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排序方式: 共有597条查询结果,搜索用时 15 毫秒
101.
Yamada Y Maeda K Ohkubo K Karlin KD Fukuzumi S 《Physical chemistry chemical physics : PCCP》2012,14(27):9654-9659
The catalytic durability of an organic photocatalyst, 9-mesityl-10-methyl acridinium ion (Acr(+)-Mes), has been dramatically improved by the addition of [{tris(2-pyridylmethyl)amine}Cu(II)](ClO(4))(2) ([(tmpa)Cu(II)](2+)) in the photocatalytic oxygenation of p-xylene by molecular oxygen in acetonitrile. Such an improvement is not observed by the addition of Cu(ClO(4))(2) in the absence of organic ligands. The addition of [(tmpa)Cu](2+) in the reaction solution resulted in more than an 11 times higher turnover number (TON) compared with the TON obtained without [(tmpa)Cu(II)](2+). In the photocatalytic oxygenation, a stoichiometric amount of H(2)O(2) formation was observed in the absence of [(tmpa)Cu(II)](2+), however, much less H(2)O(2) formation was observed in the presence of [(tmpa)Cu(II)](2+). The photocatalytic mechanism was investigated by laser flash photolysis measurements in order to detect intermediates. The reaction of O(2)˙(-) with [(tmpa)Cu(II)](2+) monitored by UV-vis spectroscopy in propionitrile at 203 K suggested formation of [{(tmpa)Cu(II)}(2)O(2)](2+), a transformation which is crucial for the overall 4-electron reduction of molecular O(2) to water, and a key in the observed improvement in the catalytic durability of Acr(+)-Mes. 相似文献
103.
The local structure of phosphorus and silicon in the molten CaO–SiO2–PO2.5 slag system was investigated by magic angle spinning nuclear magnetic resonance (MAS-NMR). The 31P MAS-NMR spectra revealed that phosphorus was present primarily as the monophosphate complex ion PO43?, with a small amount of diphosphate ion also present. Their relative ratio to total phosphorus was independent of the phosphate concentration of the sample. In the case of the 29Si MAS-NMR, the mean number of the non-bridging oxygen atoms associated with tetrahedrally coordinated silicon decreased as the phosphate concentration increased at a fixed CaO/SiO2 ratio. This indicates that the nonbridging oxygen atoms around the silicon were replaced by bridging oxygen atoms around the phosphorus as the phosphate concentration in the samples increased.To elucidate the basicity dependence of the structure of slag, the relationship between the structure and optical basicity was also investigated. The relative ratio of Qn (Qn means the silicon atoms tetrahedrally bonded with “n” number of bridging oxygen atoms) strongly depends on the optical basicity. These optical basicity dependencies of the structures of phosphorus and silicon can be explained clearly by the basicity equalization concept (Duffy and Ingram, 1976) [12]. 相似文献
104.
K Nagai M Arito Y Takakuwa S Ooka T Sato MS Kurokawa K Okamoto T Uchida N Suematsu T Kato 《Electrophoresis》2012,33(13):2028-2035
Anti-ribonucleoprotein (anti-RNP) antibodies are one of the representative autoantibodies detectable in patients with systemic lupus erythematosus (SLE) and mixed connective tissue disease (MCTD). Generally, posttranslational modifications (PTMs) on autoantigens are proposed to be involved in the production of autoantibodies. In this study, we tried to detect the alteration in PTMs on a U1 small nuclear RNP 68k subunit (U1-68k), a major antigen of anti-RNP antibodies. Peripheral blood mononuclear cells (PBMCs) were obtained from patients with MCTD, SLE, and rheumatoid arthritis (RA), and from healthy donors. U1-68ks in the PBMCs were detected by 2D Western blot (WB), where extracted nuclear proteins were separated by 2DE, followed by the detection of U1-68k using WB. More than 20 PTM isoforms were detected with different molecular weights of 65.0 , 66.5, and 68.0kDa, and different pIs between 6.0 and 8.5. Importantly, the relative intensity of the spot with 66.5 kDa and pI 7.5 was significantly increased in the MCTD and SLE groups compared to the RA and healthy groups. Further, this U1-68k isoform, in particular, in its RS domain, was found to have significantly decreased phosphorylation compared to the other isoforms. The PTM alternation may be one of the steps to generate the anti-RNP antibodies. 相似文献
105.
Hironobu Kunieda Hamidul Kabir Kenji Aramaki Kazuki Shigeta 《Journal of Molecular Liquids》2001,90(1-3):157-166
Cloud temperatures, phase behavior, and the structures of liquid crystals were investigated in the aqueous systems of homogenous hexaethylene glycol dodecyl ether(C12EO6) and mixed C12EO4-C12EO8, C12EO2-EO8, C12EO2-C12EO8, and C12EO0-C12EO8 In the mixed surfactant systems, the average polyoxyethylene- (EO-) chain lengths are kept constants, the same as C12EO6. The change in cloud temperatures is small in all the systems, whereas the phase behavior is successively changed with increasing the difference in EO-chain length in the mixture. Lamellar liquid crystal is developed in the phase diagrams and it intrudes in the two-phase region above the cloud temperature. Hence, the phase pattern of the present mixed surfactant systems resembles that of C12EO5 system, but both cloud point and W+L region appear at much higher temperature. Hence, the Hydrophile-Lipophile Balance of the surfactant is not largely changed by mixing the surfactants but the SAXS results show that the surfactant molecules are more tightly packed in the hexagonal and lamellar phases by mixing. It is considered that when surfactants of different EO-chain lengths are mixed, the considerable reduction in repulsion between the hydrophilic moieties takes place and the surfactant molecules are more tightly packed. 相似文献
106.
