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131.
Kenichi Takeo Kimiko Nagayoshi Kenichi Nishimura Shinichi Kitamura 《Journal of carbohydrate chemistry》2013,32(8):1159-1177
Abstract The 8-methoxycarbonyloctyl β-glycosides of the trisaccharides O-β-d-Glcp-(1 → 6)- O-β-d-Glcp-(1 → 3)-d-Glcp and O-β-d-Glcp-(1 → 3)-O-[β-d -Glcp-(1 → 6)]-d-Glcp and of the tetrasaccharide O-β-d-Glcp-(1 → 3)-O-[β-d-Glcp-(1 → 6)]-O-β-d-Glcp-(1 → 3)-d-Glcp, corresponding to the fragments of schizophyllan, have been synthesized by using mono- to tetrasaccharide 1-thioglycosides as glycosyl donors, each bearing a participating benzoyl group in the 2-position, and N-iodosuccinimide and silver triflate as promoter. Saponification of the tri- and tetrasaccharide β-glycosides, followed by attachment to bovine serum albumin of the resulting sugar derivatives having a carboxyl group at the aglycon terminal, provided neoglycoproteins for immunological studies of the polysaccharide. 相似文献
132.
Warô Nakanishi Satoko Hayashi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1833-1837
The lone pair-lone pair repulsion plays an important role in the nonbonded P;;;P interaction in naphthalene 1,8-positions. The conformations around P and Se in 8-(PhSe)-1-(Ph 2 P=O)C 10 H 6 are determined by the attractive O;;;Se--C 3c-4e type interaction. The P;;;Se interaction in the 1,8-positions is also discussed. 相似文献
133.
Abstract Postpolymerization of vinyl monomers initiated by pendant peroxycarbonate groups of grafted polymer chains on carbon black (CB) was investigated. The grafting of polymers having pendant peroxycarbonate groups onto CB was achieved by the trapping of polymer radicals formed by the thermal decomposition of copolymers of t-butylperoxy-2-methacryloyloxyethyl-carbonate (HEPO) with vinyl monomers such as vinyl acetate (VAc), styrene (St) and methyl methacrylate (MMA). The copolymers having pendant peroxycarbonate groups were prepared by copolym-erization of HEPO with vinyl monomers using azo initiator under irradiation of UV light at room temperature. The amount of remaining pendant peroxycarbonate groups of the poly(VAc-co-HEPO)-grafted CB obtained from the reaction at 90°C was maximum and decreased above the temperature. Furthermore, the postpolymerization of vinyl monomers, such as St, MMA, and VAc was initiated in the presence of poly(VAc-co-HEPO)-grafted and poly(St-co-HEPO)-grafted CB and the corresponding polymers were postgrafted onto CB to give branched polymer-grafted CB. The percentage of poly(St)-postgrafting (proportion of post-grafted poly(St) to poly(MMA-co-HEPO)-grafted CB used) increased with increasing polymerization time, but became constant at 20% after 4 hours. 相似文献
134.
Joaquim I. GOES Nobuhiko Handa Satoru Taguchi Takeo Hama 《Photochemistry and photobiology》1995,62(4):703-710
Abstract— The impact of ultraviolet-B radiation (UVBR) on the biosynthesis and the composition of intracellular dissolved free and combined amino acids was examined in nitrate-replete and nitrate-deficient cultures of Tetraselmis sp. Several similarities were observed in the response of Tetraselmis sp. to nitrogen deficiency and exposure to UVBR, in support of a view that UVBR affects amino acid synthesis in phytoplankton via its inhibitory effects on nitrogen assimilation into the cells. At levels that still permitted the uptake of carbon into the cells, both nitrogen deficiency and UVBR exposure resulted in a reduction in the overall rates of carbon incorporated into amino acids, an increase in the absolute concentrations of amino acids within the intracellular dissolved free amino acid (INDFAA) pool and a decrease in the total cellular amino acid (TCAA) pool. An examination of the patterns of carbon assimilation into individual amino acids in cells exposed to UVBR revealed similarities with the patterns in cells subject to nitrogen deficiency. The most conspicuous changes from the controls included an increased incorporation of 13 C into glutamic' acid (glutamic acid + glutamine) and aspartic acid and a marked reduction into alanine and valine. Changes in the concentrations of amino acids within the INDFAA and TCAA pools were also similar in nitrate-deficient and UVBR-exposed cells and resembled the carbon assimilation patterns. These results strongly suggest that UVBR-induced changes in the biosynthesis and composition of amino acids are probably via its suppression of nitrogen assimilation into the cells. 相似文献
135.
