Investigating
substituent effects on the fragmentation spectra of protonated peptides
modified to create N-terminal imines
Nelson, Robert; van Stipdonk,
Michael; Patterson, Khiry.
Department of
Chemistry and Biochemistry
Duquesne
University
Tandem
mass spectrometry (MSn) and collision induced dissociation (CID) are among the
most important tools used to identify peptides and proteins in proteomics. Fragmentation of gas-phase, protonated
peptides creates product ions that reveal amino acid sequence. Recently we found that conversion of peptides
to N-terminal imines (as Schiff bases) enhances the sequence information
revealed by the MSn approach. Further
investigation of substituent effects on the fragmentation spectra through the
interchange of the aldehyde/ketone reactant in the modification step may reveal
even more important sequence information. It is the goal of this research to
prepare peptide-imines in the gas phase, investigate the influence of
substituents on product ion distributions and assess improvements to MSn sequencing gained by the modification.
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