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51.
The additive Pummerer reaction of several heteroaromatic sulfilimines has been investigated. The overall process involves the reaction of the sulfilimine with TFAA to produce a transient N-tosyl-N-trifluoroacetyl sulfonium ion. Nucleophilic attack at the adjacent vinyl carbon results in the ejection of the sulfonamide group and the resulting thionium ion loses a proton to give the observed product. 相似文献
52.
Moribe K Tsuchiya M Tozuka Y Yamaguchi K Oguchi T Yamamoto K 《Chemical & pharmaceutical bulletin》2004,52(5):524-529
We prepared and characterized a grinding-induced equimolar complex of thiourea with ethenzamide. When thiourea and ethenzamide were co-ground at a molar ratio of 3 : 1, new powder X-ray diffraction (PXRD) peaks were observed in addition to PXRD peaks of thiourea crystals. The optimum stoichiometry of the new structure was confirmed as 1 : 1 mol/mol. Effect of grinding time on the thiourea-ethenzamide equimolar complex formation was investigated by using PXRD, differential scanning calorimetry and Fourier transform infrared spectroscopy. The equimolar crystal structure was confirmed by X-ray diffraction measurements of the single crystal which was recrystallized from ethanol. It was found that the intermolecular hydrogen bond formations between thiourea and ethenzamide molecules contributed to the equimolar complex formation. The complex formation was not observed in the cases where benzamide, salicylamide or 3-ethoxybenzamide was co-ground with thiourea. 2-Alcoxyl benzamide structures should be required for the grinding-induced equimolar complex formation with thiourea. 相似文献
53.
Takegawa Y Deguchi K Ito S Yoshioka S Nakagawa H Nishimura S 《Rapid communications in mass spectrometry : RCM》2005,19(7):937-946
To investigate the possibility of structural assignment based on negative-ion MS2 spectral matching, three isomeric pairs of 2-aminopyridine (PA)-derivatized non-fucosylated, fucosylated, and sialylated oligosaccharides (complex type N-glycans) were analyzed using high-performance liquid chromatography/ion trap mass spectrometry (HPLC/ITMS) with a sonic-spray ionization (SSI) source. In the SSI negative-ion mode the deprotonated molecule [M-2H]2- becomes prominent. Negative-ion MS2 spectra derived from such ions contain many fragment types (B and Y, C and Z, A, and D) and therefore are more informative than the positive-ion MS2 spectra derived from [M+H+Na]2+ ions, which usually consist mainly of B and Y fragment ions. In particular the internal ions (D- and E-type ions) provided useful information about the alpha1-6 branching patterns and the bisecting GlcNAc residue. Spectral matching based on the correlation coefficients between negative-ion MS2 spectra was performed in a manner similar to the positive-ion MS2 spectral matching previously reported. It was demonstrated that negative-ion MS2 spectral matching is as useful and applicable to the structural assignment of relatively large non-fucosylated, fucosylated, and sialylated PA-oligosaccharide isomers as its positive-ion counterpart. 相似文献
54.
T. Tsuchiya T. Sei Y. Watanabe M. Mori T. Kineri 《Journal of Sol-Gel Science and Technology》1997,8(1-3):685-688
Gold-dispersed BaTiO3, PGO and PLT thin films, which will be used for third-order nonlinear optical devices, were prepared by sol-gel process with
spin-coating using HAuCl44H2O, Ba(CH3COO)2, Ti[O(CH2)3CH3]4, Pb(CH3COO)23H2O, Ge[O-n-C4H9]4, La(CH3COO)31.5 H2O as starting materials. The thin films were heat-treated in air at temperatures ranging from 400 to 800 for 1 h. The nonlinear
optical property of these thin films was measured by the degenerate four-wave mixing (DFWM) method using a frequency-doubled
Nd: YAG laser with 20 ps pulse duration. Third-order nonlinear susceptibility χ(3) of gold-dispersed BaTiO3, PGO and PLT thin films with 5 vol% of gold were 1.410−6 esu, 3.510−7 esu respectively. The large χ(3) may be ascribed to the high dielectric constant of the films. 相似文献
55.
