An alternative GC–MS library for methylation analysis of polysaccharides via partially methylated aldononitrile acetates

The accurate characterization of glycosyl linkages in complex carbohydrates is always a challenging task due to the occurrence of isomer diversity and the unavailability of known standards. Because of the significant difference between head and tail in structures, this article built a complete methylation analysis library based on partially methylated aldononitrile acetates (PMANs) for facilitated identification of complex glycosidic linkages in polysaccharides. This library covered full EI-MS spectra and detailed fragmentation behaviors of corresponding PMANs ascribed to 46 aldohexoses, 32 aldopentoses and 16 deoxyhexoses. Furthermore, the elute behaviors of these PMANs are summarized on two capillary columns ascribed to complementary polarities. It is quite benefit to elucidate the glycosyl linkages of polysaccharides for inexperienced researchers in this field. The newly established PMAN library has been conformed to be an effective and alternative strategy for glycosyl linkage analysis of polysaccharides.