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Investigation of intramolecular proton migration in a series of model, metal‐cationized tripeptides using in situ generation of an isotope label
Author(s) -
Bulleigh Kellis,
Howard Angela,
Do Trang,
Wu Qun,
Anbalagan Victor,
Stipdonk Michael Van
Publication year - 2005
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.2299
Subject(s) - chemistry , intramolecular force , tripeptide , peptide , scrambling , collision induced dissociation , dissociation (chemistry) , deuterium , amide , isotope , mass spectrometry , in situ , stereochemistry , crystallography , tandem mass spectrometry , chromatography , organic chemistry , biochemistry , linguistics , philosophy , physics , quantum mechanics
Abstract In this study we used an isotope label, generated in situ , to investigate intramolecular proton migration or scrambling during formation of [b 2 +17+Li] + products by collision‐induced dissociation (CID) of Li + ‐cationized tripeptides. To generate the isotope label, we used a McLafferty‐type rearrangement of N‐terminally acetylated, C‐terminal peptide tert ‐butyl esters in which all amide positions were exchanged with deuterium. Using a set of small, model peptides, we show that intramolecular proton scrambling occurs during CID, particularly amongst adjacent sites along a peptide backbone, on the time scales employed for low‐energy collisional activation in an ion‐trap mass spectrometer. Copyright © 2005 John Wiley & Sons, Ltd.