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Deviation from the mobile proton model in amino‐modified peptides: implications for multiple reaction monitoring analysis of peptides
Author(s) -
Locke Steven J.,
Leslie Andrew D.,
Melanson Jeremy E.,
Pinto Devanand M.
Publication year - 2006
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2512
Subject(s) - chemistry , fragmentation (computing) , peptide , tandem mass spectrometry , amino acid , selected reaction monitoring , mass spectrum , tandem , combinatorial chemistry , ion , tyrosine , mass spectrometry , chromatography , biochemistry , organic chemistry , materials science , computer science , composite material , operating system
Abstract The study of peptide fragmentation is important to the understanding of chemical processes occurring in the gas phase and the more practical concern of peptide identification for proteomic analysis. Using the mobile proton model as a framework, we explore the effect of amino‐group modifications on peptide fragmentation. Three aldehydes are used to transform the peptides' primary amino groups into either a dimethylamino or a heterocyclic structure (five‐ or six‐membered). The observed fragmentation patterns deviate strongly from those observed for the analogous underivatised peptides. In particular, the a 1 ion is the base peak in most tandem mass spectra of the derivatised peptides. The a 1 ion intensity depends strongly on the N‐terminal amino acid, with tyrosine and phenylalanine having the strongest enhancement. Despite the change in fragmentation patterns of the derivatised peptides, they still provide high‐quality tandem mass spectra that, in many cases, are more amenable to database searching than the spectra of underivatised peptides. In addition, the reliable presence of the a 1 ion facilitates rapid quantitative measurements using the multiple reaction monitoring approach. Copyright © 2006 John Wiley & Sons, Ltd.