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111.
Yoshio Takahashi Naoya Ohtaku Satoshi Mitsunobu Kouichi Yuita Masaharu Nomura 《Analytical sciences》2003,19(6):891-896
The details of a method used to determine the As(III)/As(V) ratio in soil by arsenic K-edge XANES spectroscopy are described. The spectra of mixtures of NaAs(III)O2 and NaH2As(V)O4, conducted for an As(III)/As(V) calibration, were well-fitted by combining normalized spectra of NaAsO2 and Na2HAsO4, where the coefficients multiplied by the normalized spectra were identical to the molar ratio of As(III) and As(V) in the mixtures. XANES spectra of arsenic in soil samples could also be fitted by a linear combination of the spectra of NaAsO2 and Na2HAsO4, which enabled us to estimate the As(III)/As(V) in a soil containing 10.2 mg/kg arsenic. The As(III)/As(V) ratio in the soil was compared with that of a soil solution contacted with the soil determined by HPLC-ICP-MS, showing that As(III) is distributed to water more readily than As(V). The application of the XANES method is important for a better understanding of the behavior of As(III) and As(V) independently in a natural aquifer. 相似文献
112.
Miki K Yokoi T Nishino F Kato Y Washitake Y Ohe K Uemura S 《The Journal of organic chemistry》2004,69(5):1557-1564
The reaction of alkenes with conjugated ene-yne-ketones, such as 1-benzoyl-2-ethynylcycloalkenes, with a catalytic amount of Cr(CO)(5)(THF) gave 5-phenyl-2-furylcyclopropane derivatives in good yields. The key intermediate of this cyclopropanation is a (2-furyl)carbene complex generated by a nucleophilic attack of carbonyl oxygen to an internal alkyne carbon in pi-alkyne complex or sigma-vinyl cationic complex. A wide range of late transition metal compounds, such as [RuCl(2)(CO)(3)](2), [RhCl(cod)](2), [Rh(OAc)(2)](2), PdCl(2), and PtCl(2), also catalyzes the cyclopropanation of alkenes with ene-yne-ketones effectively. When the reactions were carried out with dienes as a carbene acceptor, the more substituted or more electron-rich alkene moiety was selectively cyclopropanated with the (2-furyl)carbenoid intermediate. 相似文献
113.
Takenori Tomohiro Kouichi Uoto Takehiko Shimura Hiroaki Okuno 《Journal of heterocyclic chemistry》1988,25(5):1463-1465
Tetra-aza macrocycles with 28- to 44-membered rings can be readily synthesized by reaction of dibromide and ditosyldiamide without use of a high dilution method. The reaction proceeded very smoothly with a 10 mM concentration in DMF, and gave the macrocycles in excellent yields (60–80%). Favorable effects of cesium ion on the cyclization have been observed. 相似文献
114.
Spagnol G Shiraishi K Rajca S Rajca A 《Chemical communications (Cambridge, England)》2005,(40):5047-5049
The synthesis and magnetic characterization of pegylated bis(aminoxyl) diradical with an S= 1 ground state are presented, revealing water-induced changes in the molecular conformation and magnetic properties. 相似文献
115.
Summary
Ab initio calculations have been performed to study on the molecular structures and the vibrational levels of the low-lying ionic states (2A2 and2B1) of furan. The equilibrium molecular structures and vibrational modes of these states are presented. The theoretical ionization intensity curves including the vibrational structures of the low-lying two ionic states are also presented and compared with the photoelectron spectrum. A number of new assignments of the photoelectron spectra are proposed. 相似文献
116.
[Reaction: see text] GaCl3 is found to be a superior catalyst for the skeletal rearrangement of alpha,alpha,alpha-trisubstituted aldehydes to ketones. The rearrangement can proceed smoothly in the presence of a catalytic amount of GaCl3, and even substrates having no heteroatoms alpha to the carbonyl group or without steric strains can be used. Double activation of a carbonyl group by two molecules of GaCl3 was supported on the basis of experimental data and a DFT study. 相似文献
117.
