Abstract
A relatively simple model for calculation of the energetics of gas-phase proton transfer reactions and the maximum charge state of multiply protonated ions formed by electrospray ionization is presented. This model is based on estimates of the intrinsic proton transfer reactivity of sites of protonation and point charge Coulomb interactions. From this model, apparent gas-phase basicities (GBapp) of multiply protonated ions are calculated. Comparison of this value to the gas-phase basicity of the solvent from which an ion is formed enables a maximum charge state to be calculated. For 13 commonly electrosprayed proteins, our calculated maximum charge states are within an average of 6% of the experimental values reported in the literature. This indicates that the maximum charge state for proteins is determined by their gas-phase reactivity. Similar results are observed for peptides with many basic residues. For peptides with few basic residues, we find that the maximum charge state is better correlated to the charge state in solution. For low charge state ions, we find that the most basic sites Arg, Lys, and His are preferentially protonated. A significant fraction of the less basic residues Pro, Trp, and Gln are protonated in high charge state ions. The calculated GBapp of individual protonation sites varies dramatically in the high charge state ions. From these values, we calculate a reduced cross section for proton transfer reactivity that is significantly lower than the Langevin collision frequency when the GBapp of the ion is approximately equal to the GB of the neutral base.
Article PDF
Similar content being viewed by others
References
Fenn, J. B.; Mann, M.; Meng, C. K.; Whitehouse, C. M. Science 1989, 246, 64–71.
Smith, R. D.; Loo, J. A.; Ogorzalek Loo, R. R.; Busman, M.; Udseth, H. R. Mass Spectrom. Rev. 1991, 10, 359–452.
Beu, S. C.; Senko, M. W.; Quinn, J. P.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 1993, 4, 190–192.
Nohmi, T.; Fenn, J. B. J. Am. Chem. Soc. 1992, 114, 3241–3246.
Fenn, J. B. J. Am. Soc. Mass Spectrom. 1993, 4, 524–535.
Dole, M.; Mach, L. L.; Hines, R. L.; Mobley, R. C.; Ferguson, L. P.; Alice, M. B. J. Chem. Phys. 1968, 49, 2240–2249.
Schmelzeisen-Redecker, G.; Bütfering, L.; Röllgen, F. W. Int. J. Mass Spectrom. Ion Processes 1989, 90, 139–150.
Iribarne, J. V.; Thomson, B. A. J. Chem. Phys. 1976, 64, 2287–2294.
Kebarle, P.; Tang, L. Anal. Chem. 1993, 65, 972A-986A.
Covey, T. R.; Bonner, R. F.; Shushan, B. I.; Henion, J. Rapid Commun. Mass Spectrom. 1988, 2, 249–256.
Chowdhury, S. K.; Katta, V.; Chait, B. T. J. Am. Chem. Soc. 1990, 112, 9012–9013.
Mirza, U.; Cohen, S.; Chait, B. T. Anal. Chem. 1993, 65, 1–6.
Loo, J. A.; Edmonds, C. G.; Udseth, H. R.; Smith, R. D. Anal. Chem. 1990, 62, 693–698.
Loo, J. A.; Ogorzalek Loo, R. R.; Udseth, H. R.; Edmonds, C. G.; Smith, R. D. Rapid Commun. Mass Spectrom. 1991, 5, 101–105.
Guevremont, R.; Siu, K. W. M.; LeBlanc, J. C. Y.; Berman, S. S. J. Am. Soc. Mass Spectrom. 1992, 3, 216–224.
LeBlanc, J. C. Y.; Siu, K. M.; Guevremont, R. Anal. Chem. 1994, 66, 3289–3296.
Kelly, M. A.; Vestling, M. M.; Fenselau, C. C.; Smith, P. B. Org. Mass Spectrom. 1992, 27, 1143–1147.
Ashton, D. S.; Beddell, C. R.; Cooper, D. J.; Green, B. N.; Oliver, R. W. A. Org. Mass Spectrom. 1993, 28, 721–728.
Tang, L.; Kebarle, P. Anal. Chem. 1993, 65, 3654–3666.
LeBlanc, J. C. Y.; Wang, J.; Guevremont, R.; Siu, K. W. M. Org. Mass Spectrom. 1994, 29, 587–593.
Wang, G.; Cole, R. B. Org. Mass Spectrom. 1994, 29, 419–427.
Ogorzalek Loo, R. R.; Smith, R. D. J. Mass Spectrom. 1995, 30, 339–347.
Gulcicek, E. E.; Shen, S.; Boyle, J. D.; Whitehouse, C. M.; Harrison, D. H.; Moore, P. B.; Proceedings of the 39th ASMS Conference on Mass Spectrometry and Allied Topics Nashville, TN, 1991; pp 1245–1246.
McLuckey, S. A.; Van Berkel, G. J.; Glish, G. L. J. Am. Chem. Soc. 1990, 112, 5668–5670.
Cassady, C. J.; Wronka, J.; Laukien, F. H. Rapid Commun. Mass Spectrom. 1994, 8, 394–400.
Ogorzalek Loo, R. R.; Smith, R. D. J. Am. Soc. Mass Spectrom. 1994, 5, 207–220.
Ogorzalek Loo, R. R.; Winger, B. E.; Smith, R. D. J. Am. Soc. Mass Spectrom. 1994, 5, 1064–1071.
