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A New Matrix Assisted Ionization Method for the Analysis of Volatile and Nonvolatile Compounds by Atmospheric Probe Mass Spectrometry

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

Matrix assisted ionization of nonvolatile compounds is shown not to be limited to vacuum conditions and does not require a laser. Simply placing a solution of analyte dissolved with a suitable matrix such as 3-nitrobenzonitrile (3-NBN) or 2,5-dihydroxyacetophenone on a melting point tube and gently heating the dried sample near the ion entrance aperture of a mass spectrometer using a flow of gas produces abundant ions of peptides, small proteins, drugs, and polar lipids. Fundamental studies point to matrix-mediated ionization occurring prior to the entrance aperture of the mass spectrometer. The method is analytically useful, producing peptide mass fingerprints of bovine serum albumin tryptic digest consuming sub-picomoles of sample. Application of 100 fmol of angiotensin I in 3-NBN matrix produces the doubly and triply protonated molecular ions as the most abundant peaks in the mass spectrum. No carryover is observed for samples containing up to 100 pmol of this peptide. A commercial atmospheric samples analysis probe provides a simple method for sample introduction to an atmospheric pressure ion source for analysis of volatile and nonvolatile compounds without using the corona discharge but using sample preparation similar to matrix-assisted laser desorption/ionization.

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References

  1. Watson, J.T., Sparkman, O.D.: Introduction to Mass Spectrometry: Instrumentation; Applications and Strategies for Data Interpretation, 4th edn. Wiley, New York (2007)

    Book  Google Scholar 

  2. Cody, R.B., Laramée, J.A., Durst, H.D.: Versatile new ion source for the analysis of materials in open air under ambient conditions. Anal. Chem. 77, 2297–2302 (2005)

    Google Scholar 

  3. McEwen, C.N., McKay, R.G., Larsen, B.S.: Analysis of solids, liquids, and biological tissues using solids probe introduction at atmospheric pressure on commercial LC/MS instruments. Anal. Chem. 77, 7826–7831 (2005)

    Google Scholar 

  4. Saha, S., Chen, L.C., Mandal, M.K., Hiraoka, K.: Leidenfrost phenomenon-assisted thermal desorption (LPTD) and its application to open ion sources at atmospheric pressure mass spectrometry. J. Am. Soc. Mass Spectrom. 24, 341–347 (2013)

    Article  CAS  Google Scholar 

  5. Karas, M., Bachman, D., Bahr, U., Hillenkamp, F.: Matrix-assisted ultraviolet laser desorption of non-volatile compounds. Int. J. Mass Spectrom. Ion Processes. 78, 53–68 (1987)

    Article  CAS  Google Scholar 

  6. Fenn, J.B., Mann, M., Meng, C.K., Wong, S.F., Whitehouse, C.M.: Electrospray ionization for analysis of large molecules. Science 246, 64–67 (1989)

    Article  CAS  Google Scholar 

  7. Venter, A., Nefliu, M., Cooks, R.G.: Ambient desorption ionization mass spectrometry. Trends Anal. Chem. 27, 284–290 (2008)

    Article  CAS  Google Scholar 

  8. Takats, Z., Wiseman, J.M., Gologan, B., Cooks, R.G.: Mass spectrometry sampling under ambient conditions with desorption electrospray ionization. Science 306, 471–473 (2004)

    Article  CAS  Google Scholar 

  9. Shiea, J., Huang, M.-Z., Hsu, C.-Y., Lee, C.-H., Yuan, I., Beech, J.: Electrospray-assisted laser desorption/ionization mass spectrometry for direct ambient analysis of solids. Rapid Commun. Mass Spectrom. 19, 3701–3704 (2005)

    Article  CAS  Google Scholar 

  10. Chen, H., Venter, A., Cooks, R.G.: Extractive electrospray ionization for direct analysis of undiluted urine, milk, and other complex mixtures without sample preparation. Chem.Commun. 2042–2044 (2006)

  11. Hiraoka, K., Nishidate, K., Mori, K., Asakawa, D., Suzuki, S.: Development of probe electrospray using a solid needle. Rapid Commun. Mass Spectrom. 21, 3139–3144 (2007)

    Article  CAS  Google Scholar 

  12. Mandal, M.K., Chen, L.C., Yu, Z., Nonami, H., Erra-Balsells, R., Hiraoka, K.: Detection of protein from detergent solutions by probe electrospray ionization mass spectrometry (PESI-MS). J. Mass Spectrom. 46, 967–975 (2011)

