Abstract
Reduction of the oligomers formed from on-line electropolymerization of aniline, the compound N-phenyl-1,4-phenylenediimine, and the thiazine dye thionin was observed in both an atmospheric pressure chemical ionization and an atmospheric pressure photoionization source. The reduction, which alters the mass of these analytes by 2 Da, was shown to occur by means of a surface-assisted process which involves reactive species, possibly hydrogen radicals, generated from protic solvents in the ionization plasma. Reduction was minimized by limiting protic solvents, by using a high heated nebulizer temperature, and by using a clean, heated nebulizer probe liner. The expected generality of this reduction process, and the possibility of similar reduction processes in other plasma ionization sources are discussed in relation to the use of these ion sources for on-line electrochemistry/mass spectrometry experiments.
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Karancsi, T.; Slegel, P. Reliable Molecular Mass Determination of Aromatic Nitro Compounds: Elimination of Gas-Phase Reduction Occurring During Atmospheric Pressure Chemical Ionization. J. Mass Spectrom. 1999, 34, 975–977.
Carroll, D. L.; Dzidic, I.; Horning, E. C.; Stillwell, R. N. Atmospheric Pressure Ionization Mass Spectrometry. Applied Spectrom. Rev. 1981, 17, 337–406.
Budzikiewicz, H. Reactions Between Substrate Molecules and Chemical Ionization Reagent Gas Prior to Ionization. Org. Mass Spectrom. 1988, 23, 561–565.
McEwen, C. N.; Layton, S. F.; Taylor, S. K. Field Desorption and Electron Impact Mass Spectra of Ionic Dyes. Anal. Chem. 1977, 49, 922–926.
Gale, P. J.; Bentz, B. L.; Chait, B. T.; Field, F. H.; Cotter, R. J. Reduction in Liquid Secondary Ion Mass Spectrometry. Comparison of the Fission Fragment and Liquid Secondary Ion Mass Spectra of Organic Dyestuffs. Anal. Chem. 1986, 58, 1070–1076.
Ballard, J. M.; Betwoski, L. D. Thermospray Ionization and Tandem Mass Spectrometry of Dyes. Org. Mass Spectrom. 1986, 21, 575–588.
Turnipseed, S. B.; Roybal, J. E.; Rupp, H. S.; Hurlbut, J. A.; Long, A. R. Particle Beam Liquid Chromatography-Mass Spectrometry of Triphenylmethane Dyes: Application to Confirmation of Malachite Green in Incurred Catfish Tissue. J. Chromatogr. B 1995, 670, 55–62.
Robb, D. B.; Covey, T. R.; Bruins, A. P. Atmospheric Pressure Photoionization: An Ionization Method for Liquid Chromatography-Mass Spectrometry. Anal. Chem. 2000, 72, 3653–3659.
Volk, K. J.; Yost, R. A.; Brajter-Toth, A. Electrochemistry On-Line with Mass Spectrometry: Insight into Biological Redox Reactions. Anal. Chem. 1992, 64, 21A-33A.
Diehl, G.; Liesener, A.; Karst, U. Liquid Chromatography with Post-Column Electrochemical Treatment and Mass Spectrometric Detection of Non-Polar Compounds. Analyst 2001, 126, 288–290.
Johnson, K. A.; Shira, B. A.; Anderson, J. L.; Amster, I. J. Chemical and On-Line Electrochemical Reduction of Metallo-proteins with High Resolution Electrospray Ionization Mass Spectrometry Detection. Anal. Chem. 2001, 73, 803–808.
Kertesz, V.; Van Berkel, G. J. Electropolymerization of Methylene Blue Investigated Using On-Line Electrochemistry/Electrospray Mass Spectrometry. Electroanalysis, in press.
Deng, H.; Van Berkel, G. J.; Takano, H.; Gazda, D.; Porter, M. D. Electrochemically-Modulated Liquid Chromatography Coupled On-line with Electrospray Mass Spectrometry. Anal. Chem. 2000, 72, 2641–2647.
Jurva, U.; Wikstrom, H. V.; Bruins, A. P. In Vitro Mimicry of Metabolic Oxidation Reactions by Electrochemistry/Mass Spectrometry. Rapid Commun. Mass Spectrom. 2000, 14, 529–533.
Pretty, J. R.; Deng, H.; Goeringer, D. E.; Van Berkel, G. J. Electrochemically-Modulated Preconcentration and Matrix Elimination for Organic Analytes Coupled On-Line with Electrospray Mass Spectrometry. Anal. Chem. 2000, 72, 2066–2074.
