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Sequencing of sulfonic acid derivatized peptides by electrospray mass spectrometry
Author(s) -
Bauer Mark D.,
Sun Yiping,
Keough Thomas,
Lacey Martin P.
Publication year - 2000
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/(sici)1097-0231(20000530)14:10<924::aid-rcm967>3.0.co;2-x
Subject(s) - chemistry , protonation , fragmentation (computing) , mass spectrometry , tandem mass spectrometry , electrospray ionization , derivatization , chromatography , peptide , protein mass spectrometry , collision induced dissociation , ion , organic chemistry , biochemistry , computer science , operating system
We report the application of nanoelectrospray ionization tandem mass spectrometry (nES‐MS/MS) and capillary LC/microelectrospray MS/MS (cLC/µES‐MS/MS) for sequencing sulfonic acid derivatized tryptic peptides. These derivatives were specifically prepared to facilitate low‐energy charge‐site‐initiated fragmentation of C‐terminal arginine‐containing peptides, and to enhance the selective detection of a single series of y‐type fragment ions. Both singly and doubly protonated peptides were analyzed by MS/MS and the results were compared with those from their derivatized counterparts. Model peptides and peptides from tryptic digests of gel‐isolated proteins were analyzed. Derivatized singly protonated peptides fragment in the same way by nES‐MS/MS as they do by post‐source decay matrix‐assisted laser desorption/ionization mass spectrometry (PSD‐MALDI‐MS). They produce fragment ion spectra dominated by y‐ions, and the simplified spectra are readily interpreted de novo . Doubly protonated peptides fragment in much the same way as their non‐derivatized doubly protonated counterparts. The fragmentation of doubly protonated derivatives is especially useful for sequencing peptides that possess a proline residue near the N‐terminus of the molecule. The singly protonated forms of these proline‐containing derivatives often show enhanced fragmentation on the N‐terminal side of the proline and considerably reduced fragmentation on the C‐terminal side. In addition, sulfonic acid derivatization increases the in‐source fragmentation of arginine‐containing peptides. This could be useful for sequence verification and sequence tagging for use in single stage mass spectrometry. Copyright © 2000 John Wiley & Sons, Ltd.