Investigation of intramolecular proton migration in a series of model, metal-cationized tripeptides using in situ generation of an isotope label
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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.
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Rapid Commun. Mass Spectrom.