化胺离子的碰撞诱导解离
Arnold Steckel1, Dávid Papp1,2, Katalin Uray3
1MTA-ELTE Lendület Ion Mobility Mass Spectrometry Research Group, Department of Analytical Chemistry, ELTE Eötvös Loránd University, Budapest 1117, Hungary.
概括
负电子喷射电离 (ES-) 双重质谱 (MS/MS) 揭示了从素化中受益的HNCO损失,提供了补充的结构见解. 这项研究详细介绍了ES-中的HNCO损失机制,有助于区分素酸和脱酸序列.
科学领域:
- 蛋白质组学和分析化学
- 质谱测量质量谱测量
- 翻译后修改 翻译后修改
背景情况:
- 阳性电喷电离 (ES+) 双重质谱法 (MS/MS) 是用于标识的标准.
- 负电喷射电离 (ES-) 提供了补充的结构信息,特别是在翻译后修改 (PTM) 时.
- 在ES-中素的碎片化以前没有被研究过.
研究的目的:
- 使用负电喷射电离 (ES-) MS/MS.探索素化的碎片化.
- 描述ES-中素化的HNCO损失,并提出一个反应机制.
- 为了将ES-碎片化模式与ES+进行比较,并确定素的诊断离子.
主要方法:
- 通过循序渐进的碰撞能量依赖测量,研究了9种素.
- 在QTOF和Q-Orbitrap仪器上利用了高分辨率,高精度的质谱学.
- 分析了碎片化模式,包括中性损失和序列离子形成.
主要成果:
- 观察到有利的,从前体和ES-中的碎片中选择性丧失HNCO,类似于ES+.
- 在ES-中,HNCO损失强度往往高于ES+.
- 确定了对Asp和Glu残留物的偏好裂解N端,以及来自序列离子的显著中性损失.
结论:
- 这项研究描述了ES-中素化的HNCO损失,并首次提出了一个机制.
- 在ES-MS/MS中,有利的HNCO损失和N端切割到Asp/Glu残留物可以区分氨酸和脱胺序列.
- 虽然ES-光谱需要人工检查,但这些发现增强了它在蛋白质组学中用于PTM分析的实用性.
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