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991.
Selective growth of WO2, W and WO3−x crystals from amorphous WO3 film by vacuum heating at 400–900°C was clarified. The grown WO3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO2 crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO2 crystal consumes WO3 microcrystallites with various orientations. The growth speed of the WO2 depended on WO3 microcrystallites orientation. The origin of the wavy growth front of WO2 was due to an orientation dependence of the WO3 microcrystallites. 相似文献
992.
Dr. Hajime Yamamoto Takashi Imai Dr. Yuki Sakai Prof. Dr. Masaki Azuma 《Angewandte Chemie (International ed. in English)》2018,57(27):8170-8173
Colossal negative thermal expansion (NTE) with a volume contraction of about 8 %, the largest value reported so far for NTE materials, was observed in an electron‐doped giant tetragonal perovskite compound Pb1?xBixVO3 (x=0.2 and 0.3). A polar tetragonal (P4mm) to non‐polar cubic structural transition took place upon heating. The coefficient of thermal expansion (CTE) and the working temperature could be tuned by changing the Bi content, and La substitution decreased the transition temperature to room temperature. Pb0.76La0.04Bi0.20VO3 exhibited a unit cell volume contraction of 6.7 % from 200 K to 420 K. Interestingly, further gigantic NTE of about 8.5 % was observed in a dilametric measurement of a Pb0.76La0.04Bi0.20VO3 polycrystalline sample. The pronounced NTE in the sintered body should be attributed to an anisotropic lattice parameter change. 相似文献
993.
Ryo Mizunuma Teruhiko Tanaka Yoshihiro Nakamura Yuki Kamijima Yoshio Kabe 《Tetrahedron》2018,74(5):544-548
Recent reports describe the different products resulting from the reaction of C60 with benzyne generated from anthranilic acid derivatives and isoamyl nitrate in the presence and absence of triethylamine. Reinvestigation here via 1H, 13C, HMBC NMR and Mass spectroscopy elucidates that these products are the [6,6] closed C60-fused δ lactones, and not the [5,6] open fulleroids which would result from benzyne addition. Furthermore, theoretical calculations show that the open isomer [5,6] benzyne addition is less stable than the [5,6] closed isomer as an isolable product. 相似文献
994.
Koichi Hatada Susumu Kokan Toshikazu Niinomi Koh Miyaji Heimei Yuki 《Journal of polymer science. Part A, Polymer chemistry》1975,13(9):2117-2124
The polymerization of methyl α-ethylacrylate was carried out in toluene by n-BuLi at various temperatures. The yield of the polymer decreased with increase in the polymerization temperature and at 30°C and above no polymer was obtained, indicating that the ceiling temperature of this monomer lay between 0 and 30°C. The isotacticity increased with an increase in the polymerization temperature and at 0°C a highly isotactic polymer was obtained. The fractionation of the polymer obtained at ?78°C showed that the polymer was a mixture of isotactic and syndiotactic ones. Upon the addition of a small amount of methanol or water in the polymerization mixture the isotacticity of the polymer increased while the yield decreased. Syndiotactic polymer was obtained in the polymerization by n-BuLi in tetrahydrofuran as well as by diisobutyl aluminum diphenylamide in toluene. 相似文献
995.
Yoshio Okamoto Eiji Yashima Koichi Hatada Heimei Yuki Hiroyuki Kageyama Kunio Miki Nobutami Kasai 《Journal of polymer science. Part A, Polymer chemistry》1984,22(8):1831-1837
Asymmetric selective (or stereoelective) polymerization of racemic 1,2-diphenylethyl methacrylate (DPEMA) with ethylmagnesium bromide (EtMgBr)-(?)-sparteine catalyst was studied in toluene at ?78°C. In the polymerization (S) enantiomer was consumed preferentially and the enantiomeric excess of initially polymerized (S) enantiomer was consumed preferentially and the enantiomeric excess of initially polymerized DPEMA was greater than 90%. Optically pure (R) monomer was recovered at about 70% polymer yield. Poly(DPEMA) obtained with EtMgBr-(?)-sparteine complex was highly isotactic. It was found in the polymerization of optically active DPEMA that optical rotation of poly(DPEMA) was dependent on the tacticity and that isotactic and syndiotactic poly(DPEMA)s showed opposite optical rotations. Circular dichroism spectra of the optically active polymers were measured. 相似文献
996.
