Structure of electron-capture dissociation fragments from charge-tagged peptides probed by tunable infrared multiple photon dissociation.

Abstract : 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.
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https://hal.archives-ouvertes.fr/hal-00467063
Contributeur : Gilles Frison <>
Soumis le : jeudi 25 mars 2010 - 22:24:33
Dernière modification le : mercredi 20 mars 2019 - 12:12:02

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Gilles Frison, Guillaume van der Rest, Frantisek Turecek, Thierry Besson, Joël Lemaire, et al.. Structure of electron-capture dissociation fragments from charge-tagged peptides probed by tunable infrared multiple photon dissociation.. Journal of the American Chemical Society, American Chemical Society, 2008, 130 (45), pp.14916-14917. ⟨10.1021/ja805257v⟩. ⟨hal-00467063⟩

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