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排序方式: 共有132条查询结果,搜索用时 500 毫秒
1.
A phosphine/Cu(II) complex catalyzes the dehydrative glycosylation of tri-O-benzylated 1-hydroxyribofuranose to give the ribofuranoside with high stereoselectivity. 相似文献
2.
A chiral amino alcohol/Ir complex catalyzes the asymmetric oxidative lactonizations of meso-diols to give the corresponding lactones in up to 81% ee. 相似文献
3.
Nishimura K Suzuki T Momchilova S Miyashita K Katsura E Itabashi Y 《Journal of chromatographic science》2005,43(9):494-499
A simple and highly sensitive method for determining the fatty acid composition of food lipids containing conjugated linoleic acid (CLA) is described. The method is based on the separation of the 9-anthrylmethyl ester derivatives of saturated and unsaturated (conjugated and non-conjugated) fatty acids by reversed-phase high-performance liquid chromatography with fluorescence detection. Just like the other fatty acids, CLA reacts readily with 9-anthryldiazomethane at room temperature to produce 9-anthrylmethyl esters without isomerization and decomposition of the conjugated double bonds. Clear resolution of the individual fatty acids as their 9-anthrylmethyl esters is achieved on a highly efficient octadecylsilylated silica column (150- x 3-mm i.d., 3-microm particle size) using a stepwise gradient elution with methanol-water. The method is standardized with commercially available CLA isomers (cis-9, trans-11 and trans-10, cis-12-octadecadienoic acids, and their cis,cis and trans,trans isomers) and applied for determination of the fatty acid compositions of milk and sdairy products. 相似文献
4.
Eiki Itabashi 《Journal of Electroanalytical Chemistry》1978,88(2):205-217
The process of reduction and reoxidation of cobalt(II) in thiocyanate solution at hanging mercury drop electrode has been investigated by cyclic voltammetric, chronoamperometric and anodic stripping methods. In 0.1 M NaSCN and 0.4 M NaClO4 solution containing 1×10?3M cobalt(II), the voltammogram on the first cycle at 0.05 V s?1 gives a cathodic peak at ?1.06 V with hysteresis on reversal, and an anodic wave with a peak potential of ?0.28 V and with two shoulders near ?0.38 and ?0.45 V, respectively. Multicyclic voltammograms under the same conditions give a cathodic peak at ?0.90 V and an anodic peak at ?0.45 V. The reduction and reoxidation of cobalt(II) in thiocyanate solution is accelerated by the reduction products of thiocyanate ion, cyanide and sulphide ions, which are produced during the electroreduction of cobalt(II).A mechanism of reduction and reoxidation of cobalt(II) which involves a chemical reduction of thiocyanate ion by electroreduced metallic cobalt and takes into account cyanide and sulphide ions is proposed. The hysteresis on the cathodic wave is caused by the difference in reduction potentials of cobalt(II)-thiocyanate and-cyanide complexes. Cyclic voltammetric study of cobalt(II) in perchlorate solution containing trace amounts of cyanide and sulphide ions supports these conclusions. 相似文献
5.
Kubo M Takizawa T Wakai C Matubayasi N Nakahara M 《The Journal of chemical physics》2004,121(2):960-969
The site-selective H/D exchange reaction of phenol in sub- and supercritical water is studied without added catalysts. In subcritical water in equilibrium with steam at 210-240 degrees C, the H/D exchange proceeds both at the ortho and para sites in the phenyl ring, with no exchange observed at the meta site. The pseudo-first-order rate constants are of the order of 10(-4) s(-1); 50% larger for the ortho than for the para site. In supercritical water, the exchange is observed also at the meta site with the rate constant in the range of 10(-6)-10(-4) s(-1). As the bulk density decreases, the exchange slows down and the site selectivity toward the ortho is enhanced. The enhancement is due to the phenol-water interaction preference at the atomic resolution. The site selectivity toward the ortho is further enhanced when the reaction is carried out in benzene/water solution. Using such selectivity control and the reversible nature of the hydrothermal deuteration/protonation process, it is feasible to synthesize phenyl compounds that are deuterated at any topological combination of ortho, meta, and para sites. 相似文献
6.
