Fragmentation studies of cationized amino acids and small peptides as studied using guided ion beam tandem mass spectrometry (GIBMS) are reviewed. After a brief examination of the key attributes of the GIBMS approach, results for a variety of systems are examined, compared, and contrasted. Cationization of amino acids, diglycine, and triglycine with alkali cations generally leads to dissociations in which the intact biomolecule is lost. Exceptions include most lithiated species as well as a few examples for sodiated and one example for potassiated species. Like the lithiated species, cationization by protons leads to numerous dissociation channels. Results for protonated glycine, cysteine, asparagine, diglycine, and a series of tripeptides are reviewed, along with the thermodynamic consequences that can be gleaned. Finally, the important physiological process of the deamidation of asparagine (Asn) residues is explored by the comparison of five dipeptides in which the C-terminal partner (AsnXxx) is altered. The GIBMS thermochemistry is shown to correlate well with kinetic results from solution phase studies.

中文翻译：

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使用引导离子束串联质谱法探索阳离子氨基酸和肽分解的能量学和机制

综述了使用引导离子束串联质谱 (GIBMS) 研究的阳离子化氨基酸和小肽的断裂研究。在对 GIBMS 方法的关键属性进行简要检查后，对各种系统的结果进行了检查、比较和对比。氨基酸、二甘氨酸和三甘氨酸与碱性阳离子的阳离子化通常会导致解离，从而使完整的生物分子丢失。例外情况包括大多数锂化物质以及一些钠化物质和钾化物质的一个例子。与锂化物质一样，质子的阳离子化导致许多解离通道。回顾了质子化甘氨酸、半胱氨酸、天冬酰胺、二甘氨酸和一系列三肽的结果，以及可以收集到的热力学结果。最后，通过比较 C 端伴侣 (AsnXxx) 发生改变的五种二肽，探索了天冬酰胺 (Asn) 残基脱酰胺的重要生理过程。GIBMS 热化学显示与溶液相研究的动力学结果密切相关。