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表面诱导解离:一种探测质子化肽段结构、能量学及碎裂机制的有效工具。

Surface-induced dissociation: an effective tool to probe structure, energetics and fragmentation mechanisms of protonated peptides.

作者信息

Dongré A R, Somogyi A, Wysocki V H

机构信息

Department of Chemistry, Virginia Commonwealth University, Richmond 23284-2006, USA.

出版信息

J Mass Spectrom. 1996 Apr;31(4):339-50. doi: 10.1002/(SICI)1096-9888(199604)31:4<339::AID-JMS322>3.0.CO;2-L.

DOI:10.1002/(SICI)1096-9888(199604)31:4<339::AID-JMS322>3.0.CO;2-L
PMID:8799282
Abstract

The utility of surface-induced dissociation (SID) to probe the structure, energetics and fragmentation mechanisms of protonated peptides is discussed and demonstrated. High internal energy deposition provided by low-energy (eV range) ion-surface collisions yields extensive fragmentation of protonated peptides, allowing relatively uncomplicated and rapid sequence analysis of oligopeptides. SID of multiply protonated peptides is illustrated for peptides with molecular mass of up to approximately 5000 u. It is also illustrated that SID combined with electrospray ionization (ESI) provides a distinctive experimental technique to determine the energetics and mechanisms of peptide fragmentation. The relative position of ESI/SID fragmentation efficiency curves (plots of percentage fragmentation vs. laboratory collision energy) for peptides can be utilized to estimate relative energetics of peptide fragmentation and even to predict proton localization sites. The observed trends support the essential role of the mobile proton model in understanding peptide fragmentation by low-energy tandem mass spectrometry.

摘要

本文讨论并展示了表面诱导解离(SID)在探测质子化肽段的结构、能量学和碎裂机制方面的效用。低能(电子伏特范围)离子-表面碰撞所提供的高内能沉积会导致质子化肽段发生广泛碎裂,从而实现对寡肽相对简单且快速的序列分析。对于分子量高达约5000 u的肽段,展示了多质子化肽段的SID情况。还表明,SID与电喷雾电离(ESI)相结合提供了一种独特的实验技术,用于确定肽段碎裂的能量学和机制。肽段的ESI/SID碎裂效率曲线(碎裂百分比与实验室碰撞能量的关系图)的相对位置可用于估计肽段碎裂的相对能量学,甚至预测质子定位位点。观察到的趋势支持了移动质子模型在理解低能串联质谱法中肽段碎裂过程中的重要作用。

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