Electron transfer dissociation of peptide anions

  • Joshua J. Coon
  • Jeffrey Shabanowitz
  • Donald F. Hunt
  • John E. P. Syka
Short Communication

Abstract

Ion/ion reactions of multiply deprotonated peptide anions with xenon radical cations result in electron abstraction to generate charge-reduced peptide anions containing a free-radical site. Peptide backbone cleavage then occurs by hydrogen radical abstraction from a backbone amide N to facilitate cleavage of the adjacent C-C bond, thereby producing a- and x-type product ions. Introduction of free-radical sites to multiply charged peptides allows access to new fragmentation pathways that are otherwise too costly (e. g., lowers activation energies). Further, ion/ion chemistry, namely electron transfer reactions, presents a rapid and efficient means of generating odd-electron multiply charged peptides; these reactions can be used for studying gas-phase chemistries and for peptide sequence analysis.

References

  1. 1.
    Syka, J. E. P.; Coon, J. J.; Schroeder, M. J.; Shabanowitz, J.; Hunt, D. F. Peptide and protein sequence analysis by electron transfer dissociation mass spectrometry; Proceedings of the National Academy of Sciences of the United States of America; 2004; pp 9528–9533.Google Scholar
  2. 2.
    Coon, J. J.; Syka, J. E. P.; Schwartz, J. C.; Shabanowitz, J.; Hunt, D. F. Anion dependence in the partitioning between proton and electron transfer in ion/ion reactions. Int. J. Mass Spectrom. 2004, 236, 33–42.CrossRefGoogle Scholar
  3. 3.
    Zubarev, R. A.; Kelleher, N. L.; McLafferty, F. W. Electron capture dissociation of multiply charged protein cations. A nonergodic process. J. Am. Chem. Soc. 1998, 120, 3265–3266.CrossRefGoogle Scholar
  4. 4.
    Herron, W. J.; Goeringer, D. E.; Mcluckey, S. A. Gas-phase electron-transfer reactions from multiply charged anions to rare-gas cations. J. Am. Chem. Soc. 1995, 117, 11555–11562.CrossRefGoogle Scholar
  5. 5.
    Stephenson, J. L.; McLuckey, S. A. Charge reduction of oligonucleotide anions via gas-phase electron transfer to xenon cations. Rapid Commun. Mass Spectrom. 1997, 11, 875–880.CrossRefGoogle Scholar
  6. 6.
    Wu, J.; McLuckey, S. A. Ion/ion reactions of multiply charged nucleic acid anions: Electron transfer, proton transfer, and ion attachment. Int. J. Mass Spectrom. 2003, 228, 577–597.CrossRefGoogle Scholar
  7. 7.
    Budnik, B. A.; Haselmann, K. F.; Zubarev, R. A. Electron detachment dissociation of peptide di-anions: An electron-hole recombination phenomenon. Chem. Phys. Lett. 2001, 342, 299–302.CrossRefGoogle Scholar
  8. 8.
    Hunter, T. Signaling—2000 and beyond. Cell 2000, 100, 113–127.CrossRefGoogle Scholar
  9. 9.
    Huddleston, M. J.; Annan, R. S.; Bean, M. F.; Carr, S. A. Selective detection of phosphopeptides in complex-mixtures by electrospray liquid-chromatography mass-spectrometry. J. Am. Soc. Mass Spectrom. 1993, 4, 710–717.CrossRefGoogle Scholar
  10. 10.
    Annan, R. S.; Huddleston, M. J.; Verma, R.; Deshaies, R. J.; Carr, S. A. A multidimensional electrospray MS-based approach to phosphopeptide mapping. Anal. Chem. 2001, 73, 393–404.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 2005

Authors and Affiliations

  • Joshua J. Coon
    • 1
  • Jeffrey Shabanowitz
    • 1
  • Donald F. Hunt
    • 1
    • 4
  • John E. P. Syka
    • 2
    • 3
  1. 1.Department of ChemistryUniversity of VirginiaCharlottesvilleUSA
  2. 2.Engineering Physics ProgramUniversity of VirginiaCharlottesvilleUSA
  3. 3.Thermo ElectronSan Jose
  4. 4.the Department of Pathology, Health Sciences CenterUniversity of VirginiaCharlottesville

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