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1.
2.
A nanosecond laser photolysis study was carried out for the Cr(III) porphyrin complexes of 2,3,7,8,12,13,17,18-octaethylporphyrin, [Cr(OEP)(Cl)(L)], and of 5,10,15,20-tetramesitylporphyrin, [Cr(TMP)(Cl)(L)], in toluene containing water and an excess amount of L (L = axial ligand). The laser photolysis generates the triplet excited state of the parent complex as well as a five-coordinate complex, [Cr(porphyrin)(Cl)], produced by the photodissociation of the axial ligand L. The yields for the formation of the triplet state and the photodissociation of L are found to markedly depend on the nature of both L and porphyrin ligand. The five-coordinate [Cr(porphyrin)(Cl)] readily reacts with both H(2)O and L in the bulk solution to give [Cr(porphyrin)(Cl)(H(2)O)] and [Cr(porphyrin)(Cl)(L)], respectively. The axial H(2)O ligand in [Cr(porphyrin)(Cl)(H(2)O)] is then substituted by the ligand L to regenerate the original complex [Cr(porphyrin)(Cl)(L)]. In principle, the substitution reaction takes place by the dissociative mechanism: the first step is the dissociation of H(2)O from [Cr(porphyrin)(Cl)(H(2)O)], followed by the reaction of the five-coordinate [Cr(porphyrin)(Cl)] with the ligand L to regenerate [Cr(porphyrin)(Cl)(L)]. The rate constants for this ligand substitution reaction are found to exhibit bell-shaped ligand concentration dependence. The detailed kinetic analysis revealed that both ligands L and H(2)O in toluene make a hydrogen bond with the axial H(2)O ligand in [Cr(porphyrin)(Cl)(H(2)O)] to yield dead-end complexes for the substitution reaction. The reaction mechanisms are discussed on the basis of the substituent effects of the porphyrin peripheral groups and the kinetic parameters determined from the temperature dependence of the rate constants. 相似文献
3.
Ikuo Ashikawa Mariko Kito Kimiyuki Satoh Hiroyuki Koike Yorinao Inoue Kayoko Saiki Kiyoshi Tsukida Yasushi Koyama 《Photochemistry and photobiology》1987,46(2):269-275
All- trans β-carotene-5,6-epoxide has been found in the thylakoid membranes of spinach and of the cyanobacterium Synechococcus vulcanus Copeland. The epoxide was extracted from the thylakoid membranes with acetone, and was isolated by high-performance liquid chromatography (HPLC). The structure of the epoxide was identified by means of mass, Raman, and electronic absorption spectroscopy. Changes in the amount of the epoxide, as a result of epoxidation and (apparent) de-epoxidation reactions in the membranes, were traced by analysis of extracts on HPLC. In isolated thylakoid membranes, only the epoxidation reaction took place. The reaction was caused by irradiation or by the addition of ferricyanide, suggesting that electron transport reactions in the membranes are involved in the epoxidation. In intact spinach leaves, however, both epoxidation and de-epoxidation took place; the extent of epoxidation correlated with the intensity of light incident on the leaves. The epoxidation and de-epoxidation of all- trans β-carotene are contrasted with those of xanthophylls (in the violaxanthin cycle). 相似文献
4.
A rapid spectrophotometric method has been developed for the stepwise determination for mercury, cadmium, and zinc in mixtures. Optimal conditions have been established for the extraction efficiency of cadmium and mercury with a chloroform solution of tribenzylamine pre-equilibrated with hydrobromic acid. After addition of dithizone solution to the organic layers the absorbance at 490 nm or 510 nm is measured for mercury or cadmium, respectively. Even when the ratio of mercury, cadmium, and zinc is 10-1 : 1 : 10-5 , the metals can be determined successively. 相似文献
5.
Nambu H Hata K Matsugi M Kita Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):719-727
The combination of the water-soluble radical initiator, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VA-044) and the surfactant, cetyltrimethyl-ammonium bromide (CTAB), was found to be the most suitable condition for the effective and direct synthesis of useful active thioesters (pentafluorophenyl thioesters) in water. In addition, the direct amidation of aldehydes was achieved by the addition of the amines to the thioesterification reaction mixture in water. 相似文献
6.
