König S, Leary J A
College of Chemistry, University of California, Berkeley 94720-1460, USA.
J Am Soc Mass Spectrom. 1998 Nov;9(11):1125-34. doi: 10.1016/S1044-0305(98)00096-8.
A methodology to determine the linkage position of oligosaccharides is presented. In order to illustrate this technique, several oligosaccharides and disaccharides were ionized by electrospray and analyzed in a Paul trap mass spectrometer. Multiple stage tandem mass spectrometry experiments were used to determine linkage and structural information for the following four cobalt coordinated and singly charged ([M + Co-H]+) pentasaccharides: Lacto-N-fucopentaose I, II, III, and V. In order to differentiate between linkage positions, multiple low energy collision induced experiments with mass selected C type ions have been carried out in an ion trap mass spectrometer. Because of the coordination with cobalt, which directs the dissociation pathways, these C type ions undergo specific fragmentation reactions upon low energy collision induced dissociation. These dissociation pathways are unambiguously dependent on their linkage position, thus allowing differentiation between 1-->2, 1-->3, 1-->4, and 1-->6 linkage positions throughout the oligomers. Studies on various linked disaccharides and N-acetyl-disaccharides, which are smaller constituents of the pentasaccharides, were used to verify and confirm the results obtained from the pentasaccharides.
本文提出了一种确定寡糖连接位置的方法。为了说明该技术，几种寡糖和二糖通过电喷雾离子化，并在保罗阱质谱仪中进行分析。多级串联质谱实验用于确定以下四种钴配位且单电荷（[M + Co - H]+）的五糖的连接和结构信息：乳糖-N-岩藻五糖I、II、III和V。为了区分连接位置，在离子阱质谱仪中对质量选择的C型离子进行了多次低能碰撞诱导实验。由于与钴的配位作用引导了解离途径，这些C型离子在低能碰撞诱导解离时会发生特定的碎片化反应。这些解离途径明确依赖于它们的连接位置，从而能够区分整个寡聚物中1→2、1→3、1→4和1→6的连接位置。对各种连接二糖和N-乙酰二糖（五糖的较小组成部分）的研究用于验证和确认从五糖获得的结果。
