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111.
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
112.
Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light 下载免费PDF全文
Dr. Jiale Wang Dr. Fabiane J. Trindade Caroline B. de Aquino Joana C. Pieretti Prof. Dr. Sergio H. Domingues Prof. Dr. Romulo A. Ando Prof. Dr. Pedro H. C. Camargo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9889-9894
Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl4?(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O2 through the transfer of SPR‐excited hot electrons to O2 molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O2 molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O2 charge‐transfer process. 相似文献
113.
Yoshio Kabe Houjin Hachiya Daisuke Shimizu Kazuharu Suzuki Wataru Ando 《Journal of organometallic chemistry》2009,694(13):1988-10153
The addition of silyl diazomethane (1a-d) to fullerene C60 at room temperature provided the mono-adducts, the bis- and tris-adducts of silyl fulleroid (3a-d) in moderate yields. The structures of the silyl fulleroids were characterized by mass spectroscopy, as well as 1H and 13C NMR. The gated 1H NMR and 13C-1H COLOC analyses of 3a-d showed a correlation between the methine proton resonances and three fullerene carbons. These observations, as well as the 1H NMR chemical shifts of the methine protons, suggest a remarkable diastereoselectivity, with the silyl groups located above a five-membered ring. Two transition states of the thermal nitrogen-extrusion of pyrazoline intermediate (2a) were theoretically obtained, the structures of which disclosed that the diastereoselectivity is a consequence of minimization of the repulsive interaction between the silyl groups and the N2 moiety. The bridgehead CC double bond of the silyl fulleroid is thought to be reactive by POAV analyses. The silyl fulleroids (3a,b) were found to react with singlet oxygen to afford the silyl enol ether (9a,b) via 1,3-silyl migration of a diketone (8a,b). This is the first example of 1O2 oxygenation of fulleroids. 相似文献
114.
Application of the muramyldipeptide derivative B30-MDP to liposomal vaccines will aid in the development of improved high immunogenicity vaccines. To give full play to the effectiveness of B30-MDP as a liposomal vaccine, it is important to evaluate the effect of cholesterol, dimyristoylphosphatidylcholine (DMPC) or distearoylphosphatidylcholine (DSPC) incorporation on the chemical stability of B30-MDP and physicochemical properties of B30-MDP/lipid mixed vesicles from the view point of pharmaceutics.The observed degradation rate constants of B30-MDP by hydrolysis in B30-MDP/cholesterol mixed vesicles were increased with increasing concentration of cholesterol, however, those in B30-MDP/DMPC and B30-MDP/DSPC mixed vesicles were unchanged with increasing concentration of DMPC and DSPC. The degradation behavior of B30-MDP was then compared with physicochemical properties of B30-MDP/lipid mixed vesicles, such as membrane fluidity and particle size. It was apparent that the degradation of B30-MDP in B30-MDP/cholesterol mixed vesicles was influenced by the particle size, but not by the fluidity of the membranes. In the case of B30-MDP/phospholipid mixed vesicles, MDP/phospholipid mixed vesicles, the degradation of B30-MDP was not influenced by either the membranes' fluidity or the particle size of the mixed vesicles.It is considered that the degradation of B30-MDP in the mixed vesicles is dependent on the membrane state, and the addition of cholesterol to B30-MDP vesicle inhibits the mutual interaction of MDP regions, whereas the addition of phospholipids hardly influences the mutual interaction of MDP regions, possibly owing to phase separation between B30-MDP and phospholipids. 相似文献
115.
116.
Kiyoshi Ando 《Journal of Graph Theory》2009,60(2):99-129
An edge of a 5‐connected graph is said to be contractible if the contraction of the edge results in a 5‐connected graph. Let x be a vertex of a 5‐connected graph. We prove that if there are no contractible edges whose distance from x is two or less, then either there are two triangles with x in common each of which has a distinct degree five vertex other than x, or there is a specified structure called a K4?‐configuration with center x. As a corollary, we show that if a 5‐connected graph on n vertices has no contractible edges, then it has 2n/5 vertices of degree 5. © 2008 Wiley Periodicals, Inc. J Graph Theory 60: 99–129, 2009 相似文献
117.
Kuga Yoshikazu Okauchi Keiko Takeda Daiki Ohira Yuichi Ando Koji 《Journal of nanoparticle research》2001,3(2-3):175-183
Size distribution measurements and classification tests by a low pressure differential mobility analyzer (LPDMA) for nanometer-sized silver particles and cesium iodide particles under low pressure conditions (123–300 Torr) were performed using a transmission electron microscope (TEM) and the tandem DMA technique. When the ratio of the sheath gas flow rate and the aerosol gas flow rate was set at 5 : 1, the targeted sizes calculated from the classification voltage applied to the LPDMA at 160 Torr are found to be in good correlation with the count mean Feret diameter obtained from the TEM observation of the particles collected after a classification ranging from 6 to 25 nm, although the targeted sizes set by the LPDMA were approximately 15% greater than the count mean Feret diameter measured by the TEM after classification. The geometric standard deviations of DMA-classified particles measured by TEM and those obtained from the tandem DMA method ranged from 1.08 to 1.17 and from 1.05 to 1.13, respectively. They were slightly greater than the ideal geometric standard deviations (1.05) of the particles classified with the LPDMA, which was calculated by neglecting the broadening effects due to Brownian diffusion. We experimentally demonstrated the validity of our LPDMA system for size measurements and classification of the nanometer-sized particles under low pressure conditions. 相似文献
118.
119.
In order to obtain some insight into the structure of an ultrahigh-molecular-weight polyethylene sample, 13C CP/MAS NMR experiments have been carried out at temperatures from 23 to ?108°C. The peak for the crystalline component moves upfield with a decrease in temperature, which is contrary to what was reported previously for a melt-crystallized polyethylene sample. On the basis of x-ray diffraction results and quantum-chemical calculations, it is suggested that the methylene carbons are in the distorted orthorhombic form at low temperatures. 相似文献
120.
Yutaka Nagasawa Ayako Watanabe Yoshito Ando Tadashi Okada 《Journal of Molecular Liquids》2001,90(1-3):295-302
We have studied femtosecond ground state recovery dynamics of phenol blue (PB) by pump-probe spectroscopy with a time resolution of 33 fs. Multiexponential decay with time constants extending from 300 fs to 10 ps were observed. Some low frequency intramolecular quantum beats were also observed. Solvent dependence of these decays and beats are discussed. 相似文献