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111.
O1s core‐electron binding energies (CEBE) of the atomic oxygens on different Ag surfaces were investigated by the symmetry adapted cluster‐configuration interaction (SAC‐CI) method combined with the dipped adcluster model, in which the electron exchange between bulk metal and adsorbate is taken into account properly. Electrophilic and nucleophilic oxygens (Oelec and Onuc) that might be important for olefin epoxidation in a low‐oxygen coverage condition were focused here. We consider the O1s CEBE as a key property to distinguish the surface oxygen states, and series of calculation was carried out by the Hartree–Fock, Density functional theory, and SAC/SAC‐CI methods. The experimental information and our SAC/SAC‐CI results indicate that Oelec is the atomic oxygen adsorbed on the fcc site of Ag(111) and that Onuc is the one on the reconstructed added‐row site of Ag(110) and that one‐ and two‐electron transfers occur, respectively, to the Oelec and Onuc adclusters from the silver surface. © 2013 Wiley Periodicals, Inc. 相似文献
112.
Atsushi Kubono Kazuki Yoshino Toshiro Ninomiya Ryuichi Akiyama Katsufumi Tanaka 《Liquid crystals》2013,40(8):1089-1095
The visco-elastic properties for binary mixtures of 4-n -hexyloxy-4′-cyanobiphenyl (6OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0–29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems. 相似文献
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114.
Akira Hasegawa Takashi Ando Akihiko Kameyama Makoto Kiso 《Journal of carbohydrate chemistry》2013,32(5):645-658
Abstract Stereocontrolled synthesis of sialyl Lex epitope and its ceramide derivative with regard to the introduction of galactose or β-D-galactosyl ceramide into the terminal N-acetylglucosamine residue of sialyl Lex determinant is described. Königs-Knorr condensation of 2-(trimethylsilyl)ethyl 2, 4, 6-tri-O-benzyl-β-D-galactopyranoside (4) with 3, 4, 6-tri-O-acetyl-2-deoxy-2-phthalimido-D-glucopyranosyl bromide (5) gave the desired β-glycoside 6, which was converted into 2-(trimethylsilyl)ethyl O-(2-acetamido-4, 6-O-benzylidene-2-deoxy-β-D-glucopyranosyl)-(l→3)-2, 4, 6-tri-O-benzyl-β-D-galactopyranoside (8) via removal of the phthaloyl and O-acetyl groups, followed by N-acetylation and 4, 6-O-benzylidenation. Glycosylation of 8 with methyl 2, 3, 4-tri-O-benzyl-1-thio-β-L-fucopyranoside (9) gave the α-glycoside (10), which was transformed by reductive ring-opening of the benzyliderie acetal into the acceptor (11). Dimethyl(methylthio)sulfonium triflate (DMTST)-promoted coupling of 11 with methyl O-(methyl 5-acetamido-4, 7, 8, 9-tetra-O-acetyl-3, 5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-2, 4, 6-tri-O-benzoyl-l-thio-β-D-galactopyra-noside (12) afforded the desired pentasaccharide (13), which was converted into the α-trichloroacetimidate 16 via reductive removal of the benzyl groups, then O-acetylation, removal of the 2-(trimethyIsilyl)ethyl group and treatment with trichloroacetonitrile. Condensation of 16 with (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octadecene-l, 3-diol (18) gave the β-glycoside 19, which was transformed into the title compound 21, via reduction of the azido group, coupling with octadecanoic acid, O-deacylation and hydrolysis of the methyl ester group. On the other hand, O-deacylation of 13 and subsequent hydrolysis of the methyl ester group gave the pentasaccharide epitope 17. 相似文献
115.
Akihiko Kameyama Hideharu Ishida Makoto Kiso Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(5):799-804
Abstract Sialoglycoconjugates such as glycoproteins and glycolipids are present as components of cell memberanes and play important roles1,2 in biological systems. Sialyl neolactotetrasyl ceramide (IV3NeuAcnLc4Cer), a complex type of ganglioside, was isolated as the major ganglioside of human erythrocytes3 and was shown to be a receptor of that this glycolipid induces granulocytic differentiation of human premyelocytic leukemia cell. 相似文献
116.
Kenji Okada Yuichiro Takamatsu Yasuaki Tokudome Atsushi Nakahira Masahide Takahashi 《Journal of Sol-Gel Science and Technology》2013,65(1):36-40
Synthesis of titanate nanotubes (TNTs) from sol–gel derived amorphous TiO2 thin films under moderate hydrothermal condition has been reported. TNTs from film possess a tubular morphology that is the same crystalline phase as one synthesized from TiO2 powder so far. TNTs obtained in this study are not entangled one another but oriented and isolated on the substrate. Growth of highly oriented TNTs is observed in micro grooves of amorphous TiO2 thin film. Their orientation is also maintained with the growth of TNTs. 相似文献
117.
Prof. Dr. Mutsumi Kimura Junya Masuo Yuki Tohata Kazumichi Obuchi Naruhiko Masaki Takurou N. Murakami Nagatoshi Koumura Kojiro Hara Atsushi Fukui Ryohsuke Yamanaka Prof. Dr. Shogo Mori 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1028-1034
A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation. 相似文献
118.
Methylene sp3 carbon–hydrogen bond activation of N-picolinoylcycloalkylamines provides a useful method for synthesizing cis-3-arylated cycloalkylamine derivatives. Pd(II) species catalyzed the γ-arylation of N-picolinoylcycloalkylamines with aryl iodides in the presence of silver carbonate to afford cis-3-arylated N-picolinoylalkylamines in up to 87% yield. Hydrolysis of the amide linkage to give the corresponding cis-3-arylated cycloalkylamines was also demonstrated. 相似文献
119.
120.
Xiaolei Wang Miho Emoto Atsushi Sugimoto Yusuke Miyake Kaori Itto Mitsuo Amasaka Shu Xu Hiroshi Hirata Hirotada Fujii Hirokazu Arimoto 《Tetrahedron letters》2014
A scalable synthetic route for 15N-labeled 4-oxo-2,2,6,6-tetraethylpiperidine nitroxide (15N-TEEPONE) is described. This 15N-labeled nitroxide is suitable for electron paramagnetic resonance imaging of brain, and its higher sensitivity compared with that of its 14N-counterpart is an important advantage of the labeled derivative. 相似文献