Abstract
Previously, the highest molecular weight for a sample yielding a unit resolution mass spectrum was 67 kDa (marginal at 86 kDa), obtained with a 6. 2 T Fourier-transform mass spectrometer with electrospray ionization. Now with a 9. 4 T instrument, resolving power of 170,000 has been achieved for chondroitinase I (997 amino acids) and II (990 amino acids), making possible molecular weight assignments of 112,509 and 111,714, respectively, versus 112,508 and 111,713 calculated. Assisting these assignments was the noise reduction in the resolved isotopic peaks achieved by the time domain data sampling technique introduced by Senko, Marshall, and co-workers.
References
Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Mass Spectrom. Rev. 1990, 9, 37–70.
Marshall, A. G.; Comisarow, M. B. Chem. Phys. Lett. 1974, 25, 282–283;
Marshall, A. G.; Grosshans, P. B. Anal. Chem. 1991, 63, 215A-229A.
Marshall, A. G.; Verdun, F. R. Fourier Transforms in NMR, Optical, and Mass Spectrometry; Elsevier: Amsterdam, 1990; Chap. 3.
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.
Winger, B. E.; Hofstadler, S. A.; Bruce, J. E.; Udseth, H. R.; Smith, R. D. J. Am. Soc Mass Spectrom. 1993, 4, 566–577.
McLafferty, F. W. Acc. Chem. Res. 1994, 27, 379–386.
Kelleher, N. L.; Costello, C. A.; Begley, T. P.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 1995, 6, 981–984.
Wood, T. D.; Chen, L. H.; Kelleher, N. L.; Little, D. P.; Kenyon, G. L.; McLafferty, F. W. Biochemistry 1995, 34, 16251–16254.
Little, D. P.; Thannhauser, T. W.; McLafferty, F. W. Proc. Natl. Acad. Sciences USA 1995, 92, 2318–2322.
Little, D. P.; Aaserud, D. J.; Valaskovic, G. A.; McLafferty, F. W. J. Am. Chem. Soc. 1996, 118, 9352–9359.
O’Connor, P. B.; McLafferty, F. W. J. Am. Chem. Soc. 1995, 227, 12826–12831.
Senko, M. W.; Beu, S. C.; McLafferty, F. W. J. Am. Soc. Mass Spectrom. 1995, 6, 52–56.
Ibid.
Speir, J. P.; Senko, M. W.; Little, D. P.; Loo, J. A.; McLafferty, F. W. J. Mass Spectrom. 1995, 30, 39–42.
Mitchell, D. W.; Smith, R. D. J. Mass Spectrom. 1996, 31, 771–790.
Pasa-Tolic, L.; Marto, J. A.; Senko, M. W.; Hendrickson, C. L.; White, F. M.; Guan, S.; Marshall, A. G. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta, GA, 1995, p 1085.
Senko, M. W.; Hendrickson, C. L.; Pasa-Tolic, L.; Marto, J. A.; White, F. M.; Guan, S.; Marshall, A. G. Rapid Commun. Mass Spectrom. 1996, 10, 1824–1828.
Siegel, M. M.; Khandke, K. M.; Tabei, K.; Berkenkamp, S.; Ingendoh, A.; Hillenkamp, F. 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta, GA, 1995, p 306.
Senko, M. W.; Guan, S.; Huang, Y.; Marshall, A. G.; McLafferty, F. W. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta, GA, 1995, p 806.
Khandke, K. M. Chondroitinase II from Proteus Vulgaris. U. S. Patent 5,498,536, 1996.
Wilm, M. S.; Mann, M. Int. J. Mass Spectrom. Ion Processes 1994, 236, 167–180.
Valaskovic, G. A.; Kelleher, N. L.; Little, D. P.; Aaserud, D. J.; McLafferty, F. W. Anal. Chem. 1995, 67, 3802–3805;
Wilm, M.; Mann, M. Anal. Chem. 1996, 68, 1–8.
Marshall, A. G.; Wang, T. C. L.; Ricca, T. L. J. Am. Chem. Soc. 1985, 207, 7893–7897.
Mann, M.; Meng, C. K.; Fenn, J. B. Anal. Chem. 1989, 61, 1702–1708.
The measured RP value of ∼170,000 assumes that the peak width is due entirely to instrument broadening of a singular mass value, such as the composition 12C4971 13C69 1H7770 14N1360 16O1525 32S22 for the most abundant peak of chondroitinase I. However, this peak is actually composed of 509 overlapping isobaric peaks (assuming those below 14% abundance do not contribute) of different isotopic composition, so that the true RP value is >170,000.
Williams, E. R.; Henry, K. D.; McLafferty, F. W. J. Am. Chem. Soc. 1990, 112, 6157–6162;
Pitsenberger, C. C.; Easterling, M. L.; Amster, I. J. Anal. Chem. 68 1996, 3732–3739.
Lee, S. A.; Jiao, C. Q.; Huang, Y.; Freiser, B. S. Rapid Commun. Mass Spectrom. 1993, 7, 819–821.
Gauthier, J. W.; Trautman, T. R.; Jacobson, D. B. Anal. Chim. Acta 1991, 246, 211–225.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kelleher, N.L., Senko, M.W., Siegel, M.M. et al. Unit resolution mass spectra of 112 kDa molecules with 3 Da accuracy. J Am Soc Mass Spectrom 8, 380–383 (1997). https://doi.org/10.1016/S1044-0305(97)00060-3
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/S1044-0305(97)00060-3