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Abstract
Relative energetics of fragmentation of protonated peptides are investigated by using electrospray ionization/surface-induced dissociation (ESI/SID) tandem mass spectrometry. ESI/SID fragmentation efficiency curves (percent fragmentation versus laboratory collision energy) are presented for 20 oligopeptides and are a measure of how easily a peptide fragments. The relative positions of the ESI/SID fragmentation efficiency curves depend on several parameters which include peptide composition (e.g., presence/absence of a basic amino acid residue) and peptide size. The ESI/SID fragmentation efficiency curves, in combination with quantum chemical calculations, provide a unique approach to substantiate and refine the mobile proton model for peptide fragmentation. Selected peptides are also investigated to further test and confirm the mobile proton model; these include doubly-protonated peptides and chemically-modified peptides (i.e., acetylated and fixed-charge derivatized peptides). Doubly-protonated peptides ...
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