Arakawa, R.; Abura, T.; Fukuo, T.; Horiguchi, H.; Matsubayashi, G. Analysis of Electrolysis Reactions of Metal Complexes Using On-Line Electrospray Ionization Mass Spectrometry with a Compact Electrolysis Flow-Through Cell. Bull. Chem. Soc. Jpn. 1999, 72, 1519–1523.
Deng, H.; Van Berkel, G. J. Electrochemical Polymerization of Aniline Investigated Using On-Line Electrochemistry/Electrospray Mass Spectrometry. Anal. Chem. 1999, 71, 4284–4293.
Deng, H.; Van Berkel, G. J. A Thin-Layer Flow Cell Coupled On-Line with Electrospray-Mass Spectrometry for the Study of Biological Redox Reactions. Electroanalysis 1999, 11, 857–865.
Iwahashi, H. 3-Hydroxyanthralinic Acid-Derived Compounds Formed Through Electrochemical Oxidation. J. Chromatogr. B 1999, 237, 237–245.
Pretty, J. R.; Van Berkel, G. J. Electrochemical Sample Pretreatment Coupled On-Line with Electrospray Mass Spectrometry for Enhanced Elemental Analysis. Rapid Commun. Mass Spectrom. 1998, 12, 1644–1652.
Iwahashi, H.; Ishii, T. Detection of the Oxidative Products of 3-Hydroxykynurenine using High-Performance Liquid Chromatography-Electrochemical Detection-Ultraviolet Absorption Detection-Electron Spin Resonance Spectrometry and High-Performance Liquid Chromatography-Electrochemical Detection-Ultraviolet Absorption Detection-Mass Spectrometry. J Chromatogr. A 1997, 773, 23–31.
Lu, W.; Xu, X.; Cole, R. B. On-Line Linear Sweep Voltammetry-Electrospray Mass Spectrometry. Anal. Chem. 1997, 69, 2478–2484.
Xu, X.; Lu, W.; Cole, R. B. On-Line Probe for Fast Electrochemistry/Electrospray Mass Spectrometry. Investigation of Polycyclic Aromatic Hydrocarbons. Anal. Chem. 1997, 69, 2478–2484.
Bond, A. M.; Colton, R.; D’Agnostino, A.; Downard, A. J.; Traeger, J. C. A Role for Electrospray Mass Spectrometry in Electrochemical Studies. Anal. Chem. 1995, 67, 1691–1695.
Zhou, F.; Van Berkel, G. J. Electrochemistry Combined On-Line with Electrospray Mass Spectrometry. Anal. Chem. 1995, 67, 3643–3649.
Kertesz, V.; Van Berkel, G. J. Minimizing Analyte Electrolysis in an Electrospray Emitter. J. Mass Spectrom. 2001, 36, 204–210.
Lunte, S. M.; Lunte, C. E.; Kissinger, P. T. In Laboratory Techniques in Electroanalytical Chemistry; Kissinger, P. T.; Heineman, W. R., Eds., Marcel Dekker: New York, 1996; Chap XXVII, pp 813–853.
Lemmon, T. L.; Westall, J. C.; Ingle, J. D., Jr. Development of Redox Sensors for Environmental Applications Based on Immobilized Redox Indicators. Anal. Chem. 1996, 68, 947–953.
Karyakin, A. A.; Karyakina, E. E.; Schmidt, H.-L. Electropolymerized Azines: A New Group of Electroactive Polymers. Electroanalysis 1999, 11, 149–155.
McEwen, C. N. Radicals in Analytical Mass Spectrometry. Mass Spectrom. Rev. 1986, 5, 521–547.
Stassen, I.; Hambitzer, G. Anodic Oxidation of Aniline and N-Alkylanilines in Aqueous Sulfuric Acid Studied by Electrochemical Thermospray Mass Spectrometry. J. Electroanal. Chem. 1997, 440, 219–228.
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Kertesz, V., Van Berkel, G.J. Surface-assisted reduction of aniline oligomers, N-phenyl-1,4-phenylenediimine and thionin in atmospheric pressure chemical ionization and atmospheric pressure photoionization. J Am Soc Mass Spectrom 13, 109–117 (2002). https://doi.org/10.1016/S1044-0305(01)00337-3
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DOI: https://doi.org/10.1016/S1044-0305(01)00337-3