Electron capture dissociation of gaseous multiply charged ions by Fourier-transform ion cyclotron resonance

Abstract

Fourier-transform ion cyclotron resonance instrumentation is uniquely applicable to an unusual new ion chemistry, electron capture dissociation (ECD). This causes nonergodic dissociation of far larger molecules (42 kDa) than previously observed (<1 kDa), with the resulting unimolecular ion chemistry also unique because it involves radical site reactions for similarly larger ions. ECD is highly complementary to the well known energetic methods for multiply charged ion dissociation, providing much more extensive protein sequence information, including the direct identification of N- versus C-terminal fragment ions. Because ECD only excites the molecule near the cleavage site, accompanying rearrangements are minimized. Counterintuitively, cleavage of backbone covalent bonds of protein ions is favored over that of noncovalent bonds; larger (>10 kDa) ions give far more extensive ECD if they are first thermally activated. This high specificity for covalent bond cleavage also makes ECD promising for studying the secondary and tertiary structure of gaseous protein ions caused by noncovalent bonding.

This is a preview of subscription content, log in to check access.

References

  1. 1.

    Comisarow, M. B.; Marshall, A. G. Chem. Phys. Lett. 1974, 25, 282–283. White, R. L.; Ledford, E. B.; Ghaderi, S.; Wilkins, S. L.; Gross, M. L. Anal. Chem. 1980, 52, 1525. Karlin, T. J.; Freiser, B. S. Anal. Chem. 1983, 55, 571–574. Castro, M. E.; Russell, D. H. Anal. Chem. 1984, 56, 578. Hunt, D. F.; Shabanowitz, J.; McIver, R. T., Jr.; Hunter, R. L.; Syka, J. E. P. Anal. Chem. 1985, 57, 765–768. Marshall, A. G.; Wang, T. C. L.; Chen. L.; Ricca, T. L. ACS Symp. Ser. 1987, 359, 21–33. Fourier-Transform Mass Spectrometry; Buchanan, M. V. Ed.; American Chemical Society: Washington, DC, 1987. Wilkins, C. L.; Chowdhury, A. K.; Nuwaysir, L. M.; Coates, M. L. Mass Spectrom Rev. 1989, 8, 67–92. Marshall, A. G.; Grosshans, P. B. Anal. Chem. 1991, 63, A215–A229. Beu, S. C.; Laude, D. A., Jr. Int. J. Mass Spectrom. Ion Processes 1992, 112, 215–230. Hofstadler, S. A.; Laude, D. A., Jr. J. Am. Soc. Mass Spectrom. 1992, 3, 615–623. Hofstadler, S. A.; Beu, S. C.; Laude, D. A., Jr. Anal Chem. 1993, 65, A245–A259. Winger, B. E.; Hofstadler, S. A.; Bruce, J. E.; Udseth, H. R.; Smith, R. D. J. Am. Soc. Mass Spectrom. 1993, 4, 566–577. Williams, E. R. Anal Chem. 1998, 70, 179A–185A. Marshall A. G.; Hendrickson, C. L; Jackson, G. S. Mass. Spectrom. Rev. 1998, 17, 1–36.

    CAS  Article  Google Scholar 

  2. 2.

    Cody, R. B., Jr.; Amster, I. J.; McLafferty, F. W. Proc. Natl. Acad. Sci. U.S.A., 1985, 82, 6367–6370. McLafferty, F. W.; Amster, I. J; Furlong, J. J. P.; Loo, J. A.; Wang, B. H.; Williams, E. R. Tandem Fourier-Transform Mass Spectrometry; M. V. Buchanan, Ed.; American Chemical Society: Washington, DC, 1987. Henry, K. D.; Williams, E. R.; Wang, B. H.; McLafferty, F. W.; Shabanowitz, J.; Hunt, D. F. Proc. Natl. Acad. Sci. U.S.A., 1989, 86, 9075–9078. Beu, S. C.; Senko, M. W.; Quinn, J. P.; Wampler, F. M., III; McLafferty, F. W. J. Am. Soc. Mass Spectrom., 1993, 4, 557–565. Senko, M. W.; Beu, S. C.; McLafferty, F. W. Annu. Rev. Biophys. Biomol. Struct. 1994, 23, 763–785.

    CAS  Article  Google Scholar 

  3. 3. (a)

    Loo, J. A.; Udseth, H. R.; Smith, R. D. Rapid Commun. Mass Spectrom. 1988, 2, 207–210.

    CAS  Article  Google Scholar 

  4. 3. (b)

    Gauthier, J. W.; Trautman, T. R.; Jacobsen, D. B. Anal. Chim. Acta 1991, 246, 211–225.

    CAS  Article  Google Scholar 

  5. 3. (c)

    Senko, M. W.; Speir, J. P.; McLafferty, F. W. Anal. Chem. 1994, 66, 2801–2808.

    CAS  Article  Google Scholar 

  6. 4.

