Does double electron capture lead to the formation of biradicals? An ECD-SORI-CID study on lacticin 481

  • Anne J. Kleinnijenhuis
  • Albert J. R. Heck
  • Marc C. Duursma
  • Ron M. A. Heeren


We studied lacticin 481, a small lantibiotic with three lanthionine bridges, by electron capture dissociation (ECD) in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Following electron capture, very little fragmentation was observed, but species formed by nondissociative single and multiple electron capture were abundant. Ions formed by double electron capture were subjected to sustained off resonance irradiation collision induced dissociation (SORI-CID) to determine whether stable biradicals were formed. In the SORI-CID spectra of the ions formed by double electron capture, some, but minor, H radical loss was observed, which was not observed at all for regularly protonated ions. A small part of the ions formed by double electron capture are thus long-lived biradicals. Apart from the observed H loss, the SORI-CID spectra of ions that captured two electrons was similar to that of regularly protonated ions and quite different from the SORI-CID spectra of radical ions formed by single electron capture. This implies that recombination of the two radical sites is the dominant process in biradical lacticin 481 ions, at least on the time scale of our SORI-CID experiments.


  1. 1.
    Breukink, E.; Wiedemann, I.; van Kraaij, C.; Kuipers, O. P.; Sahl, H.; de Kruijff, B. Science 1999, 286, 2361–2364.CrossRefGoogle Scholar
  2. 2.
    Edman, P.; Begg, G. Eur. J. Biochem. 1967, 1, 80–81.CrossRefGoogle Scholar
  3. 3.
    Kellersberger, K. A.; Fabris, D. Proceedings of the 52nd ASMS Conference on Mass Spectrometry and Allied Topics, Nashville, TN, 2004.Google Scholar
  4. 4.
    Meyer, H. E.; Heber, M.; Eisermann, B.; Korte, H.; Metzger, J. W.; Jung, G. Anal. Biochem. 1994, 223, 185–190.CrossRefGoogle Scholar
  5. 5.
    Kleinnijenhuis, A. J.; Duursma, M. C.; Breukink, E.; Heeren, R. M. A.; Heck, A. J. R. Anal. Chem. 2003, 75, 3219–3225.CrossRefGoogle Scholar
  6. 6.
    Zubarev, R. A.; Kelleher, N. L.; McLafferty, F. W. J. Am. Chem. Soc. 1998, 120, 3265–3266.CrossRefGoogle Scholar
  7. 7.
    Zubarev, R. A.; Kruger, N. A.; Fridriksson, E. K.; Lewis, M. A.; Horn, D. M.; Carpenter, B. K.; McLafferty, F. W. J. Am. Chem. Soc. 1999, 121, 2857–2862.CrossRefGoogle Scholar
  8. 8.
    Zubarev, R. A.; Haselmann, K. F.; Budnik, B. A.; Kjeldsen, F.; Jensen, F. Eur. J. Mass Spectrom. 2002, 8, 337–349.CrossRefGoogle Scholar
  9. 9.
    Cerda, B. A.; Horn, D. M.; Breuker, K.; Carpenter, B. K.; McLafferty, F. W. Eur. J. Mass Spectrom. 1999, 5, 335–338.CrossRefGoogle Scholar
  10. 10.
    Roepstorff, P.; Fohlman, J. Biomed. Mass Spectrom. 1984, 11, 601.CrossRefGoogle Scholar
  11. 11.
    Guan, Z.; Yates, N. A.; Bakhtiar, R. J. Am. Soc. Mass Spectrom. 2003, 14, 605–613.CrossRefGoogle Scholar
  12. 12.
    Mirgorodskaya, E.; Roepstorff, P.; Zubarev, R. A. Anal. Chem. 1999, 71, 4431–4436.CrossRefGoogle Scholar
  13. 13.
    Hakansson, K.; Cooper, H. J.; Emmett, M. R.; Costello, C. E.; Marshall, A. G.; Nilsson, C. L. Anal. Chem. 2001, 73, 4530–4536.CrossRefGoogle Scholar
  14. 14.
    Stensballe, A.; Jensen, O. N.; Olsen, J. V.; Haselmann, K. F.; Zubarev, R. A. Rapid Commun. Mass Spectrom. 2000, 14, 1793–1800.CrossRefGoogle Scholar
  15. 15.
