Monosaccharide composition and glycosidic linkages analysis by ultra high performance liquid chromatography-triple quadrupole tandem mass spectrometry-Case study of plant polysaccharides.

Monosaccharide composition and glycosidic linkages analysis are essential for the structural characterization and biological activity research of polysaccharides. To simplify the analysis steps and improve detection efficiency, this study developed monosaccharide compositions and glycosidic linkages detection methods based on UPLC-QqQ-MS/MS, and established a plant polysaccharide glycosidic linkages library. Furthermore, the detailed analysis process of monosaccharide compositions and glycosidic linkages was presented through a plant polysaccharide (Chinese bayberry wine polysaccharide, CPW) example. The results showed that the monosaccharide analysis method could identify and quantify 20 monosaccharides within 13 min by 6 chromatograms. By this method, 7 monosaccharides were detected in CPW, which was consistent with previous results obtained using ion chromatography. Meanwhile, the UPLC-QqQ-MS/MS based method could analyze 112 glycosidic linkages of 9 plant monosaccharides within 30 min, and the results were distributed on 11 chromatograms. According to the approach, 44 different glycosidic linkages were identified in CPW. Based on Congo red assay and molecular weight as well as our findings of monosaccharide composition and glycosidic linkages, we proposed that CPW may consist of two distinct sugar chains: One composed of 1-2,4-Rha, 1-3,4-GalA, and 1-F-Ara, and the other composed of 1-3,4-Gal, 1-4-Gal, 1-3,4,6-Gal, and 1-F-Ara.