Typing of Blood-Group Antigens on Neutral Oligosaccharides by Negative-Ion Electrospray Ionization Tandem Mass Spectrometry

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• 作者：Hongtao Zhang ; Shuang Zhang ; Guanjun Tao ; Yibing Zhang ; Barbara Mulloy ; Xiaobei Zhan ; Wengang Chai
• 刊名：Analytical Chemistry
• 出版年：2013
• 出版时间：June 18, 2013
• 年：2013
• 卷：85
• 期：12
• 页码：5940-5949
• 全文大小：616K
• 年卷期：v.85,no.12(June 18, 2013)
• ISSN：1520-6882

文摘

Blood-group antigens, such as those containing fucose and bearing the ABO(H)- and Lewis-type determinants expressed on the carbohydrate chains of glycoproteins and glycolipids, and also on unconjugated free oligosaccharides in human milk and other secretions, are associated with various biological functions. We have previously shown the utility of negative-ion electrospay ionization tandem mass spectrometry with collision-induced dissociation (ESI-CID-MS/MS) for typing of Lewis (Le) determinants, for example, Le^a, Le^x, Le^b, and Le^y on neutral and sialylated oligosaccharide chains. In the present report, we extended the strategy to characterization of blood-group A-, B-, and H-determinants on type 1 and type 2 and also on type 4 globoside chains to provide a high sensitivity method for typing of all the major blood-group antigens, including the A, B, H, Le^a, Le^x, Le^b, and Le^y determinants, present in oligosaccharides. Using the principles established, we identified two minor unknown oligosaccharide components present in the products of enzymatic synthesis by bacterial fermentation. We also demonstrated that the unique fragmentations derived from the D- and ^0,2A-type cleavages observed in ESI-CID-MS/MS, which are important for assigning blood-group and chain types, only occur under the negative-ion conditions for reducing sugars but not for reduced alditols or under positive-ion conditions.