Atsushi Takamizawa Kayoko Mishina Kenzo Hiraoka 《Journal of mass spectrometry : JMS》2012,47(2):221-225
Covalent bonds are often created by a reaction between chemicals and protein before causing various adverse effects in a cell. Dimethylaminoethyl methacrylate (DMAEMA), which has moderate toxicity, causes skin inflammation and throat irritation. For this study, we investigated a reaction mechanism between myoglobin and (DMAEMA) using a new analytical tool developed at our laboratory: laser spray mass spectrometry technique. It was found that initially DMAEMA was added to the amino group of protein by the Michael addition mechanism; the added DMAEMA was hydrolyzed to methacrylic acid using an autocatalytic system. The results of this study indicate the feasibility of the laser spray technique in analyses of reaction dynamics. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
7.
Mayumi Tsutsui Tokuhiro Watanabe Akihiro Ohta Kayoko Takizawa 《Journal of heterocyclic chemistry》1980,17(4):809-812
1 H-Nmr spectra of cis and trans isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines were taken at various temperatures. The spectra of geometrical isomers bearing the ae or ea dimethyl groups showed broadening at lower temperatures. It was clarified that the measurement of the spectra at lower temperatures is useful for the discrimination of the geometrical isomers of dimethylpiperazines. 相似文献
8.
The growth of C60 nanowhiskers (C60NWs) prepared by a modified liquid–liquid interfacial precipitation method is investigated, focusing on the effect of solvent ratio and water content in the C60–toluene–isopropyl alcohol (IPA) solution system. The precipitation of C60NWs was markedly influenced by the solvent ratio of toluene to IPA, and the C60NWs were found to grow longer above a critical diameter (Dc), which depends on the solvent ratio. The addition of a small amount of H2O to the C60–toluene–IPA solution promoted the growth of C60NWs. This catalytic effect of water on the growth of C60NWs was confirmed also by the experiment using heavy water (D2O) and by the decrease of growth activation energy of C60NWs with increase of H2O content in the C60–toluene–IPA solution. 相似文献
9.
A simple method for the rapid and simultaneous analysis of dichlorvos (DDVP), malathion, carbaryl, and 2,4-dichlorophenoxy acetic acid (2,4-D) in citrus fruit, which uses flow-injection ion spray ionization tandem mass spectrometry, has been developed for the first time. The method involves the combined use of stable isotopically labeled internal standards (DDVP-d6, malathion-d10, carbaryl-d7, and 2,4-D-d5) and a multiple reaction monitoring technique. The average recoveries for the pesticides at the same concentrations as their tolerance levels (DDVP: 0.1-0.2 μg g−1; malathion: 0.5-4.0 μg g−1; carbaryl: 1.0 μg g−1; 2,4-D: 1.0-2.0 μg g−1) ranged from 90 to 119% with the relative standard deviation (R.S.D.) ranging from 1.0 to 13.1% (n = 5). Analysis time, including sample preparation and determination, was only 15 min. The present method is effective for screening DDVP, malathion, carbaryl, and 2,4-D in citrus fruit. 相似文献
10.
Masako Maekawa Haruko Nagai Kayoko Magara 《Colloids and surfaces. A, Physicochemical and engineering aspects》2000,170(2-3):191-198
Mixture diffusion of two dyes (C.I. Direct Blue 15 (DB15) and C.I. Direct Yellow 12 (DY12)) with different affinity onto the substrate into cellulose membrane from the binary solution was studied at 55°C. Uptake curves and concentration–distance profiles were measured experimentally in the ratios (DB15:DY12) 1:0.5, 1:1 and 1:2. It was examined whether the diffusion of the dyes could be analyzed based on the parallel diffusion theory of surface and pore diffusion. It was revealed that the diffusion of DB15 with higher affinity could be analyzed based on the model in the ratios 1:0.5 and 1:1, although the theoretical value deviated slightly from the data in the concentration–distance profile in the ratio 1:1. On the other hand, the diffusion of DY12 with smaller affinity could not be described by the model, because the diffusivity of the dye changed during the adsorption process against the assumption of the model. 相似文献