Negative ion fragmentation of cysteic acid containing peptides: Cysteic acid as a fixed negative charge

Brad J. Williams, Christopher K. Barlow, Kevin L. Kmiec, William K. Russell, David H. Russell

Research output: Contribution to journalArticle

5 Scopus citations

Abstract

We present here a study of the collision induced dissociation (CID) of deprotonated cysteic acid containing peptides produced by MALDI. The effect of cysteic acid (C ox) position is interrogated by considering the positional isomers, C oxLVINVLSQG, LVINVLSQGC ox, and LVINVC oxLSQG. Although considerable variation between the CID spectra is observed, the mechanistic picture that emerges involves charge retention at the deprotonated cysteic acid side chain. Fragmentation occurs in the proximity of the cysteic acid group by charge directed mechanisms as well as remote from this group to form ions, which may be rationalized by charge remote mechanisms. Additionally, the formation of the SO 3 -• ion is observed in all cases. Fragmentation of C oxLVINVLSQC ox provides both N- and C-terminal, y and b ions, respectively indicating that the negative charge may be retained at either of the cysteic acids; however, there is some evidence that charge retention at the C-terminal cysteic acid may be preferred. Fragmentation of tryptic type peptides containing a C-terminal arginine or lysine residue is considered through comparison of three peptides C oxLVINKLSQG, C oxLVINVLSQK, and C oxLVINVLSQR. Lastly, we rationalize the formation of b n-1 + H 2O and a n-1 ions through a mechanism involving rearrangement of the C-terminal residue to form a mixed anhydride intermediate.

Original languageEnglish (US)
Pages (from-to)1622-1630
Number of pages9
JournalJournal of the American Society for Mass Spectrometry
Volume22
Issue number9
DOIs
StatePublished - Sep 1 2011
Externally publishedYes

Keywords

  • Cysteic acid-containing peptides
  • MALDI-MS
  • Negative ion tandem mass spectrometry
  • Solution-phase performic acid oxidation
  • d-type fragment ions

ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy

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