    Kelleher, N. L.; Zubarev, R. A.; Bush, K.; Furie, B.; Furie, B. C.; McLafferty, F. W.; Walsh, C. T. Anal. Chem. 1999, 71, 4250–4253.CrossRefGoogle Scholar
  16. 16.
    Mirgorodskaya, O. A.; Haselmann, K. F.; Kjeldsen, F.; Zubarev, R. A. Eur. J. Mass Spectrom. 2003, 9, 139–148.CrossRefGoogle Scholar
  17. 17.
    Zubarev, R. A. Mass Spectrom. Rev. 2003, 22, 57–77.CrossRefGoogle Scholar
  18. 18.
    Uggerud, E. Int. J. Mass Spectrom. 2004, 234, 45–50.CrossRefGoogle Scholar
  19. 19.
    Turecek, F.; Polasek, M.; Frank, A. J.; Sadilek, M. J. Am. Chem. Soc. 2000, 122, 2361–2370.CrossRefGoogle Scholar
  20. 20.
    Syrstad, E. A.; Turecek, F. J. Am. Soc. Mass Spectrom. 2005, 16, 208–224.CrossRefGoogle Scholar
  21. 21.
    Kruger, N. A.; Zubarev, R. A.; Horn, D. M.; McLafferty, F. W. Int. J. Mass Spectrom. 1999, 185/186/187, 787–793.CrossRefGoogle Scholar
  22. 22.
    Horn, D. M.; Ge, Y.; McLafferty, F. W. Anal. Chem. 2000, 72, 4778–4784.CrossRefGoogle Scholar
  23. 23.
    van den Hooven, H. W.; Lagerwerf, F. M.; Heerma, W.; Haverkamp, J.; Piard, J.; Hilbers, C. W.; Siezen, R. J.; Kuipers, O. P.; Rollema, H. S. FEBS Lett. 1996, 391, 317–322.CrossRefGoogle Scholar
  24. 24.
    Gauthier, J. W.; Trautman, T. R.; Jacobson, D. B. Anal. Chim. Acta 1991, 246, 211–225.CrossRefGoogle Scholar
  25. 25.
    Heck, A. J. R.; de Koning, L. J.; Pinkse, F. A.; Nibbering, N. M. M. Rapid Commun. Mass Spectrom. 1991, 5, 406–414.CrossRefGoogle Scholar
  26. 26.
    Mize, T. H.; Taban, I.; Duursma, M.; Seynen, M.; Konijnenburg, M.; Vijftigschild, A.; Doornik, C. V.; Rooij, G. V.; Heeren, R. M. A. Int. J. Mass Spectrom. 2004, 235, 243–253.CrossRefGoogle Scholar
  27. 27.
    Cooper, H. J.; Hakansson, K.; Marshall, A. G.; Hudgins, R. R.; Haselmann, K. F.; Kjeldsen, F.; Budnik, B. A.; Polfer, N. C.; Zubarev, R. A. Eur. J. Mass Spectrom. 2003, 9, 221–222.CrossRefGoogle Scholar
  28. 28.
    Haselmann, K. F.; Budnik, B. A.; Kjeldsen, F.; Polfer, N. C.; Zubarev, R. A. Eur. J. Mass Spectrom. 2002, 8, 461–469.CrossRefGoogle Scholar
  29. 29.
    Cooper, H. J.; Hudgins, R. R.; Hakansson, K.; Marshall, A. G. J. Am. Soc. Mass Spectrom. 2002, 13, 241–249.CrossRefGoogle Scholar
  30. 30.
    Polce, M. J.; Wesdemiotis, C. Rapid Commun. Mass Spectrom. 1996, 10, 235–241.CrossRefGoogle Scholar
  31. 31.
    Leymarie, N.; Costello, C. E.; O’Connor, P. B. J. Am. Chem. Soc. 2003, 125, 8949–8958.CrossRefGoogle Scholar
  32. 32.
    Lee, H.-L.; Li, W.-K.; Chiu, S.-W. J. Mol. Struct. Theochem. 2003, 629, 237–250.CrossRefGoogle Scholar
  33. 33.
    Sawicka, A.; Skurski, P.; Hudgins, R. R.; Simons, J. J. Phys. Chem. B 2003, 107, 13505–13511.CrossRefGoogle Scholar
  34. 34.
    Rauk, A.; Yu, D.; Taylor, J.; Shustov, G. V.; Block, D. A.; Armstrong, D. A. Biochemistry 1999, 38, 9089–9096.CrossRefGoogle Scholar
  35. 35.
    Yang, H.; Luo, G.; Karnchanaphanurach, P.; Louie, T.-M.; Rech, I.; Cova, S.; Xun, L.; Sunney Xie, X. Science 1996, 302, 262–266.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 2005

Authors and Affiliations

  • Anne J. Kleinnijenhuis
    • 1
  • Albert J. R. Heck
    • 1
    • 2
  • Marc C. Duursma
    • 2
  • Ron M. A. Heeren
    • 1
    • 2
  1. 1.Department of Biomolecular Mass Spectrometry, Bijvoet Center for Biomolecular Research and Utrecht Institute for Pharmaceutical SciencesUtrecht UniversityUtrechtThe Netherlands
  2. 2.FOM Institute for Atomic and Molecular Physics (AMOLF)AmsterdamThe Netherlands

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