Skip to main content
SpringerLink
Log in

Do charge-remote fragmentations occur under matrix-assisted laser desorption ionization post-source decompositions and matrix-assisted laser desorption ionization collisionally activated decompositions?

  • Articles
  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

The precursor ions of tetraphenylporphyrins that are substituted with fatty acids can be introduced into the gas phase by matrix-assisted laser desorption ionization (MALDI) and undergo post-source and collisionally activated decompositions (CAD) in a time-of-flight mass spectrometer. The goal of the research is to obtain a better understanding of post-source decompositions (PSD); specifically, we asked the question of whether ions undergoing PSD have sufficient energy to give charge-remote fragmentations along an alkyl chain. We chose the porphyrin macrocycle because we expected it to act as an inert “support,” allowing the molecule to be desorbed by MALDI and to be amenable to charge-remote fragmentation. MALDI-PSD and MALDI-CAD spectra are similar to high-energy CAD spectra and considerably more informative than low-energy CAD spectra, showing that charge-remote fragmentations of the fatty acid moieties do occur upon MALDI-PSD and MALDI-CAD.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Spengler, B.; Kirsch, D.; Kaufmann, R.; Jaeger, E. Peptide Sequencing by Matrix-assisted laser-desorption Mass Spectrometry. Rapid Commun. Mass Spectrom. 1992, 6, 105–108.

    Article  CAS  Google Scholar 

  2. Rouse, J. C.; Yu, W.; Martin, S. A. A Comparison of the Peptide Fragmentation Obtained from a Reflector MALDI TOF and a Tandem Four Sector Mass Spectrometer. J. Am. Soc. Mass Spectrom. 1995, 6, 822–835.

    Article  CAS  Google Scholar 

  3. Kaufmann, R.; Wingerath, T.; Kirsch, D.; Stahl, W.; Sies, H. Analysis of Carotenoids and Carotenol Fatty Acid Esters by Matrix-assisted Laser Desorption Ionization (MALDI) and MALDI-post-source-decay Mass Spectrometry. Anal. Biochem. 1996, 238, 117–128.

    Article  CAS  Google Scholar 

  4. Spengler, B.; Kirsch, D.; Kaufmann, R.; Lemoine, J. Structural Analysis of Branched Oligosaccarides Using PSD in MALDI Mass Spectrometry. Org. Mass Spectrom. 1994, 29, 782–787.

    Article  CAS  Google Scholar 

  5. Harvey, D. J. Matrix-assisted Laser Desorption/ionisation Mass Spectrometry of Oligosaccharides and Glycoconjugates. J. Chromatogr. 1996, 720, 429–446.

    Article  CAS  Google Scholar 

  6. Spengler, B.; Kaufmann, R. Gentle Probe for Tough Molecules: MALD Mass Spectrometry. Analysis 1992, 20, 91–101.

    CAS  Google Scholar 

  7. Spengler, B.; Kirsch, D.; Kaufmann, R. Fundamental Aspects of PSD in MALDI Mass Spectrometry 1. Residual Gas Effects. J. Phys. Chem. 1992, 96, 9678.

    Article  CAS  Google Scholar 

  8. Kaufmann, R.; Chaurand, P.; Kirsch, D.; Spengler, B. Post-source Decay and Delayed Extraction in Matrix-assisted Laser Desorption/Ionization-Reflectron Time-of-flight Mass Spectrometry: Are there trade-offs? Rapid Commun. Mass Spectrom. 1996, 10, 1199–1208.

    Article  CAS  Google Scholar 

  9. Ospina, M.; Powell, D. H.; Sapp, L.; Denslow, N.; Yost, R. A. Comparison of Low and High Energy CID to MALDI PSD. Proceedings of the 44th ASMS Conference on Mass Spectrometry and Allied Topics.; Palm Springs, 1997; p 90.

  10. Kaufmann, R.; Spengler, B.; Lützenkirchen, F. Mass Spectrometric Sequencing of Linear Peptides by Product-ion Analysis in a Reflectron Time-of-flight Mass Spectrometer Using Matrix-assisted Laser Desorption Ionization. Rapid Commun. Mass Spectrom. 1993, 7, 902–910.

    Article  CAS  Google Scholar 

  11. Gooden, J. K.; Byun, J.; Chen, L.; Rogan, E. G.; Cavalieri, E. L.; Gross, M. L. Application of MALDI and PSD to the Structure Determination of Adducts between DNA Bases and the Carcinogen 7H-Dibenzo[c, g]carbazole. Int. J. Mass Spectrom. Ion Processes 1997, 169/170, 241–249.

    Article  CAS  Google Scholar 

  12. Dale, M. J.; Costello, K. F.; Jones, A. C.; Langridge-Smith, P. R. R. Investigation of Porphyrins and Metalloporphyrins using Two-step Laser Mass Spectrometry. J. Mass Spectrom. 1996, 31, 590–601.

    Article  CAS  Google Scholar 

  13. Rubino, F. M.; Mascaro, P.; Banfi, S.; Quici, S. Structural Study of Mn(III)-Tetraarylporphyrin Complexes by FAB MS. Org. Mass Spectrom. 1991, 26, 161–166.

    Article  CAS  Google Scholar 

  14. Van Berkel, G. J.; McLuckey, S. A.; Glish, G. L. ESI of Porphyrins Using a Quadrupole Ion Trap for Mass Analysis. Anal. Chem. 1991, 63, 1098–1109.

