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61.
Yoshihiro Osamura Shinichi Yamabe Kichisuke Nishimoto 《International journal of quantum chemistry》1980,18(2):457-462
The photoisomerization of imine compounds is studied in terms of an ab initio MO CI calculation. The potential curves of the syn-anti isomerization via the rotation and the inversion are examined for benzaldimine. It is suggested that the photoisomerization is initiated through the rotation around the C? N bond in both singlet and triplet states. The ease of the photoisomerization is found to be determined by both the conformation of phenyl ring in the ground state and the energy difference of vertically excited states between two isomers. 相似文献
62.
Sumio Kato Masataka Ogasawara Mikio Sugai Shinichi Nakata 《Catalysis Surveys from Asia》2004,8(1):27-34
Studies on the role of oxygen vacancy in structural change of nonstoichiometric perovskites and a property of oxygen-deficient perovskite-related K2NiF4 compounds are reviewed.The structural changes on which the authors focused are cation ordering and lattice distortion. The relationship between the distortion and oxygen vacancy was investigated by comparing the structures of Sr2(Sr1-xMx)TaO6-d (M = Ca2+ and Nd3+) solid solutions. It was found that distortion of a perovskite-type lattice decreased with an increasing amount of oxygen vacancies. In order to investigate the relationship between the cation ordering on octahedral sites and oxygen vacancy, structures of stoichiometric Sr2-xLaxCo1-yTa1+yO6 and oxygen-deficient Sr2-xLaxMg1-yTa1+yO6-d solid solutions were compared. The authors' work reveals that the cation ordering affects the amount of oxygen vacancies in addition to cation charge and size. 相似文献
63.
Moriya Y Hasegawa T Hayashi K Maruyama M Nakata S Ogawa N 《Analytical and bioanalytical chemistry》2003,376(3):374-378
Visible reflection spectra of diprotonated meso-tetraphenylporphyrin adsorbates spontaneously formed at a dodecane-aqueous sulfuric acid interface have been measured using a home-made device comprising a prism-cell and variable-angle optics. The tilt angle of the pyrrole ring plane was estimated to be 47 degrees from the interface normal by use of an experimentally evaluated molecular density (1.20x10(-10) mol cm(-2)) of the diprotonated molecule in a monolayer form at the liquid-liquid interface. Positive and negative bands have been observed in the p-polarized partial internal reflection (p-PIR) spectra, whose band locations correspond to those in p-polarized external reflection (p-ER) spectra. Nevertheless, the bands in the p-PIR exhibited reversed sign to those of p-ER spectra. These suggest that the surface selection rule of the p-PIR spectrometry has a reversal rule of p-ER and p-PIR can also be used for the analysis of molecular orientation. 相似文献
64.
Akira Matsumoto Yutaka Kukimoto Kazuhiro Aoki Masayoshi Oiwa 《Journal of polymer science. Part A, Polymer chemistry》1983,21(12):3493-3502
Seven glycol bis(allyl phthalate)s (GBAP) and four glycol bis(allyl succinate)s (GBASu) as reactive oligomers were prepared and their polymerization behaviors were investigated in detail in terms of cyclopolymerization and gelation as compared with diallyl dicarboxylates. Thus, the rates of polymerization of GBAPs were reduced compared to diallyl phthalate, being attributed to the steric effect on the intermolecular propagation of the uncyclized radical, whereas those of GBASus were enhanced as a consequence of intermolecular association by dipole–dipole interaction in polar GBASu monomers. Cyclization was enhanced in the following order: diallyl aliphatic dicarboxylates series < GBASu series < GBAP series. Gelation was discussed according to Gordon's theory; the actual gel-point conversions increased with an increase in the molecular weight of monomers, although the discrepancy between actual and theoretical gel-point conversion inversely tended to be decreased. The decreased delay in gelation with an increase of the molecular weight of monomers is ascribed to the reduction of excluded volume effects on crosslinking. 相似文献
65.
