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亚利桑那沙门氏菌O45 O特异性多糖的结构

Structure of the O-specific polysaccharide of Salmonella arizonae O45.

作者信息

Shashkov A S, Vinogradov E V, Knirel Y A, Nifant'ev N E, Kochetkov N K, Dabrowski J, Kholodkova E V, Stanislavsky E S

机构信息

N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow.

出版信息

Carbohydr Res. 1993 Mar 17;241:177-88. doi: 10.1016/0008-6215(93)80104-m.

Abstract

The O-specific polysaccharide of Salmonella arizonae O45 (Arizona 11) is acidic and has a branched hexasaccharide repeating unit containing two residues of L-fucose, one residue each of D-galactose, D-ribose, D-glucuronic acid, and 2-acetamido-2-deoxy-D-glucose, and an O-acetyl group. It was studied with the help of 1H and 13C NMR spectroscopy, including 1D selective spin-decoupling and homonuclear Hartmann-Hahn spectroscopy, 2D homonuclear and 13C-1H heteronuclear shift-correlated (COSY) and NOE (ROESY) spectroscopy, as well as by methylation analysis, and selective cleavages with anhydrous HF (or dilute HCl) and lithium in ethylenediamine to yield two different tetrasaccharide fragments. As a result, the following structure of the polysaccharide was established: [formula: see text] Anomalous 13C chemical shifts were observed in the spectrum of the trisaccharide fragment alpha-L-Fucp-(1-->2)-beta-D-Gal p-(1-->3)-beta-D-Glc pNAc, structurally related to the Le(d) blood-group determinant, and rationalised by inter-residue proton-proton interactions.

摘要

亚利桑那沙门氏菌O45(亚利桑那11)的O-特异性多糖呈酸性,具有一个分支六糖重复单元,包含两个L-岩藻糖残基、一个D-半乳糖残基、一个D-核糖残基、一个D-葡萄糖醛酸残基、一个2-乙酰氨基-2-脱氧-D-葡萄糖残基以及一个O-乙酰基。借助1H和13C核磁共振光谱对其进行了研究,包括一维选择性自旋去耦和同核哈特曼-哈恩光谱、二维同核以及13C-1H异核位移相关(COSY)和NOE(ROESY)光谱,还通过甲基化分析以及用无水HF(或稀盐酸)和乙二胺中的锂进行选择性裂解,得到了两个不同的四糖片段。结果,确定了该多糖的以下结构:[分子式:见正文]在与Le(d)血型决定簇结构相关的三糖片段α-L-Fucp-(1→2)-β-D-Galp-(1→3)-β-D-Glc pNAc的光谱中观察到了异常的13C化学位移,并通过残基间质子-质子相互作用进行了合理化解释。

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