Skip to main content

Bipolar Mass Spectrometry of Labile Coordination Complexes, Redox Active Inorganic Compounds, and Proteins Using a Glass Nebulizer for Sonic-Spray Ionization

Abstract

In this study, we report on the development of a novel nebulizer configuration for sonic-spray ionization (SSI) mass spectrometry (MS), more specifically for a version of SSI that is referred to as Venturi easy ambient sonic-spray ionization (V-EASI) MS. The developed nebulizer configuration is based on a commercially available pneumatic glass nebulizer that has been used extensively for aerosol formation in atomic spectrometry. In the present study, the nebulizer was modified in order to achieve efficient V-EASI-MS operation. Upon evaluating this system, it has been demonstrated that V-EASI-MS offers some distinct advantages for the analysis of coordination compounds and redox active inorganic compounds over the predominantly used electrospray ionization (ESI) technique. Such advantages, for this type of compounds, are demonstrated here for the first time. More specifically, a series of labile heptanuclear heterometallic [CuII 6LnIII] clusters held together with artificial amino acid ligands, in addition to easily oxidized inorganic oxyanions of selenium and arsenic, were analyzed. The observed advantages pertain to V-EASI appearing to be a “milder” ionization source than ESI, not requiring electrical potentials for gas phase ion formation, thus eliminating the possibility of unwanted redox transformations, allowing for the “simultaneous” detection of negative and positive ions (bipolar analysis) without the need to change source ionization conditions, and also not requiring the use of syringes and delivery pumps. Because of such features, especially because of the absence of ionization potentials, EASI can be operated with minimal requirements for source parameter optimization. We observed that source temperature and accelerating voltage do not seem to affect labile compounds to the extent they do in ESI-MS. In addition, bipolar analysis of proteins was demonstrated here by acquiring both positive and negative ion mass spectra from the same protein solutions, without the need to independently adjust solution and source conditions in each mode. Finally, the simple and efficient operation of a dual-nebulizer configuration was demonstrated for V-EASI-MS for the first time.

This is a preview of subscription content, access via your institution.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6

References

  1. Hirabayashi, A., Sakairi, M., Koizumi, H.: Sonic spray ionization method for atmospheric pressure ionization mass spectrometry. Anal. Chem. 66, 4557–4559 (1994)

    Article  CAS  Google Scholar 

  2. Hirabayashi, A., Sakairi, M., Koizumi, H.: Sonic spray mass spectrometry. Anal. Chem. 67, 2878–2882 (1995)

    Article  CAS  Google Scholar 

  3. Takats, Z., Nanita, S.C., Cooks, R.G., Schlosser, G., Vekey, K.: Amino acid clusters formed by sonic spray ionization. Anal. Chem. 75, 1514–1523 (2003)

    Article  CAS  Google Scholar 

  4. Haddad, R., Sparrapan, R., Eberlin, M.N.: Desorption sonic spray ionization for (high) voltage-free ambient mass spectrometry. Rapid Commun. Mass Spectrom. 20, 2901–2905 (2006)

    Article  CAS  Google Scholar 

  5. Haddad, R., Milagre, H.M.S., Catharino, R.R., Eberlin, M.N.: Easy ambient sonic-spray ionization mass spectrometry combined with thin-layer chromatography. Anal. Chem. 80, 2744–2750 (2008)

    Article  CAS  Google Scholar 

  6. Santos, V.G., Regiani, T., Dias, F.F.G., Romão, W., Jara, J.L.P., Klitzke, C.F., Coelho, F., Eberlin, M.N.: Venturi easy ambient sonic-spray ionization. Anal. Chem. 83, 1375–1380 (2011)

    Article  CAS  Google Scholar 

  7. Schwab, N.V., Porcari, A.M., Coelho, M.B., Schmidt, E.M., Jara, J.L., Visentainer, J.V., Eberlin, M.N.: Easy dual-mode ambient mass spectrometry with Venturi self-pumping, canned air, disposable parts, and voltage-free sonic-spray ionization. Analyst 137, 2537–2540 (2012)

    Article  CAS  Google Scholar 

  8. Alberici, R.M., Simas, R.C., De Souza, V., De Sá, G.F., Daroda, R.J., Eberlin, M.N.: Analysis of fuels via easy ambient sonic-spray ionization mass spectrometry. Anal. Chim. Acta 659, 15–22 (2010)

    Article  CAS  Google Scholar 

  9. Corilo, Y.E., Vaz, B.G., Simas, R.C., Nascimento, H.D.L., Klitzke, C.F., Pereira, R.C.L., Bastos, W.L., Santos Neto, E.V., Rodgers, R.P., Eberlin, M.N.: Petroleomics by EASI(+/−) FT-ICR MS. Anal. Chem. 82, 3990–3996 (2010)

    Article  CAS  Google Scholar 

  10. Sawaya, A.C.H.F., Abdelnur, P.V., Eberlin, M.N., Kumazawa, S., Ahn, M.-R., Bang, K.-S., Nagaraja, N., Bankova, V.S., Afrouzan, H.: Fingerprinting of propolis by easy ambient sonic-spray ionization mass spectrometry. Talanta 81, 100–108 (2010)

    Article  CAS  Google Scholar 

  11. Dams, R., Benijts, T., Günther, W., Lambert, W., De Leenheer, A.: Sonic spray ionization technology: performance study and application to a LC/MS analysis on a monolithic silica column for heroin impurity profiling. Anal. Chem. 74, 3206–3212 (2002)

    Article  CAS  Google Scholar 

  12. Björkman, H.T., Edlund, P.-O., Jacobsson, S.P.: Sonic spray ionization interface for liquid chromatography-mass spectrometry. Anal. Chim. Acta 468, 263–274 (2002)

