for a wide variety of benzyl bromides facilitates the rapid creation of structural diversity of medicinal candidates in drug discovery. 相似文献
196.
A Pd(II)-catalyzed cascade reaction of chiral nonracemic allylic alcohols possessing an internal mono- or diepoxide and a terminal alcohol provided a contiguous THF-THF ring unit stereospecifically. The cyclization takes place in a 5-exo-tet-5-exo-trig fashion with high chirality transfer through a syn-S(N)2' like process for the formation of the internal THF ring. Chiral bis- and tris-THF-THF ring units were effectively prepared from acyclic precursors by the Pd-catalyzed reaction. 相似文献
197.
That there is a close connection between crude (or suspended) Hopf invariants and the reduced diagonal map has long been known. In this paper we build on a classical result of Boardman and Steer (1967) to explore some further relationships in terms of conic structures. In a related result we show that certain Toda brackets contain crude Hopf invariants as elements. In particular, using this latter observation, detection of crude Hopf invariants can be carried out. 相似文献
198.
Reiichiro Kawai 《Statistics & probability letters》2011,81(4):460-469
We discuss the local asymptotic behavior of the likelihood function associated with all the four characterizing parameters (α,β,δ,μ) of the Meixner Lévy process under high-frequency sampling scheme. We derive the optimal rate of convergence for each parameter and the Fisher information matrix in a closed form. The skewness parameter β exhibits a slower rate alone, relative to the other three parameters free of sampling rate. An unusual aspect is that the Fisher information matrix is constantly singular for full joint estimation of the four parameters. This is a particular phenomenon in the regular high-frequency sampling setting and is of essentially different nature from low-frequency sampling. As soon as either α or δ is fixed, the Fisher information matrix becomes diagonal, implying that the corresponding maximum likelihood estimators are asymptotically orthogonal. 相似文献
199.
Reiichiro Kawai Hiroki Masuda 《Journal of Computational and Applied Mathematics》2011,235(8):2873-2887
Various simulation methods for tempered stable random variates with stability index greater than one are investigated with a view towards practical implementation, in particular cases of very small scale parameter, which correspond to increments of a tempered stable Lévy process with a very short stepsize. Methods under consideration are based on acceptance-rejection sampling, a Gaussian approximation of a small jump component, and infinite shot noise series representations. Numerical results are presented to discuss advantages, limitations and trade-off issues between approximation error and required computing effort. With a given computing budget, an approximative acceptance-rejection sampling technique Baeumer and Meerschaert (2009) [11] is both most efficient and handiest in the case of very small scale parameter and moreover, any desired level of accuracy may be attained with a small amount of additional computing effort. 相似文献
200.
Yuasa J Ohno T Miyata K Tsumatori H Hasegawa Y Kawai T 《Journal of the American Chemical Society》2011,133(25):9892-9902
Highly luminescent tris[β-diketonate (HFA, 1,1,1,5,5,5-hexafluoropentane-2,4-dione)] europium(III) complexes containing a chiral bis(oxazolinyl) pyridine (pybox) ligand--[(Eu(III)(R)-Ph-pybox)(HFA)(3)], [(Eu(III)(R)-i-Pr-pybox)(HFA)(3)], and [(Eu(III)(R)-Me-Ph-pybox)(HFA)(3)])--exhibit strong circularly polarized luminescence (CPL) at the magnetic-dipole ((5)D(0) → (7)F(1)) transition, where the [(Eu(III)(R)-Ph-pybox)(HFA)(3)] complexes show virtually opposite CPL spectra as compared to those with the same chirality of [(Eu(III)(R)-i-Pr-pybox)(HFA)(3)] and [(Eu(III)(R)-Me-Ph-pybox)(HFA)(3)]. Similarly, the [(Tb(III)(R)-Ph-pybox)(HFA)(3)] complexes were found to exhibit CPL signals almost opposite to those of [(Tb(III)(R)-i-Pr-pybox)(HFA)(3)] and [(Tb(III)(R)-Me-Ph-pybox)(HFA)(3)] complexes with the same pybox chirality. Single-crystal X-ray structural analysis revealed ligand-ligand interactions between the pybox ligand and the HFA ligand in each lanthanide(III) complex: π-π stacking interactions in the Eu(III) and Tb(III) complexes with the Ph-pybox ligand, CH/F interactions in those with the i-Pr-pybox ligand, and CH/π interactions in those with the Me-Ph-pybox ligand. The ligand-ligand interactions between the achiral HFA ligands and the chiral pybox results in an asymmetric arrangement of three HFA ligands around the metal center. The metal center geometry varies depending on the types of ligand-ligand interaction. 相似文献