Presented in part at the 55th American Society for Mass Spectrometry Conference, Indiana Convention Center, Indianapolis, IN, USA, June 3– 7, 2007.
Special Feature: Tutorial
Article first published online: 25 SEP 2008
Copyright © 2008 John Wiley & Sons, Ltd.
Journal of Mass Spectrometry
Volume 43, Issue 10, pages 1301–1319, October 2008
How to Cite
Barlow, C. K. and O'Hair, R. A. J. (2008), Gas-phase peptide fragmentation: how understanding the fundamentals provides a springboard to developing new chemistry and novel proteomic tools. J. Mass Spectrom., 43: 1301–1319. doi: 10.1002/jms.1469
Dedicated to Prof. John H. Bowie on the occasion of his 70th birthday and in recognition of his many important contributions to mass spectrometry including the gas-phase fragmentation chemistry of peptide anions.
Part 60 of the series ‘Gas Phase Ion Chemistry of Biomolecules’.
- Issue published online: 25 SEP 2008
- Article first published online: 25 SEP 2008
- Manuscript Accepted: 16 JUN 2008
- Manuscript Received: 10 APR 2008
- Australian Research Council
- collision-induced dissociation;
- electron transfer dissociation;
- disulfide bond;
- metal ions
This tutorial provides an overview of the evolution of some of the key concepts in the gas-phase fragmentation of different classes of peptide ions under various conditions [e.g. collision-induced dissociation (CID) and electron transfer dissociation (ETD)], and then demonstrates how these concepts can be used to develop new methods. For example, an understanding of the role of the mobile proton and neighboring group interactions in the fragmentation reactions of protonated peptides has led to the design of the ‘SELECT’ method. For ETD, a model based on the Landau–Zener theory reveals the role of both thermodynamic and geometric effects in the electron transfer from polyatomic reagent anions to multiply protonated peptides, and this predictive model has facilitiated the design of a new strategy to form ETD reagent anions from precursors generated via ESI. Finally, two promising, emerging areas of gas-phase ion chemistry of peptides are also described: (1) the design of new gas-phase radical chemistry to probe peptide structure, and (2) selective cleavage of disulfide bonds of peptides in the gas phase via various physicochemical approaches. Copyright © 2008 John Wiley & Sons, Ltd.