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121.
Yuichi Yoshimura Tetsuya Kuze Fumiko Komiya Hiromichi Tanaka Kohei Yamada Nobuaki Kaneko 《Tetrahedron letters》2006,47(4):591-594
A practical synthesis of 4′-thioribonucleosides starting from inexpensive l-arabinose is described. 1,4-Anhydro-2,3-O-isopropylidene-4-thioribitol, which was prepared by using a novel reductive ring-contraction reaction, was converted to the 5-O-silylated sulfoxides. The Pummerer-type thioglycosylation of the sulfoxides gave the 4′-thioribonucleosides stereoselectively. 相似文献
122.
Ion chromatographic separation of hydrogen ion and other common mono- and divalent cations 总被引:1,自引:0,他引:1
We introduced an approach to the ion chromatographic determination of common mono- and divalent cations including hydrogen ion and demonstrated the ability of a C30 column dynamically coated first with dodecylsulfate and then with 18-crown-6 ether to separate the cations by ion-exchange mechanism. Using an ethylenediamine solution containing a small concentration of 18-crown-6 ether and lithium dodecylsulfate at pH 6.2 as eluent, the cations were eluted in the order Li < Na+ < NH4+ < H+ < K+ < Mg2+ < Ca2+ with symmetrical peaks. The conductivity vs. concentration plots were linear about three orders of magnitude, from millimolar to micromolar; and the detection limits were all < 0.6 microM. Rainwater was analyzed directly using this ion chromatographic system with satisfactory results. 相似文献
123.
H Koga N Mori H Yamada Y Nishimura K Tokuda K Kato T Imoto 《Chemical & pharmaceutical bulletin》1992,40(4):965-970
Employing soluble denatured protein substrates and their derivatives, the proteolytic activity of rat cathepsin H was investigated. The enzyme showed aminopeptidase activity which sequentially released amino acid from the N-terminal of the substrate. The aminopeptidase activity did not act on N alpha-acetylated peptides and showed moderate ionic-strength dependence when methionyl-methylcoumarylamide was employed as a substrate. These results indicate that the activity essentially requires an N-terminal free amino group of the substrate and recognizes it electrostatically to some extent. On the other hand, the enzyme was also indicated to exhibit endopeptidase activity by employing appropriate N alpha-acetylated peptide substrates. In contrast to the aminopeptidase activity, the endopeptidase activity showed rather strict specificity, preferring hydrophobic residues at P2 and P3 sites. Because of the broad specificity and high efficiency of the aminopeptidase activity, it was difficult to directly observe endopeptidase activity in the digestion of large peptide substrates with a free alpha-amino terminal. Thus, this is the first experimental evidence that indicates endopeptidase activity by assigning internal peptide bonds cleaved by this activity. From this data, we proposed a model of the binding site of this enzyme. 相似文献
124.
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
125.
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
126.
Takayuki Otsu Bunichiro Yamada Shigeru Sugiyama Shigeki Mori 《Journal of polymer science. Part A, Polymer chemistry》1980,18(7):2197-2207
Radical polymerization and copolymerization of some o-alkylphenyl methacrylates were carried out and the effect of the ortho-substituents on the ability to homopolymerize, on the monomer reactivities, and on the ceiling temperatures of the monomers was studied. The effect of the substituent on tacticities and thermal stabilities of the polymers formed was also discussed. The ability to honiopolymerize and the monomer reactivity were considerably decreased by the introduction of the o-substituent. 2,6-Di-tert-butylphenyl methacrylate formed no methanol-insoluble polymer at 60°C. On the basis of the tacticity determined it was noted that the o-substituted phenyl methacrylates preferred syndiotactic addition in the propagation reaction less than did phenyl methacrylate or methyl methacrylate. The polymers formed from the o-substituted monomers were thermally less stable than poly(phenyl methacrylate), and, consistent with this finding, ceiling temperatures of the o-substituted phenyl methacrylates seemed to be lower than that of phenyl methacrylate. The effects observed were characteristic of the o-substituents conformationally close to the carbon-carbon double bond of the monomer or the carbon carrying the unpaired electron of the polymer radical. 相似文献
127.
