Negative ion electrospray mass spectrometry of neutral underivatized oligosaccharides

Negative ion electrospray mass spectrometry of neutral underivatized oligosaccharides
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DOI:
10.1021/ac0010126
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发表时间:
2001-02-01
影响因子:
7.4
通讯作者:
Lawson, AM
Lawson, AM
中科院分区:
化学1区
文献类型:
--
作者:
Chai, WG;Piskarev, V;Lawson, AM

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在四极正交夜间仪器上进行碰撞诱导解离 (CID) 和 MS/MS 扫描的负离子电喷雾质谱 (ES-MS) 为中性未衍生低聚糖的结构分析提供了一种灵敏的方法。分子量信息可以很容易地从亚纳摩尔量寡糖形成的 ES 质谱中的主要 [M - H](-) 离子获得,并且 CID-MS/MS 也可以提供类似的灵敏度来给出结构细节。 14 种寡糖的 CID 谱表明,可以导出序列和部分连锁信息,并且可以区分异构体结构。系列 C 型碎片离子提供序列信息,而 3 连接的 GlcNAc 或 Glc 的双糖苷 D 型裂解和 4 连接的 GlcNAc 或 Glc 的 (0,2)A 型糖环断裂可以提供部分连接信息。独特的 D 和 A 切割对于区分 1 型和 2 型寡糖链以及定义由其岩藻糖基化类似物携带的血型 H、Le(a)、Le(X)、Le(b) 和 Le(y) 决定簇非常重要。
Negative-ion electrospray mass spectrometry (ES-MS) with collision-induced dissociation (CID) and MS/MS scanning on a quadrupole-orthoganal time-of-night instrument provide a sensitive means for structural analysis of neutral underivatized oligosaccharides. Molecular mass information can be readily obtained from the dominant [M - H](-) ions in the ES mass spectrum formed with subnanomole amounts of oligosaccharides, and similar sensitivity is available from CID-MS/MS to give structural details. The CID spectra of 14 oligosaccharides demonstrated that sequence and partial linkage information can be derived and isomeric structures can be differentiated. Series of C-type fragment ions give sequence information while the double glycosidic D-type cleavage of a 3-linked GlcNAc or Glc and the saccharide ring fragmentation of the (0,2)A-type from 4-linked GlcNAc or Glc can provide partial linkage information. The distinctive D- and A-cleavages are important for differentiation of oligosaccharide type 1 and type 2 chains and to define the blood group H, Le(a), Le(X), Le(b), and Le(y) determinants carried by their fucosylated analogues.