    Article  CAS  Google Scholar 

  13. Wang, H., Liu, J., Cooks, R.G., Ouyang, Z.: Paper spray for direct analysis of complex mixtures using mass spectrometry. Angew Chem 122, 889–892 (2010)

    Article  Google Scholar 

  14. Hu, B., So, P.K., Chen, H., Yao, Z.P.: Electrospray ionization using wooden tips. Anal Chem 83, 8201–8207 (2011)

    Article  CAS  Google Scholar 

  15. Liu, J., Wang, H., Cooks, R.G., Ouyang, Z.: Leaf spray: Direct chemical analysis of plant material and living plants by mass spectrometry. Anal. Chem. 83, 7608–7613 (2011)

    Google Scholar 

  16. Trimpin, S., Inutan, E.D., Herath, T.N., McEwen, C.N.: Laserspray ionization—a new AP-MALDI method for producing highly charged gas-phase ions of peptides and proteins directly from solid solutions. Mol. Cell. Proteomics 9, 362–367 (2010)

    Google Scholar 

  17. Trimpin, S., Inutan, E.D., Herath, T.N., McEwen, C.N.: Matrix-assisted laser desorption/ionization mass spectrometry method for selectively producing either singly or multiply charged molecular ions. Anal Chem 82, 11–15 (2010)

    Article  CAS  Google Scholar 

  18. McEwen, C.N., Pagnotti, V.S., Inutan, E.D., Trimpin, S.: New paradigm in ionization: Multiply charged ion formation from a solid matrix without a laser or voltage. Anal Chem 82, 9164–9168 (2010)

    Article  CAS  Google Scholar 

  19. Inutan, E.D., Wang, B., Trimpin, S.: Commercial intermediate pressure MALDI ion mobility spectrometry mass spectrometer capable of producing highly charged laserspray ionization ions. Anal Chem 83, 678–684 (2011)

    Article  CAS  Google Scholar 

  20. Trimpin, S., Ren, Y., Wang, B., Lietz, C.B., Richards, A.L., Marshall, A.G., Inutan, E.D.: Extending the laserspray ionization concept to produce highly charged ions at high vacuum on a time-of-flight mass analyzer. Anal Chem 83, 5469–5475 (2011)

    Article  CAS  Google Scholar 

  21. Inutan, E.D., Trimpin, S.: Matrix assisted ionization vacuum, a new ionization method for biological materials analysis using mass spectrometry. Mol. Cell. Proteomics 12(3), 792–796 (2013)

    Google Scholar 

  22. Trimpin, S., Inutan, E.D.: Matrix assisted ionization in vacuum, a widely applicable ionization method for mass spectrometry. J. Am. Soc. Mass Spectrom. doi:10.1007/s13361-012-0571-z (2013)

    Google Scholar 

  23. Trimpin, S., Inutan, E.D.: New ionization method for analysis on atmospheric pressure ionization mass spectrometers requiring only vacuum and matrix assistance. Anal. Chem. 85(4), 2005–2009 (2013)

    Google Scholar 

  24. Barrere, C., Maire, F., Afonso, C., Giusti, P.: Atmospheric solid analysis probe-ion mobility mass spectrometry of polypropylene. Anal. Chem. 84, 9349–9354 (2012)

    Google Scholar 

  25. Lindberg, J., DerMarderosian, A.: A rapid qualitative analysis of natural products by atmospheric solids analysis probe mass spectrometry (ASAP-MS). Planta Medica 78, 1262–1264 (2012)

    Google Scholar 

  26. Bruns, E.A., Greaves, J., Finlayson-Pitts, B.J.: Measurement of vapor pressures and heats of sublimation of dicarboxylic acids using atmospheric solids analysis probe mass ppectrometry. J Phys Chem A 116, 5900–5909 (2012)

    Article  CAS  Google Scholar 

  27. Rivera, S.M., Canela-Garayoa, R.: Analytical tools for the analysis of carotenoids in diverse materials. J. Chromatogr. A 1224, 1–10 (2012)

    Article  CAS  Google Scholar 

  28. Rozenski, J.: Analysis of nucleosides using the atmospheric-pressure solids analysis probe for ionization. Int. J. Mass Spectrom. 304, 204–208 (2011)

    Article  CAS  Google Scholar 

  29. Ahmed, A., Cho, Y.J., No, M.H., Koh, J., Tomczyk, N., Giles, K., Yoo, J.S., Kim, S.: Application of the mason-schamp equation and ion mobility mass spectrometry to identify structurally related compounds in crude oil. Anal. Chem. 83, 77–83 (2011)

