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

J Am Chem Soc

Laboratoire des Mécanismes Réactionnels, Department of Chemistry, Ecole Polytechnique and CNRS, 91128 Palaiseau, France.

Published: November 2008

AI Article Synopsis

  • This study presents the first spectroscopic analysis of c-type ions produced by electron capture dissociation (ECD) of a peptide.
  • There is ongoing debate about whether these ions have an enol-imine or an amide structure due to their isomeric nature, which makes mass spectrometry alone insufficient for differentiation.
  • Using a combination of a free electron laser and FT-ICR mass spectrometry, the researchers determined that c-type ions possess an amide structure, evidenced by a distinct infrared signature at 1731 cm(-1).

Article 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.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ja805257vDOI Listing

Publication Analysis

Top Keywords

c-type ions
16
ions
5
structure
4
structure electron-capture
4
electron-capture dissociation
4
dissociation fragments
4
fragments charge-tagged
4
charge-tagged peptides
4
peptides probed
4
probed tunable
4

Similar Publications

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!