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81.
Density functional theory calculations of the title reaction, P(OCH?)? + (H?O)(n) in CH?CN, were conducted, where n is the number of water molecules. Two routes, the routes suggested by (A) Aksnes and (B) Arbuzov, were traced with various n values. Both routes consist of two transition states (TSs) and one intermediate. Route B was found to be more likely than route A. In the former, the activation free energy (ΔG(?)) of n = 3 is slightly smaller than that of n = 2. The n = 3 TS geometry is composed of a nucleophile H?O, a proton donor H?O, and an auxiliary one. Indeed, the geometry appears to be plausible for ready proton relays along hydrogen bonds, but it is inconsistent with the observed third-order rate constant. Catalytic water molecules were added to the n = 2 and 3 bond-interchange circuits. Then route B with n = 2 + 2 was found to be best. By n = 2 + 10 and n = 3 + 12 models, the n = 2 based route B was confirmed to be likely. 相似文献
82.
83.
Itsuo Mori Takako Matsuo Yoshikazu Fujita Minako Toyoda Kenichi Ichitani Noriko Inoue 《Fresenius' Journal of Analytical Chemistry》1994,348(5-6):346-349
Summary A spectrofluorophotometric determination of thallium(III) is proposed. It is based on the enhancement of the fluorescence reaction of 3,4,5,6-tetrachlorofluorescein (TCF) with Pyrogallol Red (PR) by thallium(III) in the presence of Swanol (AM 301, lauryldimethyl aminoacetic acid betain) as an amphoteric surfactant. The method was found to be suitable for the determination of thallium(III) down to 4.0 g in 10.0 ml by measuring the difference in the relative fluorescence intensities of a TCF/PR/thallium(III) solution and a TCF/PR solution. The recovery test in artificial urine was satisfactory (96±2%). 相似文献
84.
Noriko Ohkami Akiko Motoyama Tamië Yamaguchi Haruo Hosoya Ivan Gutman 《Tetrahedron》1981,37(6):1113-1122
The mathematical structure of a set of the Kekulé patterns for a polycyclic aromatic hydrocarbon has been analysed graph-theoretically. By defining the proper and improper sextets, sextet pattern, Clar transformation, and sextet rotation, one can prove the important property of the sextet polynomial BG(x) as BG(1) = K(G), where K(G) is the number of the Kekulé patterns for thin polyhex graph G. For fat polyhex graphs such as coronene the above relation is found to be also valid by introducing the concept of a super sextet. All the Kekule patterns for a given G are shown to form a hierarchical tree structure by the sextet rotation. The theory developed in this paper gives a mathematical basis and interpretation for the concept of the Clar's aromatic sextet. 相似文献
85.
Dehydrotripeptides, X-CH(Ri)-ΔPhe-CH(Rk)COOMe (: X = tBOC-NH,CBZ-NH, CF3CONH and N3), were employed for the asymmetric hydrogenation catalyzed by chiral rhodium complexes and it was found that tBOC- brought about by far the best results. Stereoselective dideuteration of a tBOC- was successfully performed. 相似文献
86.
Formation of ternary ion associates using diprotic acid dyes and its application to determination of cationic surfactants 总被引:1,自引:0,他引:1
A sensitive and selective method is described for the determination of cationic surfactants, such as benzethonium, benzalkonium, cetylpyridinium and trimethylstearylammonium, based on the formation and extraction of ternary ion associates with an acid dye (bromophenol blue or bromochlorophenol blue) and quinidine. Quinidine reacts with divalent anionic dyestuffs to form a bulky 11 complex anion, which is extractable into 1,2-dichloroethane as ternary ion associates with cationic surfactants in nearly neutral media. The ternary ion associate gives a blue product. Linearity of the calibration curve is improved and the extractability of the cationic surfactants is enhanced in the presence of quinidine. In addition, many other amines do not interfere with the determination. The blue ion associates can be used for the selective and sensitive spectrophotometric determination of cationic surfactants. 相似文献
87.