Intercrystalline migration and a migration-assisted chemical reaction of adsorbed aromatic species between zeolite particles in physical contact were visualized by fluorescence microscopy coupled with a particle manipulation technique. The luminescence color characteristics of particular zeolite particles originating from the specific photochemistry of adsorbed species was exploited to follow the migration of the molecules. Two examples are shown that are relevant to the visualization of the time-dependent migration process: A one guest-two sets of zeolite crystals system: chrysene (Chry)-loaded zeolite Na+ -X (the sodium form of zeolite X) crystals were placed in contact with unloaded Tl+ -X (thallium-exchanged X) crystals and allowed to stand at room temperature. Initially, the blue fluorescence of Chry was detected only from the Na+ -X particles, but later, the development of green phosphorescence emission was discernible from the Tl+ -X which suggests that Chry migrated from the Na+ -X to the Tl+ -X crystals. A two guest-species systems: Electron-donating Chry-loaded Na+ -X crystals were placed in contact with electron-accepting 1,2,4,5-tetracyanobenzene (TCNB)-loaded Na+ -X or Na+ -Y crystals. With time, the former system (Chry/Na+ -X and TCNB/Na+ -X) gave rise to the emission of Chry-TCNB charge-transfer complexes resulting mainly from the migration of Chry while the latter system (Chry/Na+ -X and TCNB/Na+ -Y) afforded the same emission resulting largely from the migration of TCNB. The present investigation reveals that there is a certain direction for guest migration depending on the zeolite host and the nature of host-guest or guest-guest interaction. 相似文献
56.
Nonenzymatically glycated human serum albumin was incubated with ferric ion at 37 degrees C in 0.2 M phosphate buffer, pH 7.4, up to 30 days. In the incubation mixture, amino acids, tyrosine and phenylalanine, were detected, suggesting site specific cleavage of glycated human serum albumin. 相似文献
57.
Imai M Tanaka M Tanaka K Yamamoto Y Imai-Ogata N Shimowatari M Nagumo S Kawahara N Suemune H 《The Journal of organic chemistry》2004,69(4):1144-1150
Intermolecular hydroacylation between salicylaldehydes 1, 26-40 and 1,4-penta- or 1,5-hexadienes 4-13 by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso- and normal-hydroacylated products 14-25, 41-55, and 57-60. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex plays a crucial role. The ratio of iso- and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the deuterium-labeling salicylaldehyde experiments. 相似文献
58.
Keishi Nishio Yuichi Watanabe Toshio Tsuchiya 《Journal of Sol-Gel Science and Technology》2003,26(1-3):245-250
In this study, we prepared Sr
x
Ba1 – x
Nb2O6 (x = 0.3, 0.5 and 0.7) thin film on 0.75 wt% La doped SrTiO3 (100) and (110) single crystal substrates. A homogeneous coating solution was prepared with Sr and Ba acetates and Nb(OEt)5 as raw materials, and acetic acid and diethlene glycol monomethyl ether as solvents. The substrates were coated with the solution by spin coating method. As-coated thin films were heated from 973 to 1273 K in air. The grains of the thin film on La doped SrTiO3 (100) were pillar shaped and arranged in right angle to each other. On the other hand, the grains of these thin films on La doped SrTiO3 were pillar shape and arranged in one direction. The crystallographic relationship of the thin film between Sr
x
Ba1 – x
Nb2O6 and substrate that the 130 and 310 direction of the thin film on the substrate were oriented with c-axis in parallel to the substrate surface. On the other hand, (hk0) phase diffractions of Sr
x
Ba1 – x
Nb2O6 thin film on the substrate (110) were investigated in the XRD theta-2theta measurement. It is expected that the Sr
x
Ba1 – x
Nb2O6 (x = 0.3, 0.5 and 0.7) were highly oriented or epitaxial growing on La doped SrTiO3 (110) single crystal substrate. 相似文献
59.
S. Sawamura M. Tsuchiya T. Ishigami Y. Taniguchi K. Suzuki 《Journal of solution chemistry》1993,22(8):727-732
Solubility of naphthalene in water was measured at 25°C and pressures up to 200 MPa. The solubility decreased with increasing pressure. From the pressure coefficient of the solubility, the volume change V accompanying the dissolution was estimated as 13.8±0.4 cm
3
-mol
–1
. Further we estimated the volume change V
CH
accompanying hydrophobic hydration as –0.1±0.6 cm
3
-mol
–1
using the V value, the molar volume of crystalline naphthalene, and the partial molar volume of naphthalene in n-heptane. This V
CH
is much larger (i.e., less negative) than that for hydrophobic hydration of alkyl-chain compounds and suggests that the hydration structure of naphthalene differs from that of alkyl-chain compounds. 相似文献
60.
Shimizu K Suzuki H Hayashi E Kodama T Tsuchiya Y Hagiwara H Kitayama Y 《Chemical communications (Cambridge, England)》2002,(10):1068-1069
Direct 1,4-conjugate addition of naked aldehydes to vinylketones is catalysed effectively by N-methyl-3-aminopropylated FSM-16 mesoporous silica, which can be regarded as a novel heterogeneous catalysis for a practical C-C bond formation reaction. 相似文献