Fragmentation of α-radical cations of arginine-containing peptides

  • Julia Laskin
  • Zhibo Yang
  • C. M. Dominic Ng
  • Ivan K. Chu
Article

Abstract

Fragmentation pathways of peptide radical cations, M, with well-defined initial location of the radical site were explored using collision-induced dissociation (CID) experiments. Peptide radical cations were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes [salen=N,N′-ethylenebis (salicylideneiminato)]. Subsequent hydrogen abstraction from the β-carbon of the side-chain followed by Cα-Cβ bond cleavage results in the loss of a neutral side chain and formation of an α-radical cation with the radical site localized on the α-carbon of the backbone. Similar CID spectra dominated by radical-driven dissociation products were obtained for a number of arginine-containing α-radicals, suggesting that for these systems radical migration precedes fragmentation. In contrast, proton-driven fragmentation dominates CID spectra of α-radicals produced via the loss of the arginine side chain. Radical-driven fragmentation of large M peptide radical cations is dominated by side-chain losses, formation of even-electron a-ions and odd-electron x-ions resulting from Cα-C bond cleavages, formation of odd-electron z-ions, and loss of the N-terminal residue. In contrast, charge-driven fragmentation produces even-electron y-ions and odd-electron b-ions.

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Copyright information

© American Society for Mass Spectrometry 2010

Authors and Affiliations

  • Julia Laskin
    • 1
  • Zhibo Yang
    • 1
  • C. M. Dominic Ng
    • 2
  • Ivan K. Chu
    • 2
  1. 1.Chemical and Materials Sciences DivisionPacific Northwest National LaboratoryRichlandUSA
  2. 2.Department of ChemistryUniversity of Hong KongHong KongChina

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