Journal
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
Volume 308, Issue 1, Pages 89-97Publisher
ELSEVIER
DOI: 10.1016/j.ijms.2011.08.005
Keywords
Proline effect; Protonated peptides; Proline fragmentation map; Specific cleavage effect; Statistical analysis
Funding
- National Nature Foundation Committee of P.R. China [20875104, 21075138]
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An investigation of more than 130000 tandem mass spectra of praline-containing peptides extracted from Human and Ecoli peptide libraries in NIST Libraries (http://peptide.nist.gov/) is presented. In this study, fragmentation maps are drawn to show the fragmentation behavior of praline (Pro) in protonated peptides, taking the factors affecting the cleavage N-terminal to Pro as points of the map. In order to quantitatively characterize the fragmentation behavior of proline, probability of occurring selective cleavage at N-terminal side of Pro for each point is calculated. From the fragmentation maps, selective cleavage at N-terminal side of Pro is suppressed when all protons are sequestered by Args except at Asp-Pro and Glu-Pro. When protons are mobile, cleavage at N-terminal side of Pro is determined by pairwise cleavage Xxx-Pro and positions of praline in peptides. For triply and quadruply charged peptides, the Coulombic repulsion between protons affects the fragmentation of peptides and subsequently suppresses the cleavage at N-terminal side of Pro. Other fragmentation pathways influencing the fragmentation such as aspartic acid effect and y(N-2)/b(2) pathway are also found. Investigation of multiple praline containing peptides shows similar influential factors and competition between multiple prolines. (C) 2011 Published by Elsevier B.V.
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