Structure of Electron-Capture Dissociation Fragments from Charge-Tagged Peptides Probed by Tunable Infrared Multiple Photon Dissociation

被引:57
作者
Frison, Gilles [1 ,2 ]
van der Rest, Guillaume [1 ,2 ]
Turecek, Frantisek [3 ]
Besson, Thierry [4 ]
Lemaire, Joel [4 ]
Maitre, Philippe [4 ]
Chamot-Rooke, Julia [1 ,2 ]
机构
[1] Ecole Polytech, Dept Chem, Lab Mecanismes Reactionnels, F-91128 Palaiseau, France
[2] CNRS, F-91128 Palaiseau, France
[3] Univ Washington, Dept Chem, Seattle, WA USA
[4] Univ Paris 11, Chim Phys Lab, F-91405 Orsay, France
基金
美国国家科学基金会;
关键词
D O I
10.1021/ja805257v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this study, we propose the first spectroscopic structural characterization of c-type ions produced by ECD of a peptide. The structure of c-type ions formed by electron capture dissociation and the overall mechanism leading to their formation are still a question of debate. Depending on the mechanism, c-type ions have been proposed to have either an enol-imine structure (-C(OH)=NH) or an amide one (-C(O)-NH2). Since these ions are isomeric, mass spectrometry only cannot discriminate between them, but infrared spectroscopy can bring experimental evidence and help determine which scheme is operative. Using the coupling between a tunable free electron laser and a FT-ICR mass spectrometer, we show that c-type ions have an amide structure, characterized by an IR signature of the C=O stretch at 1731 cm(-1). This result is particularly interesting from the perspective of the elucidation of the ECD mechanism.
引用
收藏
页码:14916 / +
页数:3
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