Blue sepal-color of Hydrangea macrophylla might be due to a supramolecular metal-complex pigment consisting of delphinidin 3-glucoside (1), co-pigments (5-O-caffeoylquinic acid (2), and/or 5-O-p-coumaroylquinic acid (3)) and Al3+ in an aqueous solution around pH 4.0. To clarify the mechanism of blue sepal-color development of hydrangea, we tried to reproduce the blue color in vitro by mixing 1 with designed synthetic co-pigments in the presence of Al3+ at pH 4.0. We at first succeeded in clarifying the essential functional structure in the co-pigment that could form the stable blue solution. Here, we present the structure of the blue pigment caused by an Al-complex coordinating of 1 at ortho-dihydroxyl groups of the B-ring, 1-hydroxy, 1-carboxylic acid, and the carbonyl residue in the ester at 5-position of 2 and/or 3. The hydrophobic interaction between the aromatic acyl residue at 5-position and the nucleus of 1 may also contribute to stabilize the complex. 相似文献
997.
N,N,N′,N′-Tetra-n-butyl-BINOL-3,3′-dicarboxamide 5d was found to promote phenyl transfer from ethylphenylzinc to both aromatic and aliphatic aldehydes with high enantioselectivity up to 96% ee in tert-butyl methyl ether. 相似文献
998.
Origin of enhancement in open-circuit voltage by adding ZnO to nanocrystalline SnO2 in dye-sensitized solar cells 总被引:1,自引:0,他引:1
Niinobe D Makari Y Kitamura T Wada Y Yanagida S 《The journal of physical chemistry. B》2005,109(38):17892-17900
SnO2 + ZnO working electrodes for dye-sensitized solar cells were made by mixing a nanocrystalline SnO2 colloidal dispersion with ZnO or Zn(CH3COO)2. Addition of ZnO or Zn(CH3COO)2 enhanced the open-circuit voltage (V(oc)) of the cells with respect to cells containing only SnO2. Dependence of the electron lifetime in the electrodes on short-circuit photocurrent density (J(sc)) gave evidence against the assumption that the suppression of back electron transfer to the electrolyte is the origin for the V(oc) enhancement by addition of Zn. V(oc) dependence on temperatures indicated a decrease in the combined capacitance of the mixed electrode. The slope of the V(oc) dependence versus the logarithm of J(sc) indicated that the contribution of unpinning of the band to the enhancement of V(oc) could be neglected. From the cyclic voltammograms of the electrodes, the combined capacitance of the mixed electrode was 1 order of magnitude smaller than that of SnO2. The decrease in the combined capacitance in the mixed electrode could be explained by the decrease in the chemical capacitance of SnO2, thus the shift of the conduction band position toward the vacuum level. X-ray photoelectron spectra of Sn 3d(5/2) peaks showed a shift toward lower binding energy with an increasing amount of added Zn. This was attributed to an increase in the surface potential toward the negative direction, which might have resulted from a dipole moment formed by Zn on the surface of SnO2. 相似文献
999.
In order to understand the relation between the electronic structure of neurotransmitters and the brain, a model of the brain based on absolute hardness (eta) and absolute electronegativity (chi) is described. It was found that the coordinate r(chi, eta) of electronic structures of neurotransmitters obtained using the parameters eta and chi can be graphically classified into three groups: catecholamine type (group I), gamma-aminobutanoic acid (GABA) type (group II), and acetylcholine (ACh) type (group III) in the eta-chi diagram. The results suggest that the brainstem and neocortex in the brain are chemically soft and hard, respectively, because they show that the myelinated nerve is chemically soft and the unmyelinated nerve is chemically hard. If one calculates the r(chi, eta) to understand which group a drug belongs to, one can predict the target receptors of the drug from the eta-chi diagram. Using eta-chi maps, one is then able to design medications like antidepressants, tranquilizers, and ACh agonists. 相似文献
1000.
Smoothing by Fourier transform of data obtained with a laboratory-built rapid injection device is shown to be useful for peak-height measurements of the chemiluminescence rapidly produced by luminol catalyzed by hemin (t = 0.28 s); the observation time was 0.25 s. An algorithm prepared for the smoothing of data comprising a single peak is three times faster than the corresponding fast Fourier transform program and permits real-time processing. The principles of the rapid measurement are also applied to slower luminol chemiluminescence continuing for >40 s; the measurement needed just 0.5 s. 相似文献