Rivière M, Fournié J J, Monsarrat B, Puzo G
Centre de Recherche de Biochimie et Génétique Cellulaires du CNRS, Toulouse, France.
J Chromatogr. 1988 Jul 8;445(1):87-95. doi: 10.1016/s0021-9673(01)84510-6.
Partially methylated glycosides play an important role in the stereospecificity of glycolipid antigen-antibody binding reactions. A method for the structural determination of partially methylated methyl glycosides is described. The proposed method, which is an alternative to that using alditol acetates, consists in the analysis of trimethylsilyl glycoside derivatives by gas chromatography-mass spectrometry in the electron impact (EI) mode. Seven partially methylated methyl rhamnopyranosides were synthesized, then purified by high-performance liquid chromatography. After trimethylsilylation, their EI mass spectra showed characteristic fragmentation patterns allowing the determination of the position and the number of methoxy groups in the sugar ring. This method was successfully applied to the structural elucidation of partially methylated sugars contained by a quantitatively minor phenolic glycolipid antigen isolated from Mycobacterium kansasii. Moreover, the carbons involved in the glycosidic linkages of the glycolipid tetrasaccharide moiety were also identified by this method after permethylation, methanolysis and trimethylsilylation.
部分甲基化糖苷在糖脂抗原-抗体结合反应的立体特异性中起重要作用。本文描述了一种用于测定部分甲基化甲基糖苷结构的方法。所提出的方法是使用糖醇乙酸酯方法的替代方法，它包括在电子轰击（EI）模式下通过气相色谱-质谱联用对三甲基硅烷基糖苷衍生物进行分析。合成了七种部分甲基化的甲基鼠李吡喃糖苷，然后通过高效液相色谱进行纯化。三甲基硅烷基化后，它们的EI质谱显示出特征性的裂解模式，从而能够确定糖环中甲氧基的位置和数量。该方法成功应用于从堪萨斯分枝杆菌中分离出的定量少量酚糖脂抗原所含部分甲基化糖的结构解析。此外，在全甲基化、甲醇解和三甲基硅烷基化后，该方法还鉴定了糖脂四糖部分糖苷键中涉及的碳原子。
