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51.
Emission Mössbauer spectra of mixedvalence trinuclear complexes,57Co-labelled [CoFe2O(CH3CO2)6(H2O)3] and [CoFe2O(CH3CO2)6 (py)3]py were compared with that of [CoCr2O(CH3CO2)6 (py)3]py. It was found that the57Fe atoms produced in57Co-labelled [CoFe2O(CH3CO2)6(H2O)3] and [CoFe2O(CH3CO2)6 (py)3]py showed a temperature-dependent mixed-valence state as observed in the absorption Mössbauer spectra of [Fe3O(CH3CO2)6 (H2O)3] and [Fe3O(CH3CO2)6 (py)3]py, respectively, while57Co-labelled [CoCr2O(CH3CO2)6 (py)3]py showed a temperature-independent divalent iron/II/ state. The results indicate that the decayed atoms keep their position at the sites of original57Co atoms and that the valence electrons are transferred through the intramolcular bondings. 相似文献
52.
Kazumi Ohya Hiroaki Kitaoka Yasuhiko Yotsui Mitsuji Sano 《Journal of mass spectrometry : JMS》1983,18(4):139-146
The mechanism of the pyrolysis reaction of carpronium chloride [(CH3)3N+? (CH2)3? COOCH3CI?] leading to γ-butyrolactone and tetramethylammonium chloride was investigated by means of thermal analysis, pyrolysis gas chromatography mass spectrometry and field desorption mass spectrometry, using deuterium labelling. The results indicated that carpronium chloride pyrolysed to yield equimolar amounts of γ-butyrolactone and tetramethylammonium chloride, methyl transfer occurred between N and O during the pyrolysis process. The mechanism is discussed on the basis of the experimental results, and with the aid of the theoretical results calculated by the CNDO/2 method. The mechanism presented is as follows. γ-Butyrolactone is formed by the intramolecular migration of the π-orbital of C?O to the carbon adjacent to [(CH3)3N]+ via a 5-membered ring transition state, accompanied by a bimolecular reaction between [(CH3)3N]+ and the CH3 of O? CH3, resulting in the formation of tetramethylammonium chloride in an amount equimolar with γ-butyrolactone. 相似文献
53.
H. Sano 《Journal of Radioanalytical and Nuclear Chemistry》1977,36(1):105-111
Absorption Mössbauer spectra of high-spin57Fe(acac)3 incorporated in diamagnetic Co(acac)3 and in paramagnetic Mn(acac)3 and of the γ-ray irradiated (57Fe, Co) (acac)3 and (57Fe, Mn) (acac)3 were compared with emission spectra of57Co-labelled Co(acac)3. Magnetic hfs is found in the spectra of (57Fe, Co) (acac)3 at 78 to 195 K, whereas such hfs is observed neither for the spectrum of57Co-labelled Co(acac)3 nor for that of γ-ray irradiated (57Fe, Co) (acac)3). The absence of magnetic hfs in the spectrum of diamagnetic57Co-labelled cobalt(III) compounds was ascribed to the spin-spin interaction due to the radicals produced in the vicinity of the decayed atom. 相似文献
54.
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56.
Hirohito Ikeda Yukiko Sano Tomonori Matsubara Mitsunobu Kawahara Miho Yukawa Masao Fujisawa Eiji Yukawa Hatsumi Aki 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1135-1138
Propericiazine (PCZ) is an antipsychotic agent used for the treatment and the prevention of relapse of schizophrenia. We found that when an oral solution containing PCZ was mixed with a green tea drink, the residual content of PCZ was reduced by forming an insoluble complex between PCZ and tea polyphenol. In this study, the mechanism underlying the incompatibility of PCZ with green tea polyphenol (GTP) in the solution was clarified by isothermal titration microcalorimetry (ITC). Both solutions of 27.4 mM PCZ and 2.2 mM (?)-epigallocatechin gallate (EGCg), which is a main ingredient of GTP, were mixed and then PCZ in the filtrate was reduced to approximately 60 %. According to measurement at 298 K by ITC, PCZ formed an insoluble complex with EGCg at an associate constant (K) of 4.75 × 102 M?1 exothermically, ΔH = ?40.0 kJ mol?1. When (?)-epicatechin gallate (ECg) was used as the GTP, PCZ interacted with ECg with K and ΔH values of 3.74 × 102 M?1 and ?22.1 kJ mol?1, respectively. On the other hand, little heat of the reaction between PCZ and (?)-epigallocatechin or (?)-epicatechin was observed. The results indicated that the main reason for this incompatibility was the formation of an insoluble complex by PCZ and a gallate-type GTP such as EGCg and ECg in the aqueous solution. 相似文献
57.
Takehiro Arnano Kensei Yoshikawa Tatsuhiko Sano Yutaka Ohuchi Manzo Shiono Michihiro Ishiguro 《合成通讯》2013,43(5):499-507
Various types of α-arylpropionic acid esters were effectively obtained by the coupling reaction of aryl Grignard reagents and α-bromopropionic acid esters in the presence of nickel catalysts. α-Arylpropionitriles, precursors of α-arylpropionic acids, were also synthesized by the reaction of α-methanesulfonyloxypropionitrile and arylcopper reagents prepared from equimolar amount of arylmagnesium halides and copper(I) bromide. 相似文献
58.
Takuya Adachi Yasuhisa Yamamura Mafumi Hishida Mao Ueda Shunji Ito 《Liquid crystals》2013,40(11):1340-1344
Molecular dynamics in the soft crystal, E phase of 6-octyl-2-phenylazulene was studied by X-ray diffraction, and dielectric and Fourier transform infrared spectroscopies. Clear dielectric dispersion is observed due to the head-to-tail disordering in a kHz range around 400 K. The CH stretching frequencies exhibit more pronounced shifts at the phase transition point from the high-temperature ordered crystal to the E phase than that at the melting from the E phase to the isotropic liquid. The results are discussed in comparison with a typical E series, 4-n-alkyl-4′-isothiocyanatobiphenyl (n being the number of carbon atoms in the alkyl group). 相似文献
59.
Tailoring D‐Amino Acid Oxidase from the Pig Kidney to R‐Stereoselective Amine Oxidase and its Use in the Deracemization of α‐Methylbenzylamine
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Kazuyuki Yasukawa Dr. Shogo Nakano Prof. Dr. Yasuhisa Asano 《Angewandte Chemie (International ed. in English)》2014,53(17):4428-4431
The deracemization of racemic amines to yield enantioenriched amines using S‐stereoselective amine oxidases (AOx) has recently been attracting attention. However, R‐stereoselective AOx that are suitable for deracemization have not yet been identified. An R‐stereoselective AOx was now evolved from porcine kidney D ‐amino acid oxidase (pkDAO) and subsequently use for the deracemization of racemic amines. The engineered pkDAO, which was obtained by directed evolution, displayed a markedly changed substrate specificity towards R amines. The mutant enzyme exhibited a high preference towards the substrate α‐methylbenzylamine and was used to synthesize the S amine through deracemization. The findings of this study indicate that further investigations on the structure–activity relationship of AOx are warranted and also provide a new method for biotransformations in organic synthesis. 相似文献
60.
Organic single crystals of 2-methyl-4-nitroaniline (MNA) up to 3 mm in diameter and 20 mm in length have been successfully grown by the Bridgman method using the purified reagent by sublimation. The crystals are transparent and yellow in colour by controlling the growth conditions. In the spectra of yellow coloured crystals no absorption peak is observed until about 450 nm. Also, the crystals of MNA have the two cleavage planes (311 ) and (010). 相似文献