Abstract— Fourier-transform (FT) infrared (IR) absorption spectra have been measured for chlorophyll a (Chi a ), chlorophyll b (Chi b ), pheophytin a (Pheo a ), and pheophytin b (Pheo b ) in highly dilute (10-5 -10-6 M ) water-saturated carbon tetrachloride solutions. Frequencies of IR bands due to C=O stretching modes of the 9-keto group indicate that Chi a assumes largely a dimeric structure in the concentrated (10-2 -10-3 M ) water-saturated carbon tetrachloride solutions but it remains mostly a monomer with one or two coordinated water molecules in dilute (10-5 -10-6 M ) solutions. Although it seems that Chi b also assumes predominantly dimeric form in concentrated solutions and monomelic form in dilute solutions, the relative intensity change of two C=O stretching bands ascribed to the free and coordinated 3-aldehyde groups with decreasing concentration suggests that the aldehyde group is also involved in formation of the dimer. The relative intensity of two C=O stretching bands due to the free and coordinated aldehyde groups changes significantly for Pheo b in water-saturated carbon tetrachloride solutions. This observation suggests that some of Pheo b also assume dimeric form via the aldehyde group in concentrated solutions. 相似文献
118.
Kouichi Takeshita 《Theoretical chemistry accounts》1996,93(4):243-258
Ab initio calculations have been performed to study on the molecular structures and the vibrational levels of the low-lying ionic states (2B2u,2Ag,2B2g,2B3u,2Au,2B1g,2B1u, and2B3g) of tetrafluoroethylene. The equilibrium molecular structures and vibrational modes of these states are presented. The theoretical ionization intensity curves including the vibrational structures of the low-lying eight ionic states are also presented and compared with the photoelectron spectrum. Some new assignments of the photoelectron spectra are proposed. 相似文献
119.
Youichiro Naito Yoshihisa Inoue Taizo Ono Yoshio Arakawa Chikara Fukaya Kazumasa Yokoyama Yoshiro Kobayashi Kouichi Yamanouchi 《Journal of fluorine chemistry》1984,26(4):485-497
Electrochemical fluorination of N-methyldecahydroquinoline afforded mainly a mixture of and N-(F-methyl)-F-decahydroquinoline, their rearranged isomers and F-propyl-F-cyclohexane arising from the cleavage at carbon-nitrogen bonds, in a ratio of approximately 2:4:6:3. N-Methyldecahydroisoquinoline was also fluorinated electrochemically to give a mixture of and N-(F-methyl)-F-decahydroisoquinoline, their rearranged isomers and 1-(F-ethyl)-2-(F-methyl)-F-cyclohexane in a ratio of approximately 4:4:6:1. No correlation was found between the and ratio of starting materials and that of the corresponding perfluorinated amines. Fluorination of N-methyl-1,2,3,4-tetrahydroquinoline gave much lower yields. 相似文献
120.
Takahashi A Kumatani T Usui S Tsujimura R Seki T Morimoto K Ohnishi T 《Photochemistry and photobiology》2005,81(4):1010-1014
Photoreactivation (PR) is an efficient survival mechanism that helps protect cells against the harmful effects of solar-ultraviolet (UV) radiation. The PR mechanism involves photolyase, just one enzyme, and can repair DNA damage, such as cyclobutane-pyrimidine dimers (CPD) induced by near-UV/blue light, a component of sunlight. Although the balance of near-UV/blue light and far-UV light reaching the Earth's surface could be altered by the atmospheric ozone layer's depletion, experiments simulating this environmental change and its possible effects on life have not yet been performed. To quantify the strength of UVB in sunlight reaching the Earth's surface, we measured the number of CPD generated in plasmid DNA after UVB irradiation or exposure to sunlight. To simulate the increase of solar-UV radiation resulting from the ozone layer depletion, Paramecium tetraurelia was exposed to UVB and/or sunlight in clear summer weather. PR recovery after exposure to sunlight was complete at a low dose rate of 0.2 J/m2 x s, but was less efficient when the dose rate was increased by a factor of 2.5 to 0.5 J/m2 x s. It is suggested that solar-UV radiation would not influence the cell growth of P. tetraurelia for the reason of high PR activity even when the ozone concentration was decreased 30% from the present levels. 相似文献