Gross, D. S.; Williams, E. R. J. Am. Chem. Soc. 1995, 117, 883–890.
Gross, D. S.; Rodriguez-Cruz, S. E.; Bock, S.; Williams, E. R. J. Phys. Chem. 1995, 99, 4034–4038.
Schnier, P. D.; Gross, D. S.; Williams, E. R. J. Am. Chem. Soc. 1995, 117, 6747–6757.
Williams, E. R.; Gross, D. S.; Schnier, P. D.; Rodriguez-Cruz, S. E.; Fagerquist, C. K. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics; Atlanta, GA, May 21–26, 1995; TOC 11:50.
Aue, D. H.; Bowers, M. T. In Gas-Phase Ion Chemistry, Vol. 2; Bowers,, M. T., Ed.; New York: Academic Press, 1979; Chap. 9.
DeFrees, D. J.; McIver, R. T.; Hehre, W. J. J. Am. Chem. Soc. 198, 102, 3334–3338.
McLuckey, S. A.; Cameron, D.; Cooks, R. G. J. Am. Chem. Soc. 1981, 103, 1313–1317.
Javahery, G.; Petrie, S.; Wincel, H.; Wang, J.; Bohme, D. K. J. Am. Chem. Soc. 1993, 115, 6295–6301.
Bursey, M. M.; Pederson, L. G. Org. Mass Spectrom. 1992, 27, 974–975.
Petrie, S.; Javahery, G.; Wincel, H.; Wang, J.; Bohme, D. K. J. Am. Chem. Soc. 1993, 115, 6290–6294.
Suckau, D.; Shi, Y Beu, S. C.; Senko, M. W.; Quinn, J. P.; Wampler, F. W.; McLafferty, F. W. Proc. Nat’l. Acad. Sci. U. S. A. 1993, 90, 790–793.
Wood, T. D.; Chorush, R. A.; Wampler, F. M.; Little, D. P.; O’Connor, P. B.; McLafferty, F. W. Proc. Nat’l. Acad. Sci. U. S. A. 1995, 92, 2451–2454.
Creighton, T. E. Proteins, 2nd ed.; New York: W. H. Freeman and Co., 1993.
Rockwood, A. L.; Busman, M.; Smith, R. D. Int. J. Mass Spectrom. Ion Processes 1991, 111, 103–129.
Wu, J.; Lebrilla, C. B. J. Am. Chem. Soc. 1993, 115, 3270–3275.
Wu, J.; Lebrilla, C. B. J. Am. Soc. Mass Spectrom. 1995, 6, 91–101.
Wu, Z.; Fenselau, C. J. Am. Soc. Mass Spectrom. 1992, 3, 863–866.
Gorman, G. S.; Amster, I. J. J. Am. Chem. Soc. 1993, 115, 5729–5735.
Wu, Z.; Fenselau, C. Rapid Commun. Mass Spectrom. 1992, 6, 403–405.
Wu, Z.; Fenselau, C. Rapid Commun. Mass Spectrom. 1994, 8, 777–780.
Lias, S. G.; Liebman, J. F.; Levin, R. D. J. Phys. Chem. Ref. Data 1984, 13, 695–808.
Wu, Z.; Fenselau, C. Tetrahedron 1993, 49, 9197–9206.
Katta, V.; Chait, B. T. Rapid Commun. Mass Spectrom. 1991, 5, 214–217.
Kirkpatrick, C. D.; Gelatt, C. D.; Vecchi, M. P. Science 1983, 220, 671–680.
Press, W. H.; Flannery, B. P.; Teukolsky, S. A.; Vetterling, W. T. Numerical Recipes in Pascal; Cambridge, U.K.: Cambridge University Press, 1989.
Wan Abdullah, W. A. T. J. Comp. Phys. 1994, 110, 320–326.
Lide, D. R., Ed. CRC Handbook of Chemistry and Physics; Boca Raton, FL: CRC Press, 1993.
Chernushevich, I. V.; Ens, W.; Standing, K. G. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics; Atlanta, GA, May 21–26, 1995; FOD 10:30.
Loo, J. A.; Ogorzalek Loo, R. R.; Udseth, H. R.; Fulton, J. L.; Smith, R. D. Rapid Commun. Mass Spectrom. 1992, 6, 159–165.
Buck, M.; Radford, S. E.; Dobson, C. M. Biochemistry 1993, 32, 669–678.
Schwarz, F. P.; Kirchhoff, W. H. Thermochim. Acta 1988, 128, 267–275.
Schwarz, F. P. Thermochim. Acta 1989, 147, 71–91.
Covey, T.; Douglas, D. J. J. Am. Soc. Mass Spectrom. 1993, 4, 616–623.
Cox, K. A.; Julian, R. K.; Cooks, R. G.; Kaiser, R. E. J. Am. Soc. Mass Spectrom. 1994, 5, 127–136.
Ikonomou, M. G.; Kebarle, P. Int. J. Mass Spectrom. Ion Processes 1992, 117, 283–298.
Langevin, P. Ann. Chim. Phys. 1905, 5, 245.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Schnier, P.D., Gross, D.S. & Williams, E.R. On the maximum charge state and proton transfer reactivity of peptide and protein ions formed by electrospray ionization. J Am Soc Mass Spectrom 6, 1086–1097 (1995). https://doi.org/10.1016/1044-0305(95)00532-3
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/1044-0305(95)00532-3