    Article  Google Scholar 

  15. Shibue, T.; Kambe, H.; Nishide, H.; Tsuchida, E.; Akashi, S.; Ohashi, Y. Structural Characterization of Picket-fence Porphyrinatoiron with ω-Hydroxy-2,2-dimethylicosanoyl Side-Chains by FAB High-Energy CID MS/MS. J. Mass Spectrom. Soc. Jpn. 1998, 46, 250–253.

    CAS  Google Scholar 

  16. Wysocki, V. H.; Bier, M. E.; Cooks, R. G. Internal Energy Requirements for Remote Site Fragmentation. Org. Mass Spectrom. 1988, 23, 627–633.

    Article  CAS  Google Scholar 

  17. Hayes, R. N.; Gross, M. L. In Methods in Enzymology, Vol. 193, Mass Spectrometry; McCloskey, J. A., Ed.; Academic: San Diego, 1990, pp 237–262.

    Google Scholar 

  18. Cregg, B. A.; Fox, M. A.; Bard, A. J. 2,3,7,8,12,13,17,18-Octakis(β-hydroxyethyl)porphyrin and its Liquid Crystalline Derivatives: Synthesis and Characterization. J. Am. Chem. Soc. 1989, 111, 3024–3029.

    Article  Google Scholar 

  19. Cregg, B. A.; Fox, M. A.; Bard, A. J. Effects of Order on the Photophysical Properties of the Liquid Crystal Zinc Octakis(β-octoxyethyl)porphyrin. J. Phys. Chem. 1989, 93, 4227–4234.

    Article  Google Scholar 

  20. Kugimiya, S. I.; Takemura, M. Novel Liquid Crystals Consisting of Tetraphenylporphyrin Derivatives. Tetrahedron Lett 1990, 31, 3157–3160.

    Article  CAS  Google Scholar 

  21. Bonnett, R.; Ioannou, S.; James, A. G.; Pitt, C. W.; Soe, M. M. Z. Octadecyl Ethers of 5,10,15,20-tetra(4-hydroxyphenyl)porphyrin: Synthesis and Film-Forming Properties. J. Mater. Chem. 1992, 2, 823–828.

    Article  CAS  Google Scholar 

  22. Meier, G.; Sackmann, E.; Grabmaier, J. G. Applications of Liquid Crystals; Springer: Berlin, 1975; p 36.

    Google Scholar 

  23. Gross, M. L. In Methods in Enzymology, Vol. 193, Mass Spectrometry; McCloskey, J. A., Ed.; Academic: San Diego, 1990; pp 131–153.

    Google Scholar 

  24. Van Berkel, G. J.; McLuckey, S. A.; Glish, G. L. Electrochemical Origin of Radical Cations Observed in ESI Mass Spectra. Anal. Chem. 1992, 64, 1586–11593.

    Article  Google Scholar 

  25. March, J. Advanced Organic Chemistry; Wiley: New York, 1992 pp 392–396.

    Google Scholar 

  26. Adams, J. Charge-Remote Fragmentation: Analytical Applications and Fundamental Studies. Mass Spectrom. Rev. 1990, 9, 141–186.

    Article  CAS  Google Scholar 

  27. Berezin, B. D. Coordination compounds of Porphyrins and Phtalocyanines, translation by Vopian, V. G.; Wiley: New York, 1981; pp 59–67.

    Google Scholar 

  28. Smith, K. M. In Porphyrins and Metalloporphyrins Elsevier: Amsterdam, 1975; pp 11–14.

    Google Scholar 

  29. Cheng, C.; Pittenauer, E.; Gross, M. L. Charge-Remote Fragmentations are Energy-Dependent Processes. J. Am. Soc. Mass Spectrom. 1998, 9, 840–844.

    Article  CAS  Google Scholar 

  30. Karas, M.; Bahr, U.; Strupat, K.; Hillenkamp, F.; Tsarbopoulos, A.; Pramanik, B. N. Matrix Dependence of Metastable Fragmentations of Glycoproteins in MALDI TOF Mass Spectrometry. Anal. Chem. 1995, 67, 675–679.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Aveiro, Aveiro, Portugal

    M. Rosario M. Domingues, M. Graça O. S.-Marques, Carla A. M. Vale, M. Graça Neves, J. A. S. Cavaleiro & A. J. Ferrer-Correia

  2. Department of Chemistry, Washington University, St Louis, Missouri, USA

    Olga V. Nemirovskiy & Michael L. Gross

Authors
  1. M. Rosario M. Domingues
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Graça O. S.-Marques
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Carla A. M. Vale
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. Graça Neves
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. J. A. S. Cavaleiro
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. J. Ferrer-Correia
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Olga V. Nemirovskiy
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Michael L. Gross
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M. Graça O. S.-Marques.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Domingues, M.R.M., O. S.-Marques, M.G., Vale, C.A.M. et al. Do charge-remote fragmentations occur under matrix-assisted laser desorption ionization post-source decompositions and matrix-assisted laser desorption ionization collisionally activated decompositions?. J Am Soc Mass Spectrom 10, 217–223 (1999). https://doi.org/10.1016/S1044-0305(98)00144-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(98)00144-5

Keywords

Search

Navigation