Yoshiyuki Tanaka Makoto Arakawa Yohei Yamaguchi Chieko Hori Masahiro Ueno Takeyuki Tanaka Tatsushi Imahori Yoshinori Kondo 《化学:亚洲杂志》2006,1(4):581-585
A metal‐free acetylide was observed by using NMR spectroscopy. Metal‐free acetylides are closely related to reactive intermediates (carbanions) in solution; therefore, they have been regarded as unobservable species. However, we generated this highly reactive and unstable species through the deprotonation of phenylacetylene by using the strong nonmetallic phosphazene base tBu‐P4. In the presence of tBu‐P4, the J coupling between the ethynyl carbon and hydrogen nuclei (1JC,H) of phenylacetylene disappeared; this indicates the deprotonation of the alkyne terminal. Furthermore, a large low‐field shift (approximately 90 ppm) of the alkyne carbon resonance was observed. We concluded that we have observed a metal‐free carbanion with a formal charge on an sp‐hybridized carbon atom for the first time. 相似文献
7.
The resolution of reverse isomers remains a major unsolved problem in glycerolipid chromatography. We have investigated the separation of the reverse isomers of 1,2-diacyl-rac-glycerols under a variety of high-performance liquid chromatography (HPLC) conditions. The reverse isomers of diacylglycerols having various pairs of acyl groups including short and highly unsaturated chains, which were prepared by partial Grignard degradation of the corresponding triacylglycerols, were chromatographed as 3,5-dinitrophenylurethanes. Excellent resolution was achieved for the reverse isomers of very different pairs of acyl groups, such as acetate-palmitate and docosahexaenoate-palmitate, by chiral-phase HPLC on columns containing (R)- and (S)-1-(1-naphthyl)ethylamine polymeric phases, reversed-phase HPLC on a highly efficient C18 column (4 microm particle size) and silver ion HPLC on a silver loaded cation-exchange column. The chiral-phase HPLC also permitted complete enantiomer resolution for all the reverse isomers examined. No satisfactory resolution by any of the HPLC methods, however, was obtained for the reverse isomers possessing minor differences in chain lengths and degree of unsaturation, such as laurate-palmitate and oleate-linoleate. The limitations of resolution and characteristics of elution are described. 相似文献
8.
Momchilova S Tsuji K Itabashi Y Nikolova-Damyanova B Kuksis A 《Journal of separation science》2004,27(12):1033-1036
The ability of reversed-phase high-performance liquid chromatography (RP-HPLC) to separate some positionally isomeric disaturated and monounsaturated triacylglycerols (TAGs) as intact species is demonstrated for the first time. Mobile phases of acetonitrile modified with methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, acetone, or dichloromethane were tested for the separation of POP-PPO, PLP-PPL, PEP-PPE, and PDP-PPD (P-palmitic, O-oleic, L-linoleic, E-eicosapentaenoic, D-docosahexaenoic acid residue) on a single RP-HPLC column. The resolution improved with increasing number of double bonds in the acyl residues. While POP and PPO were only partially resolved, PDP and PPD were fully separated with all tested mobile phases, except those containing methanol. Also separated were the four TAGs having the same equivalent carbon number (ECN = 42), PEP, PPE, PDP, and PPD, on a single RP-HPLC column with mobile phase acetonitrile-2-propanol (70:30, v/v) at 0.8 mL/min. In all cases the isomer with the unsaturated acyl residue in either 1- or 3-position was retained more strongly than the respective 2-isomer. 相似文献
9.
10.
Shintaro Wakamatsu Yuka Takahashi Dr. Hidetsugu Tabata Dr. Tetsuta Oshitari Norihiko Tani Prof. Dr. Isao Azumaya Dr. Yukiteru Katsumoto Dr. Takeyuki Tanaka Dr. Shinzo Hosoi Prof. Dr. Hideaki Natsugari Prof. Dr. Hideyo Takahashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7056-7063
The stereochemistry around the N‐benzoylated indole moiety of indometacin was studied by restricting the rotation about the N? C7′ and/or C7′? C1′ bond. In the 2′,6′‐disubstituted ones, an atropisomeric property was found and the atropoisomers were separated and isolated as stable forms. Their biological abilities to inhibit cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) were examined. Only the aR‐isomer showed specific inhibition of COX‐1, and COX‐2 was not inhibited by either atropisomer. Conformational analysis in NMR studies and X‐ray crystallography, and CD spectra in combination with calculations were utilized to elucidate the bioactive conformations. 相似文献