Lewis acid and substituent dependency on the regioselectivity of hydrosilylation of propiolate esters 1a-c with tris(trimethylsilyl)silane (2a) was found. The reaction of methyl and ethyl propiolate esters and 2a without Lewis acid and in the presence of EtAlCl2 and Et2AlCl gave beta-silicon-substituted Z-alkenes 3 selectively. On the other hand, reaction in the presence of AlCl3 in dichloromethane gave alpha-silicon-substituted alkenes 4. In the case of trifluoroethyl propiolate ester 1c, reaction with aluminum chloride-based Lewis acids gave alpha-silicon-substituted alkenes 4 exclusively. Two competitive mechanisms, free-radical and ionic, are proposed as the source of the complementary regioselectivity displayed in these reactions. A transition state of the radical-forming step was obtained computationally. The reaction of various reactive acetylene substrates and 2a without Lewis acid and without solvent at room temperature gave beta-silicon-substituted Z-alkenes 3 selectively. 相似文献
66.
67.
The specification property for solenoidal automorphisms is discussed; a solenoidal automorphism satisfies specification iff is expansive, and satisfies weak specification but not specification iff is ergodic and central spin. These are problems set up byK. Sigmund for homeomorphisms with specification. The proofs for toral case are given byD. Lind. For solenoidal case, a key ingredient in our proofs is splitting theorems on solenoidal groups with respect to described in § 2. Moreover, the following is proved: (i) If obeys specification then satisfies weak specification and is densely periodic. But the converse is not necessarily true. (ii) Every solenoidal automorphism with specification admits a Markov partition. (iii) Every ergodic solenoidal automorphism without specification does not admit Markov partitions. (iv) There exists an expansive homeomorphism with specification which has not Markov partitions. 相似文献
68.
Enami S Yamanaka T Hashimoto S Kawasaki M Tonokura K 《The journal of physical chemistry. A》2005,109(27):6066-6070
The reactions of Cl atoms with RI (R = n-C3H7, n-C4H9, cyclo-C6H11, C6H5, C6F5, and p-CH3C6H4) have been studied using cavity ring-down spectroscopy at a temperature range of 233-313 K and at 100 Torr total pressure of N2 diluent. Visible absorption spectra of the RI-Cl adducts were recorded at 440-520 nm at 263 K. The yields of the adducts were temperature-dependent. There was no discernible reaction of the adducts in the presence of 100 Torr of O2 at 263 K. Theoretical calculations were performed for C4H9I-Cl and C6H5I-Cl for quantitative explanation of the absorption spectra and the strength of the I-Cl bonds in the charge-transfer complexes. Evidence for the adduct formation following the reaction of Cl with C6H5Br was sought but not found at 440 and 520 nm. 相似文献
69.
To evaluate the prognosis in 57 patients with old myocardial infarctions, 201Tl myocardial scintigraphy and 99mTc-HSA gated blood pool scan had been done as a 5-year follow up study. We subdivided into two groups; group I (over 60 years) and group II (under 60 years). Cardiac index (CI) and right ventricular ejection fraction (RVEF) did not change significantly, however left ventricular ejection fraction (LVEF) changed significantly (p less than 0.05). Correlationship between CAG score and delta LVEF by handgrip exercise test was y = -1.34 x +3.61 (n = 44, r = -0.400, p less than 0.01). Otherwise, Tl defect ratio between first and final examination did not show the significant change in two groups. In conclusion, nuclear examination (cardiac function and myocardial blood flow) is significant to evaluate the prognosis in patients with myocardial infarction. 相似文献
70.
Tachi Y Aita K Teramae S Tani F Naruta Y Fukuzumi S Itoh S 《Inorganic chemistry》2004,43(15):4558-4560
A dicopper(I) complex supported by a novel asymmetric pentapyridine dinucleating ligand, consisting of tetradentate and tridentate metal-binding sites, has been synthesized and characterized. The dicopper(I) complex reacted with molecular oxygen at a low temperature to give an unprecedented mu-peroxo dicopper(II) complex presumably having a mu-eta1:eta2 binding mode, the spectroscopic features and the reactivity of which have been explored in detail. 相似文献