Abstract
The efficacy of m-nitrobenzyl alcohol (NBA) as a solvent (matrix) for fast atom bombardment (FAB) mass spectrometry of a group of pyrazolate-bridged dirhodium A-frame complexes has been assessed. Although NBA is frequently used to mitigate the formation of artifacts in FAB/MS of organometallics and other materials susceptible to bombardment-induced reactions, substantial evidence indicates that such reactions cause the formation of artifacts in the spectra obtained here. Parallel absorption spectroscopic studies have established that NBA is capable of inducing both oxidation and reduction reactions independent of ion bombardment, depending on analyte reduction half-wave potential (E1/2). From the known electrochemistry of the complexes studied, it can be estimated that 1020 mV > E1/2 > 500 mV for the reaction of NBA serving as a reducing agent, while 500 mV > E1/2 > 424 mV for the reduction potential of NBA. However, in the presence of bombardment the former E1/2 must be at least as low as 356 mY, and the latter E1/2 must be at least as high as 1188 mY. The kinetics of redox reactions involving NBA, and therefore their influence on the appearance of FAB mass spectra, will be highly sample-dependent. However, this study illustrates an important potential role for redox reactions when NBA is used as a solvent, especially in the presence of bombardment in FAB/MS. Although analyte reaction products could be identified, substantial efforts aimed at identifying NBA oxidation and reduction products did not yield any definitive results due to the complexity of product mixtures.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
De Pauw, E. Mass Spectrom. Rev. 1986, 5, 191,
Reynolds, J, D.; Cook, K. D. J, Am. Soc. Mass Spectrom. 1990, 1, 149.
Keough, T. Int. J, Mass Spectrom, Ion Processes 1988, 86, 155.
Miller, J. M.; Balasanmugam, K,; Nye, J.; Deacon, G. B.; Thomas, N, C. Inorg. Chem. 1987, 26, 560,
Kyranos, J, N.; duSorbier, B. M.; Wronka, J.; Vouros, P.; Kirby, D. P. Org. Mass Spectrom. 1988, 23, 443.
Musselman, B.; Watson, J. T. Biomed. Environ. Mass Spectrom. 1987, 14, 247.
Williams, D. H.; Findeis, A. F.; Naylor, S.; Gibson, B. W. J. Am. Chem. Soc. 1987, 109, 1980.
Takayama, M.; Fukai, T.; Nomura, T. Int. J. Mass Spectrom. Ion Processes 1989, 89, R1.
Callahan, J. H.; Hool, K.; Reynolds, J. D.; Cook, K. D. Anal. Chem. 1988, 60, 714.
Miller, J.M. Mass Spectrom. Rev. 1990, 9, 319.
Mallis, L. M.; Scott, W. J. Org. Mass Spectrom. 1990, 25, 415.
Barber, M.; Bell, D.; Eckersley, M.; Morris, M.; Tetler, L. Rapid Commun. Mass Spectrom. 1988, 2, 18.
Nedderman, A. N. R.; Williams, D. H. Biological Mass Spectrom. 1991, 20. 289.
Aubagnac, J.L. Rapid Commun. Mass Spectrom. 1990, 4, 114.
Barber, M.; Bordoli, R. S.; Sedgwick, R. D.; Tyler, A. N. J. Chem. Soc. Chem. Commun. 1981, 325.
Sunner, J. A.; Morales, A.; Kebarle, P. Int. J. Mass. Spectrom. Ion Processes 1989, 87, 287.
Sunner, J. A.; Morales, A.; Kebarle, P. Anal. Chem. 1988, 60, 98.
Dube, G.; Vollhardt, D. Org. Mass Spectrom. 1990, 25, 404.
Reynolds, J. D.; Cook, K. D. J. Am. Soc. Mass Spectrom. 1990, 1, 233.
Reynolds, J. D.; Cook, K. D. Int. J. Mass Spectrom. Ion Processes 1990, 97, 325.
Callahan, J. H.; Hool, K; Reyonlds, J. D.; Cook, K D. Int. J. Mass Spectrom. Ion Processes 1987, 75, 291.
Ligon, W. V. Jr.: Dorn, S. B. Int. J. Mass Spectrom. Ion Processes 1985, 63, 315.
Ligon, W. V. Jr.: Dorn, S. B. Int. J. Mass Spectrom. Ion Processes 1986, 68, 337.
De Pauw, E.; Pelzer, G.; Dung, D. V.; Marien, J. Biomed. Biophys. Res.Commun. 1984, 123, 27.
Hand, O. W.; Scheifers, S. M.; Cooks, R. C. Int. J. Mass Spectrom. Ion Processes 1987, 78, 131.
Ligon, W. V. Jr.; Dorn, S. B. Int. J. Mass Spectrom. Ion Processes 1984, 57, 75.
Ligon, W. V. [r.: Dorn, S. B. Int. J. Mass Spectrom. Ion Processes 1987, 78, 99.
Ligon, W. V. Jr.: Dorn, S. B. Int. J. Mass Spectrom. Ion Processes 1984, 61, 113.
Ligon, W. V. [r.: Darn, S. B. Anal. Chem. 1985, 57, 1993.
Ligon, W. V. Jr.; Dorn, S, B. Fresenius Z. Anal. Chem. 1986, 325, 626.
Shiea, J.; Sunner J, Org, Mass Spectrom. 1991, 26, 38.
Todd, P. J. Org. Mass Spectrom. 1988, 23, 419.
Fraefel, A,; Seibl J., Mass Spectrom. Rev. 1985, 4, 151.
Wysocki, V. H.; Kenllamaa, H. I.; Cooks, R. G. Int. J. Mass Spectrom, Ion Processes 1987, 75, 181.
Vekey, K. Int. J. Mass Spectrom. Ion Processes. 1990, 97, 265.
Pelzer, G.; De Pauw, E.; Dung, D. V.; Marien, J. J. Phys. Chem. 1984, 88, 5065.
Cerny, R. L.; Gross, M. L. Anal. Chem. 1985, 57, 1160.
Santana-Marques, M. G. O.; Ferrer-Correia, A. J. V.; Gross M. L. Anal. Chem. 1989, 61, 1442.
Kyranos, J. N.; Vorous, P. Biomed. Environ. Mass Spectrom. 1990, 19, 628.
Prokai, L.; Hsu, B.-H.; Farag, H.; Bodor, N. Anal. Chem. 1989, 61, 1723.
Aubagnac, J. L.; Clarmont, R. M.; Sanz, D. Org. Mass Spectrom. 1990, 25, 293.
Sundholm, G. J. Electroanal. Chem. 1971, 31, 265.
Woods, C, Tortorelli, L. J.; Rillema, D. P.; Burn, J. L. E.; DePriest, J. C. Inorg, Chem. 1989, 28, 1673.
Janke, C. J.; Tortorelli, L. J.; Burn, J. J. E.; Tucker, C. A.; Woods, C. Inorg. Chem. 1986, 25, 4597.
Reynolds, J. D.; Bum, J. L. E.; Woods, C., Cook, K. D. In Proceedings 38th ASMS Conference on Mass Spectrometry and Allied Topics; Tucson, AZ, June 3–8, 1990; p. 1431.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Reynolds, J.D., Cook, K.D., Burn, J.L.E. et al. m-nitrobenzyl alcohol electrochemistry in fast atom bombardment mass spectrometry. J Am Soc Mass Spectrom 3, 113–121 (1992). https://doi.org/10.1016/1044-0305(92)87044-Y
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/1044-0305(92)87044-Y