在酸的碰撞诱导解离过程中对序列信息进行编码
Alex G Harrison1, Alex B Young, Christian Bleiholder
1Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada. aharriso@chem.utoronto.ca
Journal of the American Chemical Society
|August 10, 2006
概括
质子的碰撞诱导解离 (CID) 可以混序列信息. YAGFL-NH2的碎片化形成了一个oxazolone中间体,该中间体重新排列,产生非序列特定的碎片离子.
科学领域:
- 蛋白质组学和质谱学
- 化学动力学和碎片化机制
背景情况:
- 碰撞诱导解离 (CID) 是序列的关键技术.
- 了解碎片化途径对于准确的鉴定至关重要.
- 质子化可以表现出复杂的解离行为.
研究的目的:
- 为了研究在质子化YAGFL-NH2.2的CID中观察到的非序列特异的碎片离子.
- 阐明导致CID中的序列杂乱的反应机制.
- 为碎片化途径提供实验和理论证据.
主要方法:
- 实验性CID实验对质子YAGFL-NH2.2进行了实验.
- 理论计算以建模碎片化路径.
- 碎片离子质量和结构的分析.
主要成果:
- 初级碎片化产生一个线性YAGFLoxa b5离子与一个C端的oxazolone.
- 氧沙的中间体受到N端氨基群的分子内攻击,形成循环B5异构体.
- 质子转移反应和循环异构体的环开放导致编码的序列信息.
结论:
- 质子YAGFL-NH2的CID产生的非序列特异的碎片离子由于oxazolone的形成和随后的重新排列.
- 在CID过程中诱导序列杂乱时,oxazolone中间体起着至关重要的作用.
- 这些发现凸显了在某些情况下从CID光谱直接序列导出的局限性.
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