Noriyasu Hada Tokio Morita Takashi Ueda Kazuki Masuda Hiromi Nakane Mami Ogane Kimiaki Yamano Frank Schweizer Fumiyuki Kiuchi 《Molecules (Basel, Switzerland)》2021,26(18)
Stereocontrolled syntheses of biotin-labeled oligosaccharide portions containing the carbohydrate moiety of glycoprotein from Echinococcus granulosus have been accomplished. Trisaccharide Galβ1-3Galβ1-3GalNAcα1-R (A), tetrasaccharide Galα1-4Galβ1-3Galβ1-3GalNAcα1-R (B), and pentasaccharide Galα1-4Galβ1-3Galβ1-3Galβ1-3GalNAcα1-R (C), (R = biotinylated probe) were synthesized by stepwise condensation and/or block synthesis by the use of 5-(methoxycarbonyl)pentyl 2-azido-4,6-O-benzylidene-2-deoxy-α-d-galactopyranoside as a common glycosyl acceptor. The synthesis of the tetrasaccharide and the pentasaccharide was improved from the viewpoint of reducing the number of synthetic steps and increasing the total yield by changing from stepwise condensation to block synthesis. Moreover, hexasaccharide E, which contains the oligosaccharide sequence which occurs in E. granulosus, was synthesized from trisaccharide D. We examined the antigenicity of these five oligosaccharides by an enzyme-linked immunosorbent assay (ELISA). Although compounds of C–E did not exhibit antigenicity against cystic echinococcosis (CE) patient sera, compounds B, D, and E showed good serodiagnostic potential for alveolar echinococcosis (AE). 相似文献
107.
Hirata Kazuki Matsuda Atsunori Hirata Toshiyuki Tatsumisago Masahiro Minami Tsutomu 《Journal of Sol-Gel Science and Technology》2000,17(1):61-69
Highly proton-conductive elastic composites have been successfully prepared from H3PO4-doped silica gel and a styrene-ethylene-butylene-styrene (SEBS) block elastic copolymer. Ionic conductivities of the composites depended on the concentration of H3PO4 and the heat treatment temperature of the H3PO4-doped silica gel. It was found that H3PO4 added is present mainly as free orthophosphoric acid in the silica gel. The composite composed of H3PO4-doped silica gel with a molar ratio of H3PO4/SiO2 = 0.5 heat-treated at temperatures below 200°C and SEBS elastomer in 5 mass% showed a high conductivity of 10–5 S cm–1 at 25°C in an dry N2 atmosphere. The water adsorption during a storage in 25% relative humidity at room temperature for 1 day enhanced the ionic conductivities of composites by about one order of magnitude. Lower conductivities obtained in the composite with the H3PO4-doped silica gel heat-treated at 250°C for 1 h were due to the formation of crystalline Si3(PO4)4. The temperature dependence of conductivity of the composites was the Vogel-Tamman-Fulcher type, indicating that proton was transferred through a liquidlike phase formed in micropores of the H3PO4-doped silica gels. The temperature dependence of the modulus of the composite was similar to that of the SEBS elastomer. The thermoplastically deforming temperature of the composite was around 100°C, which was higher by 30°C than that of the SEBS elastomer. 相似文献
108.
Since the aggregation-induced emission (AIE) phenomenon was first reported by Tang et al., much effort has been devoted to the development of solid-state luminescent molecules by chemists worldwide. Our group successfully developed fluorinated tolanes as novel compact π-conjugated luminophores with blue photoluminescence (PL) in the crystalline state. Moreover, we reported the yellow-green PL molecules based on their electron-density distributions. In the present study, we designed and synthesized fluorinated tolanes with various amine-based donors and evaluated their photophysical properties. The carbazole-substituted fluorinated tolane exhibited strong PL in the solution state, whereas piperidine- or phenothiazine-substituted fluorinated tolanes showed a dramatic decrease in PL efficiency. Notably, fluorinated tolanes with piperidine or phenothiazine substituents displayed yellow-to-orange PL in the crystalline state; this may have occurred because these tolanes exhibited tightly packed structures formed by intermolecular interactions, such as H···F hydrogen bonds, which suppressed the non-radiative deactivation process. Moreover, fluorinated tolanes with amine-based donors exhibited AIE characteristics. We believe that these yellow-to-orange solid PL molecules can contribute to the development of new solid luminescent materials. 相似文献
109.
Kazuki Iwashita Kiyoharu Tadanaga Tsutomu Minami 《Journal of Sol-Gel Science and Technology》1997,10(3):301-307
SiO2-CH3SiO3/2 thin films coated on nylon-6 substrates by the sol-gel method were modified with trimethylsilyl (TMS) groups and their water permeability was evaluated. The water permeability coefficient of the nylon-6 substrates coated with TMS-modified SiO2-CH3SiO3/2 thin films was smaller than that of unmodified ones. The wettability for water of SiO2-CH3SiO3/2 thin films modified with TMS was smaller than that of unmodified ones. The decrease in the wettability by the modification with TMS resulted in the decrease in water permeability. The measurements of pore size distribution and the water permeability coefficient of coating films with different pressures of upstream side suggested that the mechanism of permeation was governed by the capillary condensation flow. This mechanism was also supported by the result that the water permeability coefficient was decreased with a decrease in wettability. 相似文献
110.
A bicyclic dipeptide derivative with fixed conformation simulating that of the two central amino acid residues in type II′ β-turn has been synthesized starting from L-glutamic acid and L-cysteine in short steps. 相似文献