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

  • Focus: FT-ICR-MS
  • Published:
Journal of the American Society for Mass Spectrometry

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.

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References

  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.

    Article  CAS  Google Scholar 

  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.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  6. 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.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  12. 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.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

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

    Article  CAS  Google Scholar 

  17. 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.

    Article  CAS  Google Scholar 

  18. 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.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    CAS  Google Scholar 

  25. 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.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  27. 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.

    Article  CAS  Google Scholar 

  28. 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.

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  30. 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.

    Article  CAS  Google Scholar 

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

    Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

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

    Article  CAS  Google Scholar 

  41. 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.

    Article  CAS  Google Scholar 

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

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

  44. 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.

    Article  CAS  Google Scholar 

  45. 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.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Baker Chemistry Laboratory, Cornell University, Ithaca, New York, USA

    Fred W. McLafferty, David M. Horn, Kathrin Breuker, Ying Ge, Mark A. Lewis, Blas Cerda, Roman A. Zubarev & Barry K. Carpenter

  2. Corning Inc., SP-FR-03-1, 14831, Corning, New York

    Mark A. Lewis

  3. Chemistry Department, Odense University, Campusvej 55, M DK-5230, Odense, Denmark

    Roman A. Zubarev

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  1. Fred W. McLafferty
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Correspondence to Fred W. McLafferty.

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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

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  • DOI: https://doi.org/10.1016/S1044-0305(00)00223-3

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