Electrospray mass spectrometry and fragmentation of N-linked carbohydrates derivatized at the reducing terminus

Electrospray mass spectrometry and fragmentation of N-linked carbohydrates derivatized at the reducing terminus
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DOI:
10.1016/s1044-0305(00)00156-2
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发表时间:
2000-10-01
影响因子:
3.2
通讯作者:
Harvey, DJ
Harvey, DJ
中科院分区:
化学3区
文献类型:
--
作者:
Harvey, DJ

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通过还原胺化从2-氨基苯甲酰胺、2-氨基吡啶、3-氨基喹啉、2-氨基吖啶酮、4-氨基-N-(2-二乙基氨基乙基)苯甲酰胺和4-氨基苯甲酸的甲酯、乙酯和丁酯制备N-连接聚糖衍生物。它们的电喷雾和碰撞诱导解离(CID)的碎片光谱进行了检查与Q-TOF质谱仪。除了用4-氨基-N-(2-二乙基氨基乙基)苯甲酰胺衍生的糖得到非常强的双电荷[M + H + Na](2+)离子外,所有衍生物的[M + Na](+)离子都得到了最强的信号。最强的[M + Na](+)离子信号来自4-氨基苯甲酸丁酯,最弱的来自2-氨基吡啶。从[M + Li](+)或[M + Na](+)离子记录了最具信息性的光谱。这些光谱占主导地位的序列揭示糖苷裂解和“内部”片段产生的离子。连接揭示交叉环裂解离子相当丰富,特别是从高甘露糖聚糖。虽然衍生物的性质被发现对片段化模式几乎没有影响,3-氨基喹啉衍生物比其他衍生物产生稍微更丰富的交叉环片段。[M + H](+)离子仅形成具有很少(如果有的话)交叉环裂解离子的糖苷片段。双电荷分子离子提供的信息较少;单电荷碎片较弱,含氢分子离子([M +2 H](2+)和[M + H + Na](2+))作为[M + H](+)单电荷离子碎片化,没有明显的交叉环裂解。(J Am Soc Mass Spectrom 2000,11,900-915)(C)2000美国质谱学会。
Derivatives were prepared from N-linked glycans by reductive amination from 2-aminobenzamide, 2-aminopyridine, 3-aminoquinoline, 2-aminoacridone, 4-amino-N-(2-diethylaminoethyl)benzamide, and the methyl, ethyl, and butyl esters of 4-aminobenzoic acid. Their electrospray and collision-induced dissociation (CID) fragmentation spectra were examined with a Q-TOF mass spectrometer. The strongest signals were obtained from the [M + Na](+) ions for all derivatives except sugars derivatized with 4-amino-N-(2-diethylaminoethyl)benzamide which gave very strong doubly charged [M + H + Na](2+) ions. The strongest [M + Na](+) ion signals were obtained from the butyl ester of 4-aminobenzoic acid and the weakest from 2-aminopyridine. The most informative spectra were recorded from the [M + Li](+) or [M + Na](+) ions. These spectra were dominated by ions produced by sequence-revealing glycosidic cleavages and "internal" fragments. Linkage-revealing cross-ring cleavage ions were reasonably abundant, particularly from high-mannose glycans. Although the nature of the derivative was found to have little effect upon the fragmentation pattern, 3-aminoquinoline derivatives gave marginally more abundant cross-ring fragments than the other derivatives. [M + H](+) ions formed only glycosidic fragments with few, if any, cross-ring cleavage ions. Doubly charged molecular ions gave less informative spectra; singly charged fragments were weak, and molecular ions containing hydrogen ([M + 2H](2+) and [M + H + Na](2+)) fragmented as the [M + H](+) singly charged ions with no significant cross-ring cleavages. (J Am Soc Mass Spectrom 2000, 11, 900-915) (C) 2000 American Society for Mass Spectrometry.