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Gas‐phase peptide fragmentation: how understanding the fundamentals provides a springboard to developing new chemistry and novel proteomic tools
Author(s) -
Barlow Christopher K.,
O'Hair Richard A. J.
Publication year - 2008
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1469
Subject(s) - chemistry , electron transfer dissociation , fragmentation (computing) , gas phase , protonation , reagent , dissociation (chemistry) , peptide , electron capture dissociation , combinatorial chemistry , polyatomic ion , ion , computational chemistry , electron transfer , mass spectrometry , tandem mass spectrometry , organic chemistry , fourier transform ion cyclotron resonance , chromatography , biochemistry , computer science , operating system
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.