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排序方式: 共有275条查询结果,搜索用时 15 毫秒
31.
In this study, we report novel and simple chemical syntheses of acyl dihydroxyacetone phosphate (DHAP) and 1-acyl glycero-3-phosphate [lysophosphatidic acid (LPA)], key intermediaries in the formation of glycerolipids containing ester and ether bonds. The synthesis of acyl DHAPs involved acylating the dimethyl ketal of DHAP by acid anhydride using 4-pyrrolidinopyridine as the catalyst, and the resulting product was deketalized by HClO(4) in acetone to produce acyl DHAP. The acid anhydride was either added directly or generated in the reaction mixture from the corresponding fatty acid using dicyclohexylcarbodiimide as the condensing agent. Using these methods, a number of acyl DHAPs having short-, medium-, and long-chain saturated and unsaturated acyl groups were synthesized, with overall yields from 37% to 75%. The activities of these acyl DHAPs as substrates for guinea pig liver peroxisomal acyl DHAP:NADPH reductase and alkyl DHAP synthase were then determined. Next, starting from these acyl DHAPs, a variety of LPAs were synthesized by chemical reduction of the ketone group. Biological activities of these LPAs were determined by measuring their relative abilities to release intracellular Ca(2+) via the LPA receptor. A combined chemical-enzymatic method is also described to prepare the natural LPA from the racemic mixture. 相似文献
32.
Hasegawa T Umeda M Numata M Li C Bae AH Fujisawa T Haraguchi S Sakurai K Shinkai S 《Carbohydrate research》2006,341(1):35-40
(1-->3)-beta-D-Glucans having various functional appendages (lactoside, ferrocene, pyrene, and porphyrin) can be prepared in an convenient, quantitative, and regioselective manner through regioselective bromination-azidation of curdlan to afford 6-azido-6-deoxycurdlan followed by chemoselective [3+2]-cycloadditions with various functional modules bearing a terminal alkyne group. The ability to monitor reaction conversions is an additional advantage of this synthetic approach over the conventional direct modifications on polysaccharides; the reaction can be readily monitored based on the intensity of azido peaks in the in situ attenuated total reflection infrared spectra. 相似文献
33.
We report here a range of new sucrose derivatives obtained from '3-ketosucrose' in aqueous medium with few reaction steps. As an intermediate, 3-amino-3-deoxy-alpha-D-allopyranosyl beta-D-fructofuranoside (1) was obtained via the classical route of reductive amination with much improved yield and high stereoselectivity. Building blocks for polymerization were synthesized by introduction of acrylic-type side chains, for example, with methacrylic anhydride. Corresponding polymers were synthesized. Aminoacyl and peptide conjugates were obtained through conventional peptide synthesis with activated and protected amino acids. Deprotection yielded new glycoderivatives having an unconventional substitution pattern, namely 3-(aminoacylamino) allosaccharides. Both mono- and di-peptide conjugates of allosucrose have been synthesized. 相似文献
34.
Oleg Bol'shakov Judit Kovacs Mamta Chahar Khanh Ha Levan Khelashvili Alan R. Katritzky 《Journal of peptide science》2012,18(11):704-709
S‐Acyl cysteine peptides containing α‐, β‐ or γ‐amino acid residues undergo long‐range S‐ to N‐acyl transfer to give analogs of native tripeptides and tetrapeptides containing additional carbon atoms in the chain. The ease of intramolecular S → N‐acyl transfer relative to intermolecular transacylation is favored increasingly for 9 < 12 < 13 ~ 10‐membered cyclic transition states; the observed order is explained on conformational and intermolecular interaction considerations. Copyright © 2012 European Peptide Society and John Wiley & Sons, Ltd. 相似文献
35.
The hydrogen bond systems of cellulose and its derivatives are one of the most important factors regarding their physical- and chemical properties such as solubility, crystallinity, gel formation, and resistance to enzymatic degradation. In this paper, it was attempted to clarify the intra- and intermolecular hydrogen bond formation in regioselectively functionalized 3-mono-O-methyl cellulose (3MC). First, the 3MC was synthesized and the cast film thereof was characterized in comparison to 2,3-di-O-methyl cellulose, 6-mono-O-methyl cellulose, and 2,3,6-tri-O-methyl cellulose by means of wide angle X-ray diffraction (WAXD) and (13)C cross polarization/magic angle spinning NMR spectroscopy. Second, the hydrogen bonds in the 3MC film were analyzed by means of FTIR spectroscopy in combination with a curve fitting method. After deconvolution, the resulting two main bands (Fig. 3) indicated that instead of intramolecular hydrogen bonds between position OH-3 and O-5 another intramolecular hydrogen bond between OH-2 and OH-6 may exist. The large deconvoluted band at 3340cm(-1) referred to strong interchain hydrogen bonds involving the hydroxyl groups at C-6. The crystallinity of 54% calculated from the WAXD supports also the dependency of the usually observed crystallization in cellulose of the hydroxyl groups at C-6 to engage in interchain hydrogen bonding. 相似文献
36.
The synthesis of novel 3-O-(2-methoxyethyl)cellulose via 2,6-di-O-thexyldimethylsilyl ethers was successfully carried out. Treatments of 3-O-(2-methoxyethyl)-2,6-di-O-thexyldimethylsilylcellulose with tetrabutylammonium fluoride trihydrate led to a complete removal of the protecting groups. Structure characterization carried out by means of 1D and 2D NMR spectroscopy proves a high regioselectivity. The novel cellulose ether is soluble in dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, and water. Size-exclusion chromatography revealed a distinct aggregation behavior in water. 相似文献
37.
Teste K Colombeau L Hadj-Bouazza A Lucas R Zerrouki R Krausz P Champavier Y 《Carbohydrate research》2008,343(9):1490-1495
This paper describes an efficient procedure for selective 3'-O- or 3-N-protection of 5'-O-tert-butyldimethylsilylthymidine, depending on the use of aprotic polar solvents with low or high dielectric constant, respectively. These syntheses were activated by either ultrasound or microwaves. Several alkyl bromides offer a convenient route to prepare 3'-O- or 3-N-protected and functionalized thymidine derivatives. 相似文献
38.
Toshifumi Miyazawa Tomoyuki Yukawa Takashi Koshiba Shinichi Ueji Ryoji Yanagihara Takashi Yamada 《Biotechnology letters》2001,23(19):1547-1550
2-(Substituted phenoxy)-1-propanols, e.g. 2-(4-chlorophenoxy)-1-propanol, belonging to primary alcohols with an oxygen atom at the stereocenter, were resolved with moderate to good enantioselectivity, as judged by the value of enantiomeric ratio E (up to 27), through the enantioselective acylation with vinyl butanoate mediated by the little-known lipase from Achromobacter sp. in diisopropyl ether, after the examination of potential factors affecting the reaction such as organic solvents and acyl donors. 相似文献
39.
Chemo-enzymatic preparation of resveratrol derivatives 总被引:1,自引:0,他引:1
Giovanni Nicolosi Carmela Spatafora Corrado Tringali 《Journal of Molecular Catalysis .B, Enzymatic》2002,16(5-6):223-229
Regioselective derivatisation of resveratrol (1) at positions 3, 5 or 4′ was achieved by a chemo-enzymatic procedure based on standard chemical reactions and esterification or alcoholysis in organic solvents catalysed by the commercially available Pseudomonas cepacia (PcL) and Candida antarctica (CaL) lipases. 相似文献
40.