    Google Scholar 

  30. Fussell, R.J., Chan, D., Sharman, M.: An assessment of atmospheric-pressure solids-analysis probes for the detection of chemicals in food. Trends Anal. Chem. 29, 1326–1335 (2010)

    Article  CAS  Google Scholar 

  31. Twohig, M., Shockcor, J.P., Wilson, I.D., Nicholson, J.K., Plumb, R.S.: Use of an atmospheric solids analysis probe (ASAP) for high throughput screening of biological fluids: Preliminary applications on urine and bile. J. Proteome Res. 9, 3590–3597 (2010)

    Article  CAS  Google Scholar 

  32. Lloyd, J.A., Harron, A.F., McEwen, C.: Combination atmospheric pressure solids analysis probe and desorption electrospray ionization mass spectrometry ion source. Anal. Chem. 81, 9158–9162 (2009)

    Google Scholar 

  33. Zydel, F., Trimpin, S., McEwen, C.N.: Laserspray ionization using an atmospheric solids analysis probe for sample introduction. J. Am. Soc. Mass Spectrom. 21, 1889–1892 (2010)

    CAS  Google Scholar 

  34. Trimpin, S., Wang, B., Inutan, E.D., Li, J., Lietz, C.B., Harron, A.F., Pagnotti, V.S., Sardelis, D., McEwen, C.N.: A mechanism for ionization of nonvolatile compounds in mass spectrometry: Considerations from MALDI and inlet ionization. J. Am. Soc. Mass Spectrom. 23, 1644–1660 (2012)

    Article  CAS  Google Scholar 

  35. Gobom, J., Nordhoff, E., Mirgorodskaya, E., Ekman, R., Roepstorff, P.: Sample purification and preparation technique based on nano-scale reversed-phase columns for the sensitive analysis of complex peptide mixtures by matrix-assisted laser desorption/ionization mass spectrometry. J. Mass Spectrom. 34, 105–116 (1999)

    Article  CAS  Google Scholar 

  36. Krause, J., Stoeckli, M., Schlunegger, U.P.: Studies on the selection of new matrices for ultraviolet matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Rapid Commun. Mass Spectrom. 10, 1927–1933 (1996)

    Article  CAS  Google Scholar 

  37. Halgand, F., Zabrouskov, V., Bassilian, S., Souda, P., Wong, D.T., Loo, J.A., Faull, K.F., Whitelegge, J.P.: Micro-heterogeneity of human saliva peptide P-C characterized by high-resolution top-down Fourier-transform mass spectrometry. J. Am. Soc. Mass Spectrom. 21, 868–877 (2010)

    Article  CAS  Google Scholar 

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Acknowledgments

This work was made possible by funding from NSF-CHE-1112289 and the Richard Houghton endowment to the University of the Sciences to CNM, and for funding and support from Wayne State University Schaap Faculty Scholar, NSF CAREER 0955975, ASMS Research Award, DuPont Young Professor Award, Waters Center of Innovation Award, and Eli Lilly Young Investigator Award in Analytical Chemistry to S.T.

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Authors and Affiliations

  1. University of the Sciences, Philadelphia, PA, USA

    Shubhashis Chakrabarty, Vincent S. Pagnotti & Charles N. McEwen

  2. Wayne State University, Detroit, MI, USA

    Ellen D. Inutan & Sarah Trimpin

Authors
  1. Shubhashis Chakrabarty
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  2. Vincent S. Pagnotti
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  3. Ellen D. Inutan
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  4. Sarah Trimpin
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  5. Charles N. McEwen
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Corresponding author

Correspondence to Charles N. McEwen.

Additional information

Shubhashis Chakrabarty and Vincent S. Pagnotti contributed equally to this work.

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Supporting Information

Figures showing mass spectra of bradykinin using 3-NBN, 2,5-DHAP, and 2,5-DHB, and angiotensin I, insulin, sphingomyelin, verapamil, hydroxycortisone, and hydroxychloroquine using 3-NBN with ASAP probe introduction are presented along with mass spectra of levofloxacin, ubiquitin, myoglobin, and saliva using 3-NBN and a voltage applied to the HESI probe. The mass spectrum of bradykinin using a Waters Xevo TQ-S mass spectrometer without an ASAP probe is also provided. (DOC 1513 kb)

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Chakrabarty, S., Pagnotti, V.S., Inutan, E.D. et al. A New Matrix Assisted Ionization Method for the Analysis of Volatile and Nonvolatile Compounds by Atmospheric Probe Mass Spectrometry. J. Am. Soc. Mass Spectrom. 24, 1102–1107 (2013). https://doi.org/10.1007/s13361-013-0634-9

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