We present our recent studies on magnetic field effects (MFEs) observed in reactions of heavy atom-centered radicals such as Si-,P-, Ge-, and Sn-radicals with a ns-laser photolysis technique under magnetic fields of 0–10 T. Although the MFES of heavy atom-centered radicals are much smaller than those of C-radicals due to the spin-orbit interaction of heavy atoms, we have found appreciable MFEs in many reactions of such heavy atom-centered radicals. Comparing the MFES of C-radicals with those of heavy atom-centered ones, we have explained the MFEs of heavy atom-centered radicals in terms of the Δg and relaxation mechanisms. We have found that the separation between the MFES due to the Δg mechanism and those due to the relaxation one is possible with the enhancement of spin relaxation by the addition of a paramagnetic ion. We have also tried to enrich magnetic isotopes of heavy atoms with the magnetic isotope effect (MIE), using the reactions which show fairly large MFES. Recently, we have succeeded in enriching 73Ge. This is the heaviest isotope which has so far been enriched with the MIE from samples of natural abundance. 相似文献
136.
Ogoshi T Yamafuji D Aoki T Kitajima K Yamagishi TA Hayashi Y Kawauchi S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(24):7493-7500
Planar chiral [2]- and [3]rotaxanes constructed from pillar[5]arenes as wheels and pyridinium derivatives as axles were obtained in high yield using click reactions. The process of rotaxane formation was diastereoselective; the obtained [2]rotaxane was a racemic mixture consisting of (pS, pS, pS, pS, pS) and (pR, pR, pR, pR, pR) forms of the per-ethylated pillar[5]arene (C2) wheel, and other possible types of the [2]rotaxane did not form. Isolation of the enantiopure [2]rotaxanes with one axle through (pS, pS, pS, pS, pS)-C2 or (pR, pR, pR, pR, pR)-C2 wheels was accomplished. Furthermore, pillar[5]arene-based [3]rotaxane was successfully synthesized by attachment of two pseudo [2]rotaxanes onto a bifunctional linker. [3]Rotaxane formed in a 1:2:1 mixture with one axle threaded through two (pS, pS, pS, pS, pS)-C2, one (pS, pS, pS, pS, pS)-C2 and one (pR, pR, pR, pR, pR)-C2 (meso form), or two (pR, pR, pR, pR, pR)-C2 wheels. The [3]rotaxane enantiomers and the meso form were successfully isolated using appropriate chiral HPLC column chromatography. The procedure developed in this study is the starting point for the creation of pillar[5]arene-based interlocked molecules. 相似文献
137.
Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile. 相似文献
138.
N-Acylhomoserine lactones (AHLs) are the conserved quorum-sensing signal molecules in Gram-negative bacteria. (Z)-N-(4-Decenoyl)homoserine lactone (1), a new AHL, was isolated from the culture broth of the fungus Mortierella alpina A-178 harboring bacterial endosymbionts, called endobacteria. The structure and absolute configuration of 1 were elucidated by EI-MS, chemical synthesis, and chiral GC analysis. The compound induced the expression of a QS-regulated reporter gene in Agrobacterium tumefaciens NTL4, although its activity was lower than that of N-decanoylhomoserine lactone (6). 相似文献
139.
Characterization of magnetic nanoparticles modified with thiol functionalized PAMAM dendron for DNA recovery 总被引:1,自引:0,他引:1
Tanaka T Shibata K Hosokawa M Hatakeyama K Arakaki A Gomyo H Mogi T Taguchi T Wake H Tanaami T Matsunaga T 《Journal of colloid and interface science》2012,377(1):469-475
Magnetic nanoparticles (MNPs) modified with the thiol functionalized polyamidoamine (PAMAM) dendron were synthesized to estimate their DNA recovery capabilities. Aminosilane-modified MNPs and MNPs surrounded by a phospholipid (distearoylphosphatidylethanolamine (DSPE)) bilayer were used as core particles. Cystamine-core PAMAM dendrimers were reduced by dithiothreitol to dendron thiols and chemically conjugated to the core particles. Characterization of the synthesis revealed an increase of the surface amine charge from generation 1 (G1) to G6, starting with an aminosilane initiator. Particle size distribution analysis indicated that G6 PAMAM-modified MNPs exhibited monodispersity in an aqueous solution. G6 PAMAM-MNPs and G6 PAMAM-PE-MNPs synthesized by the proposed method have equivalent DNA recovery abilities to PAMAM-MNPs prepared by the conventional divergent synthesis method. In optimized conditions, 96% of λDNA was recovered using G6 PAMAM-PE-MNPs. Therefore, the method for preparing PAMAM-MNPs and PAMAM-PE-MNPs proposed in this study will be a novel approach for producing DNA carriers for efficient DNA purification by magnetic separation. 相似文献
140.
Ohshima T Hayashi Y Agura K Fujii Y Yoshiyama A Mashima K 《Chemical communications (Cambridge, England)》2012,48(44):5434-5436
A simple NaOMe catalyst provides superior accessibility to a wide variety of functionalized amides including peptides through direct amination of esters in an atom-economical and environmentally benign way. 相似文献