    Little, D. P.; Chorush, R. A.; Speir, J. P.; Senko, M. W.; Kelleher, N. L.; McLafferty, F. W. J. Am. Chem. Soc. 1994, 116, 4893–4897.

    CAS  Article  Google Scholar 

  7. 5.

    Price, W. D.; Schnier, P. D.; Williams, E. R. Anal Chem. 1996, 68, 859–866.

    CAS  Article  Google Scholar 

  8. 6. (a)

    McCormack, A. L.; Jones, J. L.; Wysocki, V. H. J. Am. Soc. Mass Spectrom. 1992, 3, 859–862.

    CAS  Article  Google Scholar 

  9. 6. (b)

    Chorush, R. A.; Little, D. P.; Beu, S. C.; Wood, T. D.; McLafferty, F. W. Anal. Chem. 1995, 67, 1042–1046.

    CAS  Article  Google Scholar 

  10. 7.

    Guan, Z.; Kelleher, N. L.; O’Connor, P. B.; Aaserud, D. J.; Little, D. P.; McLafferty, F. W. Int. J. Mass Spectrom. Ion Processes 1996, 157, 357–364.

    Article  Google Scholar 

  11. 8. (a)

    Mirgorodskaya, E.; Roepstorff, P.; Zubarev, R. Anal. Chem. 1999, 71, 4431–4436.

    CAS  Article  Google Scholar 

  12. 8. (b)

    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.

    CAS  Article  Google Scholar 

  13. 8. (c)

    Fridriksson, E. K.; Beavil, A.; Holowka, D.; Gould, H. J.; Baird, B.; McLafferty, F. W. Biochemistry 2000, 39, 3369–3376.

    CAS  Article  Google Scholar 

  14. 8. (d)

    Schey, K. L.; Finley, E. L. Acc Chem. Res. 2000, 33, 299–306.

    CAS  Article  Google Scholar 

  15. 8. (e)

    Shi, S. D.-H.; Hemling, M. E.; Carr, S. A.; Horn, D. M.; Lindh, I.; McLafferty, F. W. Anal. Chem., submitted.

  16. 9. (a)

    Zubarev, R. A.; Kelleher, N. L.; McLafferty, F. W. J. Am. Chem. Soc. 1998, 120, 3265–3266.

    CAS  Article  Google Scholar 

  17. 9. (b)

    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.

    CAS  Article  Google Scholar 

  18. 9. (c)

    Zubarev, R. A.; Horn, D. M.; Fridriksson, E. K.; Kelleher, N. L.; Kruger, N. A.; Lewis, M. A.; Carpenter, B. K.; McLafferty, F. W. Anal. Chem. 2000, 72, 563–573.

    CAS  Article  Google Scholar 

  19. 9. (d)

    Horn, D. M.; Ge, Y.; McLafferty, F. W. Anal. Chem., 2000, 72, 4778–4784.

    CAS  Article  Google Scholar 

  20. 10.

    Turecek, F.; McLafferty, F. W. J. Am. Chem. Soc. 1984, 106, 2525–2528.

    CAS  Article  Google Scholar 

  21. 11. (a)

    Biemann, K. In Methods in Enzymology; McCloskey, J. A., Ed., Academic: San Diego, 1990; Vol. 193, p 887.

    Google Scholar 

  22. 11. (b)

    Andersen, J. S.; Svensson, B.; Roepstorff, P. Nature Biotechnol. 1996, 14, 449–457.

    CAS  Article  Google Scholar 

  23. 11. (c)

    Qin, J.; Chait, B. T. Anal. Chem. 1997, 69, 4002–4009.

    CAS  Article  Google Scholar 

  24. 11. (d)

    Kuster, B.; Mann, M. Curr. Opin. Chem. Biol. 1998, 8, 393–400.

    CAS  Google Scholar 

  25. 11. (e)

    Jensen, K.; Pasa-Tolic, L.; Anderson, G. A.; Horner, J. A.; Lyston, M. S.; Bruce, J. E.; Smith, R. D. Anal. Chem. 1999, 71, 2076–2084.

    CAS  Article  Google Scholar 

  26. 12. (a)

    McLafferty, F. W. Acc. Chem. Res. 1994, 27, 379–386.

    CAS  Article  Google Scholar 

  27. 12. (b)

    McLafferty, F. W.; Kelleher, N. L.; Begley, T. P.; Fridriksson, E. K.; Zubarev, R. A.; Horn, D. M. Curr. Opin. Chem. Biol. 1998, 2, 571–578.

    CAS  Article  Google Scholar 

  28. 12. (c)

    Kelleher, N. L.; Lin, H. Y.; Valaskovic, G. A.; Aaserud, D. J.; Fridriksson, E. K.; McLafferty, F. W. J. Am. Chem. Soc. 1999, 121, 806–812.

    CAS  Article  Google Scholar 

  29. 12. (d)

    McLafferty, F. W.; Fridriksson, E. K.; Horn, D. M.; Lewis, M. A.; Zubarev, R. A. Science (Washington, D. C.) 1999, 284, 1289–1290.