INDUCTION OF UMUC+ GENE EXPRESSION IN Escherichia coli IRRADIATED BY NEAR ULTRAVIOLET LIGHT 总被引:1,自引:0,他引:1
Noriko Sato Takeo Ohnishi Keizo Tano Kazuo Yamamoto Kehchi Nozu 《Photochemistry and photobiology》1985,42(2):135-139
Abstract— The induction of umu + gene expression caused by irradiation with near ultraviolet light (BLB; black light blue) was studied in Escherichia coli K-12 strains with special reference to the effects of SOS repair deficiencies. The umuC + gene expression was measured as the enzymic activity of (J-galactosidase which is regulated by the promoter of the umuC + operon carried in a plasmid DNA carrying a promoter of umuC* operon, a umuD + gene and a umuC +- lacZ + gene fusion. A high induction of the umuC + gene expression was observed in the uvrA cells in the case of BLB or UV irradiation as compared with the parental wild-type cells. Caffeine inhibited the induction of the umuC* gene expression due to BLB or UV irradiation in both strains. There was very little induction in lexA and recA mutants. In contrast with UV irradiation, there was no killing of cells by BLB irradiation in any strain (wild, uvrA, lexA and recA). Possible implications of the present experimental results were discussed. 相似文献
88.
The first total synthesis of kazusamycin A, a potent antitumor compound from an actinomycete, has been achieved, and its absolute structure was determined. Paterson's stereoselective aldol reaction was successfully applied to construct the contiguous chiral centers by using an originally designed optically active 2-acyl-1,3-propanediol derivative. 相似文献
89.
Ando K Tsuji E Ando Y Kuwata N Kunitomo J Yamashita M Ohta S Kohno S Ohishi Y 《Organic & biomolecular chemistry》2004,2(4):625-635
Novel 3-acetoacetylaminobenzo[b]furan derivatives having a modified triene system at the 3-position were synthesized starting with 3-aminobenzo[b]furans. The enol isomers, 3-[(3-hydroxybut-2-enonyl)amino]benzo[b]furans (), of the 3-acetoacetylaminobenzo[b]furans were obtained as stable isomers owing to formation of a hydrogen bonding between the enol hydroxyl group and the amidocarbonyl group. The planarity of the C-2 substituent through the C-3 side chain suggested the existence of a modified conjugational triene system in the enol compound. Cysteinyl leukotriene 1 and 2 receptor antagonistic activities for these compounds were evaluated. 2-(4-Cyanobenzoyl or ethoxycarbonyl)-3-[(2-cyano-3-hydroxybut-2-enonyl)amino]benzo[b]furans (, ) were moderately active. 相似文献
90.
Thiam MM Kondo T Horimoto N Kato HS Kawai M 《The journal of physical chemistry. B》2005,109(33):16024-16029
The initial growth of a water (D2O) layer on (1 x 1)-oxygen-covered Ru(0001) has been studied in comparison with that on bare Ru(0001) by means of temperature-programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS). Although water molecules adsorbed on both bare and (1 x 1)-oxygen-covered Ru(0001) commonly tend to form hydrogen bonds with each other when mobility occurs upon heating, the TPD and IRAS measurements for the two surfaces exhibit distinct differences. On (1 x 1)-oxygen-covered Ru(0001), most of the D2O molecules were desorbed with a peak at 160 K, even at submonolayer coverage, as condensed water desorption. The vibration spectra of adsorbed D2O also showed broad peaks such as a condensed water phase, from the beginning of low coverage. For submonolayer coverage, in addition, we found a characteristic O-D stretching mode at around 2650 cm(-1), which is never clearly observed for D2O on bare Ru(0001). Thus, we propose a distinctive water adsorption structure on (1 x 1)-oxygen-covered Ru(0001) and discuss its influence on water layer growth in comparison with the case of D2O on bare Ru(0001). 相似文献