Analysis of Chain and Blood Group Type and Branching Pattern of Sialylated Oligosaccharides by Negative Ion Electrospray Tandem Mass Spectrometry

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• 作者：Wengang Chai ; Vladimir E. Piskarev ; Barbara Mulloy ; Yan Liu ; Philip G. Evans ; Helen M. I. Osborn ; and Alexander M. Lawson
• 刊名：Analytical Chemistry
• 出版年：2006
• 出版时间：March 1, 2006
• 年：2006
• 卷：78
• 期：5
• 页码：1581 - 1592
• 全文大小：395K
• 年卷期：v.78,no.5(March 1, 2006)
• ISSN：1520-6882

文摘

We previously reported sequence determination of neutraloligosaccharides by negative ion electrospray tandemmass spectrometry on a quadrupole-orthogonal time-of-flight instrument with high sensitivity and without theneed of derivatization. In the present report, we extendour strategies to sialylated oligosaccharides for analysisof chain and blood group types together with branchingpatterns. A main feature in the negative ion mass spectrometry approach is the unique double glycosidic cleavage induced by 3-glycosidic substitution, producing characteristic D-type fragments which can be used to distinguish the type 1 and type 2 chains, the blood grouprelated Lewis determinants, 3,6-disubstituted core branching patterns, and to assign the structural details of eachof the branches. Twenty mono- and disialylated linear andbranched oligosaccharides were used for the investigation,and the sensitivity achieved is in the femtomole range.To demonstrate the efficacy of the strategy, we havedetermined a novel complex disialylated and monofucosylated tridecasaccharide that is based on the lacto-N-decaose core. The structure and sequence assignment wascorroborated by methylation analysis and ¹H NMR spectroscopy.