Abstract
We determine the elemental compositions of aromatic nitrogen model compounds as well as a petroleum sample by atmospheric pressure photoionization (APPI) and electrospray Ionization (ESI) with a 9.4 Tesla Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. From the double-bond equivalents calculated for the nitrogen-containing ions from a petroleum sample, we can infer the aromatic core structure (pyridinic versus pyrrolic nitrogen heterocycle) based on the presence of M+· (odd-electron) versus [M+H]+ (even-electron) ions. Specifically, nitrogen speciation can be determined from either a single positive-ion APPI spectrum or two ESI (positive- and negative-ion) spectra. APPI operates at comparatively higher temperature than ESI and also produces radical cations that may fragment before detection. However, APPI fragmentation of aromatics can be eliminated by judicious choice of instrumental parameters.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Marshall, A. G.; Hendrickson, C. L.; Jackson, G. S. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: A Primer. Mass Spectrom. Rev. 1998, 17, 1–35.
Marshall, A. G.; Rodgers, R. P. Petroleomics: The Next Grand Challenge for Chemical Analysis. Acc. Chem. Res. 2004, 37, 53–59.
Rodgers, R.; Schaub, T.; Marshall, A. Petroleomics: MS Returns to Its Roots. Anal. Chem. 2005, 77, 20A-27A.
Zhan, D. L.; Fenn, J. B. Electrospray Mass Spectrometry of Fossil Fuels. Int. J. Mass Spectrom. 2000, 194, 197–208.
Rodgers, R. P.; Klein, G. C.; Stanford, L. A.; Kim, S.; Marshall, A. G. Characterization of Heavy, Biodegraded Crude Oils by High Resolution ESI FT-ICR Mass Spectrometry. Am. Chem. Soc. Abstr. 2004, 228, U654.
Rodgers, R. P.; Hendrickson, C. L.; Emmett, M. R.; Marshall, A. G. Reading Chemical Fine Print: Resolution and Identification of 3000 Nitrogen-containing Aromatic Compounds from a Single Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrum of Heavy Petroleum Crude Oil. Energy Fuels 2001, 15, 492–498.
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.
Syage, J. A.; Evans, M. D. Photoionization Mass Spectrometry. Spectroscopy 2001, 16, 14–21.
Tubaro, M.; Marotta, E.; Seraglia, R.; Traldi, P. Atmospheric Pressure Photoionization Mechanisms: 2. The Case of Benzene and Toluene. Rapid Commun. Mass Spectrom. 2003, 17, 2423–2429.
Raffaelli, A.; Saba, A. Atmospheric Pressure Photoionization Mass Spectrometry. Mass Spectrom. Rev. 2003, 22, 318–331.
Hughey, C. A.; Rodgers, R. P.; Marshall, A. G. Resolution of 11,000 Compositionally Distinct Components in a Single Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrum of Crude Oil. Anal. Chem. 2002, 74, 4145–4149.
Purcell, J. M.; Hendrickson, C. L.; Rodgers, R. P.; Marshall, A. G. Atmospheric Pressure Photoionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry for Complex Mixture Analysis. Anal. Chem. 2006, 78, 5906–5912.
Senko, M. W.; Hendrickson, C. L.; Pasa-Tolic, L.; Marto, J. A.; White, F. M.; Guan, S.; Marshall, A. G. Electrospray Ionization Fourier Transform Ion Cyclotron Resonance at 9.4 T. Rapid Commun. Mass Spectrom. 1996, 10, 1824–1828.
Rudzinski, W. E.; Aminabhavi, T. M.; Sassman, S.; Watkins, L. M. Isolation and Characterization of the Saturate and Aromatic Fractions of a Maya Crude Oil. Energy Fuels 2000, 14, 839–844.
Håkansson, K.; Chalmers, M. J.; Quinn, J. P.; McFarland, M. A.; Hendrickson, C. L.; Marshall, A. G. Combined Electron Capture and Infrared Multiphoton Dissociation for Multistage MS/MS in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. Anal. Chem. 2003, 75, 3256–3262.
Marshall, A. G.; Verdun, F. R. Fourier Transforms in NMR, Optical, and Mass Spectrometry: A User’s Handbook; Elsevier: Amsterdam, 1990.
Senko, M. W.; Beu, S. C.; McLafferty, F. W. Automated Assignment of Charge States from Resolved Isotopic Peaks for Multiply Charged Ions. J. Am. Soc. Mass Spectrom. 1995, 6, 52–56.
Emmett, M. R.; Caprioli, R. M. Micro-Electrospray Mass Spectrometry: Ultra-high-sensitivity Analysis of Peptides and Proteins. J. Am. Soc. Mass Spectrom. 1994, 5, 605–613.
McLafferty, F. W.; Turececk, F. Interpretation of Mass Spectra; 4th ed.; University Science Books: Mill Valley, CA, 1993.
Rapp, U.; Staab, H. A.; Wunsche, C. NIST 2005 [NIST/EPA/NIH Mass Spectral Library 2005 (Upgrade)]; Wiley: Hoboken, NJ, 2005.
Hughey, C. A.; Hendrickson, C. L.; Rodgers, R. P.; Marshall, A. G.; Qian, K. Kendrick Mass Defect Spectrum: A Compact Visual Analysis for Ultrahigh-Resolution Broadband Mass Spectra. Anal. Chem. 2001, 73, 4676–4681.
Hagman, C.; Tsybin, Y. O.; Häkansson, P. Solution-phase Deuterium/Hydrogen Exchange at a Specific Residue Using Nozzle-Skimmer and Electron Capture Dissociation Mass Spectrometry. Rapid Commun. Mass Spectrom. 2006, 20, 661–665.
Loo, J. A.; Edmonds, C. G.; Smith, R. D. Tandem Mass-Spectrometry of Very Large Molecules—Serum-Albumin Sequence Information from Multiply Charged Ions Formed by Electrospray Ionization. Anal. Chem. 1991, 63, 2488–2499.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online April 10, 2007
Rights and permissions
About this article
Cite this article
Purcell, J.M., Rodgers, R.P., Hendrickson, C.L. et al. Speciation of nitrogen containing aromatics by atmospheric pressure photoionization or electrospray ionization fourier transform ion cyclotron resonance mass spectrometry. J Am Soc Mass Spectrom 18, 1265–1273 (2007). https://doi.org/10.1016/j.jasms.2007.03.030
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2007.03.030