    Article  Google Scholar 

  13. Van Berkel, G.J., Asano, K.G., Kertesz, V.: Enhanced study and control of analyte oxidation in electrospray using a thin-channel, planar electrode emitter. Anal. Chem. 74, 5047–5056 (2002)

    Article  Google Scholar 

  14. Chen, M., Cook, K.D.: Oxidation artifacts in the electrospray mass spectrometry of Aβ peptide. Anal. Chem. 79, 2031–2036 (2007)

    Article  CAS  Google Scholar 

  15. Boys, B.L., Kuprowski, M.C., Noël, J.J., Konermann, L.: Protein oxidative modifications during electrospray ionization: solution phase electrochemistry or corona discharge-induced radical attack? Anal. Chem. 81, 4027–4034 (2009)

    Article  CAS  Google Scholar 

  16. Plattner, S., Erb, R., Chervet, J.-P., Oberacher, H.: Ascorbic acid for homogenous redox buffering in electrospray ionization-mass spectrometry. Anal. Bioanal. Chem. 404, 1571–1579 (2012)

    Article  CAS  Google Scholar 

  17. Available at: www.Meinhard.com Meinhard. Accessed January 24 (2013)

  18. Paredes, E., Bosque, J., Mermet, J.M., Todolí, J.L.: Influence of nebulizer design and aerosol impact bead on analytical sensitivities of inductively coupled plasma mass spectrometry. Spectrochim. Acta B 65, 908–917 (2010)

    Article  Google Scholar 

  19. Moini, M., Jones, B.L., Rogers, R.M., Jiang, L.: Sodium trifluoroacetate as a tune/calibration the mass range of 100–4000 Da. J. Am. Soc. Mass Spectrom. 9, 977–980 (1998)

    Article  CAS  Google Scholar 

  20. Zilch, L.W., Maze, J.T., Smith, J.W., Ewing, G.E., Jarrold, M.F.: Charge separation in the aerodynamic breakup of micrometer-sized water droplets. J. Phys. Chem. A 112, 13352–13363 (2008)

    Article  CAS  Google Scholar 

  21. Valaskovic, G.A., Kelleher, N.L., Little, D.P., Aaserud, D.J., McLafferty, F.W.: Attomole-sensitivity electrospray source for large-molecule mass spectrometry. Anal. Chem. 67, 3802–3805 (1995)

    Article  CAS  Google Scholar 

  22. Wahl, J.H., Gale, D.C., Smith, R.D.: Sheathless capillary electrophoresis-electrospray ionization mass spectrometry using 10 μm i.d. capillaries: analyses of tryptic digests of cytochrome c. J. Chromatogr. A 659, 217–222 (1994)

    Article  CAS  Google Scholar 

  23. Sterling, H.J., Prell, J.S., Cassou, C.A., Williams, E.R.: Protein conformation and supercharging with DMSO from aqueous solution. J. Am. Soc. Mass Spectrom. 22, 1178–1186 (2011)

    Article  CAS  Google Scholar 

  24. Sopasis, G.J., Canaj, A.B., Philippidis, A., Siczek, M., Lis, T., O’Brien, J.R., Antonakis, M.M., Pergantis, S.A., Milios, C.J.: Heptanuclear heterometallic [Cu6Ln] clusters: trapping lanthanides into copper cages with artificial amino acids. Inorg. Chem. 51, 5911–5918 (2012)

    Article  CAS  Google Scholar 

  25. Riccio, M.F., Saraiva, S.A., Marques, L.A., Alberici, R., Haddad, R., Moller, J.C., Eberlin, M.N., Catharino, R.R.: Easy mass spectrometry for metabolomics and quality control of vegetable and animal fats. Eur. J. Lipid Sci. Technol. 112, 434–438 (2010)

    Article  CAS  Google Scholar 

  26. Afton, S., Kubachka, K., Catron, B., Caruso, J.A.: Simultaneous characterization of selenium and arsenic analytes via ion-pairing reversed phase chromatography with inductively coupled plasma and electrospray ionization ion trap mass spectrometry for detection applications to river water, plant extract and urine matrices. J. Chromatogr. A 1208, 156–163 (2008)

    Article  CAS  Google Scholar 

  27. Hannis, J.C., Muddiman, D.C.: A dual electrospray ionization source combined with hexapole accumulation to achieve high mass accuracy of biopolymers mass spectrometry. J. Am. Soc. Mass Spectrom. 11, 876–883 (2000)

    Article  CAS  Google Scholar 

  28. Chambers, A.G., Ramsey, J.M.: Microfluidic dual emitter electrospray ionization source for accurate mass measurements. Anal. Chem. 84, 1446–1451 (2012)

    Article  CAS  Google Scholar 

  29. Jiang, L., Moini, M.: Development of multi-ESI-sprayer, multi-atmospheric-pressure-inlet mass spectrometry and its application to accurate mass measurement using time-of-flight mass spectrometry. Anal. Chem. 72, 20–24 (2000)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank Meinhard and Elemental Scientific for providing nebulizers for this project.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Spiros A. Pergantis.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

ESM 1

(DOCX 8325 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Antonakis, M.M., Tsirigotaki, A., Kanaki, K. et al. Bipolar Mass Spectrometry of Labile Coordination Complexes, Redox Active Inorganic Compounds, and Proteins Using a Glass Nebulizer for Sonic-Spray Ionization. J. Am. Soc. Mass Spectrom. 24, 1250–1259 (2013). https://doi.org/10.1007/s13361-013-0668-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13361-013-0668-z

Key words

  • Sonic-spray ionization mass spectrometry
  • Venturi easy ambient sonic-spray ionization
  • Coordination compounds
  • Oxyanions
  • Bipolar MS
  • Proteins