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Fragmentation of negative ions from N-linked carbohydrates, Part 4. Fragmentation of complex glycans lacking substitution on the 6-antenna

机译:N-连接碳水化合物中负离子的裂解,第4部分。6天线上缺乏取代的复杂聚糖的裂解

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Negative ion CID spectra of N-linked glycans released from glycoproteins contain many ions that are diagnostic for specific structural features such as the detailed arrangement of antennae and the location of fucose residues. Identification of such ions requires reference glycans that are often difficult to acquire in a pure state. The recent acquisition of a sample of N-glycans from a patient lacking the enzyme N-acetylglucosaminyltransferase-2 provided an opportunity to investigate fragmentation of glycans lacking a 6-antenna. These glycans contained one or two galactose-N-acetylglucosamine-chains attached to the 3-linked mannose residue of the trimannosyl-chitobiose core with and without fucose substitution. The spectra from the patient sample clearly defined the antenna distribution and showed striking differences from the spectra of isomeric compounds obtained from normal subjects. Furthermore, they provided additional information on previously identified antenna-specific fragment ions and indicated the presence of additional ions that were diagnostic of fucose substitution. Glycans obtained from such enzyme-deficient patients can, thus, be a valuable way of obtaining spectra of specific isomers in a relatively pure state for interpretation of mass spectra.
机译:从糖蛋白释放的N-连接聚糖的负离子CID谱包含许多离子,这些离子可诊断特定的结构特征,例如触角的详细排列和岩藻糖残基的位置。对此类离子的鉴定需要参考聚糖,这些参考聚糖通常很难以纯净状态获得。最近从缺乏酶N-乙酰氨基葡萄糖氨基转移酶2的患者身上获取了N-聚糖样品,这为研究缺乏6天线的聚糖片段化提供了机会。这些聚糖含有一个或两个半乳糖-N-乙酰氨基葡糖链,该链连接到三甘露糖基-壳二糖核心的3-连接的甘露糖残基上,具有和不具有岩藻糖取代基。来自患者样品的光谱清楚地定义了天线分布,并显示出与从正常受试者获得的异构化合物的光谱显着差异。此外,他们提供了有关先前确定的天线特异性碎片离子的其他信息,并指出了诊断岩藻糖替代的其他离子的存在。因此,从此类缺乏酶的患者那里获得的聚糖可以成为获得相对纯净状态的特定异构体光谱的一种有价值的方法,用于解释质谱。

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