Abstract
Analytical and Chemical Sciences, Research Triangle Institute, Research Triangle Park, North Carolina, USA Negative ion electrospray (ES) operating on a single quadrupole mass spectrometer for the detection of low-molecular-weight molecules is discussed. The ES interface was operated at a positive cylindrical electrode potential to produce negative ions, and the results obtained were compared to the positive ion mode. As in the case of operation in the more common positive mode, negative ions with varying degrees of solvation and structurally relevant fragments can be obtained from a variety of solute species, including β-lactam antibiotics, aminoglycosides, aminocyclitols, tetracyclines, sulfonamides, nucleotides, peptides, and explosives. No fragmentation of parent species, except those from some labile explosives, was provided because low potential differences are applied between the capillary and the first skimmer, and electrical discharge is avoided in the gas phase. An increase in the capillary voltage resulted in collision-induced decomposition to produce structurally relevant fragment ions in both operation modes. An evaluation of representative chromatographic solvents indicated that 2-propanol added with oxygen in the ES bath gas is best suited to suppress electrical (corona) discharge phenomena in negative ion operation, whereas it aids in solution nebulization, desolvation, and transfer of ions in solution to the gas phase. For positive ion mode, no such precaution was necessary. Conditions that promote the formation of ions in solution usually improve ES response. Therefore, an increase in the solvent pH can increase the sensitivity in negative ion ES ionization. Negative ion ES offers the advantage of providing complementary structural information to help in the characterization of an unknown compound or to confirm a certain tentatively proposed structure. Nucleotides and explosives were best characterized in negative ion mode owing to the ease with which they form anions in solution, and they could be detected down to the l-pg /gML level.
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References
Micelson, D. Electrostatic Atomization; Adam Hilger; Bristol, 1990.
Embo, A. IEEE Trans. Comput. 1972, C-21, 942–948.
Dole, M.; Mack, L. C.; Hines, K. L.; Mobley, R C.; Ferguson, L. D.; Alice, M. B. J. Chem. Phys. 1968, 49, 2240–2249.
Simons, D. S.; Colby, 8. N.; Evans, C. A. Jr. Int. J. Mass Spectrom. Ion Phys. 1974, 75, 291–302.
Yamashita, M.; Fenn, J. B. J. Phys. Chem. 1984, 88, 4451–4459.
Yamashita, M.; Fenn J. B. J. Phys. Chem. 1984, 88, 4671–4675.
Whitehouse, C. M.; Dreyer, R. N., Yamashita, M.; Fenn, J. B. Anal. Chem. 1985, 57, 675–679.
Wong S. F.; Meng, C. K.; Fenn, J. B. J. Phys. Chem. 1988, 92, 546–550.
Fenn, J. B.; Mann, M.; Meng, C. K.; Wang, S. F. Mass Spectrom. Rev. 1990, 37-70.
Fenn, J. B.; Mann, M.; Meng, C. K.; Wang, S. F.; Whitehouse, C. Science 1989, 246, 64–71.
Whitehouse, C. M.; Shen, S.; Fenn, J. B. Presented at the 40th ASMS Conference on Mass Spectrometry and Allied Topics; Washington, DC, May 31–June 5, 1992; Paper TOA 1:15.
Bruins, A. I’.; Covey, T. R.; Henion, J. D. Anal. Chem. 1987, 59, 2642–2646.
Iribarne, J. V.; Thomson, B. A. J. Chem. Phys. 1976, 64, 2287–2289.
Thomson, B. A.; Iribarne, J. V. J. Chem. Phys. 1979, 71, 4451–4463.
Loo, J. A.; Udseth, H. R.; Smith, R. D. Rapid Commun. Mass Spectrom. 1988, 2, 207–210.
Wang, Y. Y.; Lyttle, M. H.; Borer, P. N. Nucleic Acids Res. 1990, 18, 3347–3352.
Bruins, A. P.; Weidolf, L. 0. G.; Henion, J. D.; Budde, W. L. Anal. Chem. 1987, 59, 2647–2652.
Edlund, P. 0.; Lee, E. D.; Henion, J. D.; Budde, W. L. Anal. Chem. 1989, 18, 233–240.
Straub, R; Voyksner, R. D. J. Chromatogr. 1992, 627, 173–166.
Rose, M. E.; Wycherlcy, D.; Preece. S. W. Ogr. Mass Spectrom. 1992, 27, 876–882.
