Journal of the American Society for Mass Spectrometry

, Volume 17, Issue 9, pp 1315–1321

Structures of α-type ions formed in the 157 nm photodissociation of singly-charged peptide ions


  • Liangyi Zhang
    • Department of ChemistryIndiana University
  • Weidong Cui
    • Department of ChemistryIndiana University
  • Matthew S. Thompson
    • Department of ChemistryIndiana University
    • Department of ChemistryIndiana University
Application Note

DOI: 10.1016/j.jasms.2006.06.007

Cite this article as:
Zhang, L., Cui, W., Thompson, M.S. et al. J Am Soc Mass Spectrom (2006) 17: 1315. doi:10.1016/j.jasms.2006.06.007


One hundred fifty-seven nm photodissociation of singly-charged peptide ions induces the cleavage of α-carbon to carbonyl-carbon bonds along the backbone. an + 1 radical ions are observed as the primary photolysis products of peptides with N-terminal arginines in a linear ion trap mass spectrometer. The radical elimination pathways undertaken by the an + 1 radical ions to form more stable even-electron species are studied in hydrogen-deuterium (H/D) exchange experiments. Two types of an ions along with d-type ions are observed as secondary elimination products. The relative abundance of each depends on the C-terminal residue of the radical fragment ion.

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© American Society for Mass Spectrometry 2006