A new family of quaternary carbon and nitrogen containing Rare Earth (RE: Sc, Y, Ho, Er, Tm and Lu) borides: REB15.5CN, has been synthesized and structurally characterized by powder X-ray diffraction data. They are all isotypic with Sc1−xB15.5CN whose structure was solved based on single-crystal X-ray data and HRTEM investigations. The structure refinement converged at a R(F2) value of 0.044 for 364 reflections. The new structure type of Sc1−xB15.5CN is composed of a three-dimensional network based on interconnected slabs of boron (B12)ico icosahedra and (B6)oct octahedra. A linear [CBC] chain and nitrogen tightly bridges icosahedra. Sc partially occupies voids in the sheets of boron octahedra. It crystallizes with the trigonal space group P3m1, with Z=2. Lattice parameters (nm) are as follows: for RE: Sc, a,b=0.5568(4), c=1.0756(2); Y, a,b=0.55919(6), c=1.0873(2); Ho, a,b=0.55883(7), c=1.0878(6); Er, a,b=0.55889(5), c=1.0880(6); Tm, a,b=0.5580(1), c=1.0850(6); Lu, a,b=0.55771(9), c=1.0839(4). Magnetic characterization of ErB17C1.3N0.6 has been performed. 相似文献
128.
When a THF solution of beta-lactam having propargyl phosphate was warmed in the presence of 5 mol % of Pd(2)(dba)(3) x CHCl(3), 20 mol % of a bidentate ligand, and sodium acetate (1.5 equiv) at 40 degrees C for 22 h, carbapenam was produced in high yield. In this reaction, the lactam nitrogen attacked the central carbon of a eta(3)-propargylpalladium complex, which was formed from propargyl phosphate and Pd(0). 相似文献
129.
Yo Ueda K
ichi Mori Keiki Kouno Tokihiro Nhya 《Journal of mass spectrometry : JMS》1976,11(10):1027-1036
The mass spectra of 30 sulfinamide derivatives (RSONHR', R' alkyl or p-XC6H4) are reported. Most of the spectra had peaks attributable to thermal decomposition products. For some compounds these were identified by pyrolysis under similar conditions to be: RSO2NHR', RSO2SR, RSSR and NH2R' (in all kinds of sulfinyl amides); RSNHR' (in the case of arylsulfinyl arylamides); RSO2C6H4NH2, RSOC6H4NH2 and RSC6H4NH2 (in the case of arylsulfinyl arylamides of the type of X = H) The mass spectra of the three thermally stable compounds showed that there are several kinds of common fragment ions. The mass spectra of the thermally labile compounds had two groups of ions; (i) characteristic fragment ions of the intact molecules and (ii) the molecular ions of the thermal decomposition products. It was concluded that the sulfinamides give the following ions after electron impact: [M]+, [M ? R]+, [M ? R + H]+, [M ? SO]+, [RS]+, [NHR']+, [NHR' + H]+, [RSO]+, [RSO + H]+, [R]+, [R + H]+, [R']+ and [M ? OH]+, and that the thermal decomposition products give the following ions: [RSO2SR]+, [RSSR]+, [M ? O]+, [M + O]+ and [RSOC6H4NH2]+. 相似文献
130.
[reaction: see text]. The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H4(13)CH(Me)18OC(O)C6F5 in 50/50 (v/v) trifluoroethanol/water, k(solv) + k(iso) = 1.22 x 10(-5) s(-1), is larger than k(solv) = 1.06 x 10(-5) s(-1) for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k(-1) = 7 x 10(9) s(-1) for internal return by unimolecular collapse of the ion pair, which is significantly larger than k(Nu) = 5 x 10(8) M(-1) x s(-1) for bimolecular nucleophilic addition of carboxylate anions to 4-MeC6H4CH(Me)+. 相似文献