    CAS  Article  Google Scholar 

  30. 13.

    Green, M. K.; Lebrilla, C. B. Mass. Spectrom. Rev. 1997, 16, 53–72. Brodbelt, J. S. Mass Spectrom Rev. 1997, 16, 91–110. Ranatunga, T. D.; Kennady, J. M.; Kenttamaa, H. I. J. Am. Chem. Soc. 1997, 119, 5200–5207. McLuckey, S. A.; Stephenson, J. L. Mass Spectrom. Rev. 1998, 17, 369–407.

    CAS  Article  Google Scholar 

  31. 14.

    McLafferty, F. W. In Mass Spectrometry in the Analysis of Large Molecules; McNeal, C. J., Ed., Wiley: New York, 1986, pp 107–120.

    Google Scholar 

  32. 15.

    McLafferty, F. W.; Turecek, F. In Interpretation of Mass Spectra, 4th ed. University Science Books: Mill Valley, CA, 1993.

    Google Scholar 

  33. 16.

    McLafferty, F. W.; Stauffer, D. A.; Loh, S. Y.; Wesdemiotis, C. J. Am. Soc. Mass Spectrom. 1999, 10, 1229–1240.

    CAS  Article  Google Scholar 

  34. 17. (a)

    Kruger, N. A.; Zubarev, R. A.; Carpenter, B. K.; Kelleher, N. L.; Horn, D. M.; McLafferty, F. W. Int. J. Mass Spectrom. 1999, 182, 1–5.

    Article  Google Scholar 

  35. 17. (b)

    Kruger, N. A.; Zubarev, R. A.; Horn, D. M.; McLafferty, F. W. Int. J. Mass Spectrom. 1999, 185, 787–793.

    Article  Google Scholar 

  36. 18.

    Horn, D. M.; Zubarev, R. A.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 2000, 11, 320–332.

    CAS  Article  Google Scholar 

  37. 19.

    Horn, D. M.; Zubarev, R. A.; McLafferty, F. W. Proc. Natl. Acad. Sci. U.S.A., 2000, 97, 10313–10317.

    CAS  Article  Google Scholar 

  38. 20.

    Cerda, B. A.; Horn, D. M.; Breuker, K.; Carpenter, B. K.; McLafferty, F. W. Eur. Mass Spectrom. 1999, 5, 335–338.

    CAS  Article  Google Scholar 

  39. 21.

    Cerda, B. A.; Horn, D. M.; Breuker, K.; McLafferty, F. W. J. Am Chem. Soc., submitted.

  40. 22.

    McLafferty, F. W.; Guan, Z.; Haupts, U.; Wood, T. D.; Kelleher, N. L. J. Am. Chem. Soc. 1998, 120, 4732–4740.

    CAS  Article  Google Scholar 

  41. 23.

    Speir, J. P.; Senko, M. W.; Little, D. P.; Loo, J. A.; McLafferty, F. W. J. Mass Spectrom. 1995, 30, 39–42. Little, D. P.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 1996, 7, 209–210. Fridriksson, E. K.; Baird, B.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 1999, 10, 453–455.

    CAS  Article  Google Scholar 

  42. 24.

    Horn, D. M.; Breuker, K.; Cerda, B. A.; Ge, Y.; McLafferty, F. W., unpublished.

  43. 25.

    Horn, D. M.; Breuker, K.; Frank, A. J.; McLafferty, F. W. J. Am. Chem. Soc., submitted.

  44. 26.

    Ganem, B.; Li, Y. -T.; Henion, J. D. J. Am. Chem. Soc. 1991, 113, 6294–6296. Li, Y.-T.; Henion, J. D.; Senko, M. W.; McLafferty, F. W.; Ganem, B. J. Am. Chem. Soc. 1993, 115, 8409–8413. Loo, J. A. Mass Spectrom. Rev. 1997, 16, 1–23.

    CAS  Article  Google Scholar 

  45. 27.

    Mann, M.; Wilm, M. Anal. Chem. 1994, 66, 4390–4399. Mortz, E.; O’Connor, P. B.; Roepstorff, P.; Kelleher, N. L.; Wood, T. D.; McLafferty, F. W.; Mann, M. Proc. Natl. Acad. Sci. U.S.A. 1996, 93, 8264–8267.

    CAS  Article  Google Scholar 

Download references

Author information

Affiliations

Authors

Corresponding author

Correspondence to Fred W. McLafferty.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

McLafferty, F.W., Horn, D.M., Breuker, K. et al. Electron capture dissociation of gaseous multiply charged ions by Fourier-transform ion cyclotron resonance. J Am Soc Mass Spectrom 12, 245–249 (2001). https://doi.org/10.1016/S1044-0305(00)00223-3

Download citation

Keywords

  • Electron Capture Dissociation
  • Noncovalent Bond
  • Electron Capture Dissociation Spectrum
  • High Rydberg State
  • Electron Capture Dissociation Product