Smith, R. D.; Loo, J. A.; Edmonds, C. G.; Barinaga, C. J.; Udseth, H. R. Anal. Chem. 1990, 62, 882–899.
Loo, J. A.; Ogorzalek-Loo, R. R.; Light, K. J.; Edmonds, C. G.; Smith R. D. Anal. Chem. 1992, 62, 81–88.
Kulik, W.; Heerma, W. Biol. Mass Spectrom. 1991, 20.553–558.
Stults, J. T.; Marsters, J. C. Rapid Commun. Mass Spectrom. 1991, 5, 359–363.
Hiraoka, K.; Kudaka, I. Rapid Commun. Mass Spectrom. 1992, 6, 265–268.
Ikonomou, M. G.; Blades, A. T.; Kebarle, P. J. Am. Soc. Mass Spectrom. 1991, 2, 497–505.
Chowdhury, 5. K.; Katta, V.; Chait, B. T. J. Am. Chem. Soc. 1990, 212, 9012–9013.
Cole, R. B.; Harrata, A. K. Rapid Commun. Mass Spectrom. 1992, 8, 536–539.
Ikonomou, M. G.: Blades, A. H.; Kebarle, P. Anal. Chem. 1990, 62, 957–967.
30 Blades, A. T.; Jayaweera, P.; Ikonomou, M. G.; Kebarle, P. J. Chem. Phys. 1990, 92, 5900–5929.
Smith, D. P. H. IEEE Trans. Ind. Appl. 1986, 1A-22, 527–535.
Hayati, 1.; Bailey, 1.; Tadros, T. F. Nature 1986, 319, 41–43.
Tang, L.; Kebarle, P. Anal. Chem. 1991, 63, 2709–2715.
Tyczkowska, K. L.; Voyksner, R. D.; Aronson, A. L. J. Chromatogr 1991, 594, 195–201.
Whelton, A., Ed. The Aminoglycosides; Marcel Dekker: New York, 1982.
Voyksner, R. D.; Pack, T. Rapid Commun. Mass Spectrom. 1991, 5, 263–268.
McLaughlin, L. G.; Henion, J. D. J. Chromatogr. 1992, 591, 195–206.
Perkins, J. R.; Parker, C. E.; Tamer, K. B. J. Am. Soc. Mass Spectrom. 1992, 3, 139–149.
Straub, R. F.; Voyksner, R. D. Presented at the 40th ASMS Conference on Mass Spectrometry and Allied Topics; Washington, DC, May 31–June 5,1992; pp 1879–1880.
Straub, R. F.; Voyksner, R. D. Presented at the 9th (Montreux) Symposium on Liquid Chromatography Mass Spectrometry, Montreux, Switzerland, November 4–6, 1992.
Crow, F. W.; Tamer, K. B.; Gross, M. L.; McCloskey, J. A.; Bergstrom, D. E. Anal. Biochern. 1984, 139, 243–262.
Slowikowski, D. L.; Schram, K. H. Nucleosides Nucleotides 1985, 4, 309–345.
Tomer, K. B.; Gross, M. L.; Deinzer, M. L. Anal. Chem. 1986, 58, 2527–2534.
Yinon, J.; Zitrin, S.The Analysis of Explosives; Pergamon Press: Oxford, 1981.
Parker, C. E.; Voyksner, R. D.; Tondeur, Y.; Henion, J. D.; Harvan, D. J.; Hass, J. R.; Yinon, J. J. Forensic Sci. 1982, 27, 4955505.
Yinon, J. Int. J. Mass Spectrom. ion Phys. 1983, 48, 253–256.
Yinon, 1.; Hwang, D. G. J. Chromatogr. 1983, 268, 45–53.
Vouros, P.; Petersen, B. A.; Karger, B. L.; Harris, H. Anal. Chem. 1977, 49,1039–1044.
Douse, J. M. F. J. Chromatogr. 1985, 328, 155–165.
Voyksner, R. D.; Yinon J. J. Chromatogr. 1986, 354, 393–405.
McLuckey, S. A.; Glish, G. L.; Asano, K. G. Anal. Chim: Acta 1989, 225, 25–35.
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Straub, R.F., Voyksner, R.D. Negative ion formation in electrospray mass spectrometry. J Am Soc Mass Spectrom 4, 578–587 (1993). https://doi.org/10.1016/1044-0305(93)85019-T
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DOI: https://doi.org/10.1016/1044-0305(93)85019-T