Skip to main content
Log in

In-source decay of hyperbranched polyesteramides in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

Hyperbranched polyesteramides (DA2), prepared from hexahydrophthalic anhydride (D) and diisopropanolamine (A) have been characterized, by use of matrix-assisted laser desorption/ ionization time-of-flight mass spectrometry (MALDI-TOF-MS), field desorption (FD)-MS, and electrospray ionization (ESI)-MS. MALDI of polyesteramides produces protonated molecules. The spectra show a complex chemical composition distribution and end-group distribution which are mainly composed of two series of homologous oligomers D n A n+1mzH2O and D n A n mH2O, where m = 1–2. Signals from protonated molecules D n A n+1 and D n A n are almost absent in the MALDI spectrum, whereas these ions are responsible for the base peak of D n A n+1mH2O and D n A n mH2O (m = 1–2) clusters in the ESI spectrum. The absence of −OH end-groups signals in the MALDI spectrum is due to a metastable decay of protonated D n A n+1 and DnAn ions in the ion source of the MALDI mass spectrometer prior to ion extraction. In-source decay results in the formation of protonated lower D n A n+1mH2O and D n A n mH2O oligomers and their corresponding neutrals, leading to wrong conclusions concerning the relative end-group distribution as a function of the degree of polymerization and the chemical composition.

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

Access this article

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

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Karas, M.; Bachmann, D.; Bahr, U.; Hillenkamp, F. Matrix-assisted ultraviolet laser desorption of non-volatile compounds. Int. J. Mass Spectrom. Ion Processes 1987, 78, 53–68.

    Article  CAS  Google Scholar 

  2. Karas, M.; Hillenkamp, F. Laser desorption ionization of proteins with molecular masses exceeding 10,000 Daltons. Anal. Chem. 1988, 60, 2299–2301.

    Article  CAS  Google Scholar 

  3. Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida, Y.; Yoshida, T. Protein and polymer analysis up to m/z 100,000 by laser ionization time-of-flight mass spectrometry. Rapid Commun. Mass Spectrom. 1988, 2, 151.

    Article  CAS  Google Scholar 

  4. Brown, R. S.; Lennon, J. L. Mass resolution improvement by incorporation of pulsed ion extraction in a matrix-asisted laser desorption/ionization linear time-of-flight mass spectrometer. Anal. Chem. 1995, 67, 1998–2003.

    Article  CAS  Google Scholar 

  5. Weidner, S.; Kühn, G. Chemical end-group derivatization of poly(ethyleneglycol)—Investigation by matrix-asisted laser desorption/ionization mass spectrometry. Rapid Commun. Mass Spectrom. 1996, 10, 942–946.

    Article  CAS  Google Scholar 

  6. Van der Hage, E. R. E.; Duursma, M. C.; Heeren, R. M. A.; Boon, J. J.; Nielen, M. W. F.; Weber, A. J. M.; de Koster, C. G.; de Vries, N. K. Structural analysis of polyoxyalkyleneamines by matrix-asisted laser desorption/ionization on an external ion source FT-ICR-MS and NMR. Macromolecules 1997, 30, 4302–4309.

    Article  Google Scholar 

  7. Gooden, J. K.; Gross, M. L.; Mueller, A.; Stefanescu, A. D.; Wooley, K. L. Cyclization in hyperbranched polymer synthesis: characterization by MALDI-TOF mass spectrometry. J. Am. Chem. Soc. 1998, 129, 10180–10186.

    Article  Google Scholar 

  8. Wilczek-Vera, G.; Danis, P. O.; Eisenberg, A. Individual block-length distributions of block copolymers polystyrene-block-poly (α-methylstyrene) by MALDI/TOF mass spectrometry. Macromolecules 1996, 29, 4036–4044.

    Article  CAS  Google Scholar 

  9. van Rooij, G. J.; Duursma, M. C.; de Koster, C. G.; Heeren, R. M. A.; Boon, J. J.; Schuyl, P. J. W.; van der Hage, E. R. E. Determination of block length distributions of poly(oxypropyle) and poly(oxyethylene) block copolymers by MALDI-FTICR mass spectrometry. Anal. Chem. 1998, 70, 843–850.

    Article  Google Scholar 

  10. Schriemer, D. C.; Liang, L. Detection of high molecular weight narrow polydisperse polymers up to 1.5 million daltons by MALDI mass spectrometry. Anal. Chem. 1996, 68, 2721–2725.

    Article  CAS  Google Scholar 

  11. Jackson, A. T.; Yates, H. T.; Scrivens, J. H.; Critchley, G.; Brown, J.; Green, B. R.; Bateman, R. H. The application of matrix-asisted laser desorption/ionization combined with collision induced dissociation to the analysis of synthetic polymers. Rapid Commun. Mass Spectrom. 1996, 10, 1668–1674.

    Article  CAS  Google Scholar 

  12. Brown, R. S.; Lennon, J. J. Sequence-specific fragmentation of matrix-assisted laser-desorbed protein/peptide ions. Anal. Chem. 1995, 67, 3990–3999.

    Article  CAS  Google Scholar 

  13. Katta, V.; Chow, D. T.; Rohde, M. F. Applications of in-source fragmentation of protein ions for direct sequence analysis by delayed extraction MALDI-TOF mass spectrometry. Anal. Chem. 1998, 70, 4410–4416.

    Article  CAS  Google Scholar 

  14. Reiber, D. C.; Brown, R. S.; Weinberger, S.; Kenny, J.; Bailey, J. Unknown peptide sequencing using matrix-assisted laser desorption/ionization and in-source decay. Anal. Chem. 1998, 70, 1214–1222.

    Article  CAS  Google Scholar 

  15. Brown, R. S.; Carr, B. L.; Lennon, J. J. Factors that influence the observed fast fragmentation of peptides in matrix-assisted laser desorption. J. Am. Soc. Mass Spectrom. 1996, 7, 225–232.

    Article  CAS  Google Scholar 

  16. Patterson, S. D.; Katta, V. Prompt fragmentation of disulfide-linked peptides during matrix-asisted laser desorption/ionization mass spectrometry. Anal. Chem. 1994, 66, 3727–3732.

    Article  CAS  Google Scholar 

  17. Naven, T. J. P.; Harvey, D. J.; Brown, J.; Critchley, G. Fragmentation of complex carbohydrates following ionization by matrix-assisted laser desorption with an instrument fitted with time-lag focussing. Rapid Commun. Mass Spectrom. 1997, 11, 1681–1686.

    Article  CAS  Google Scholar 

  18. Harvey, D. J.; Hunter, A. P.; Bateman, R. H.; Brown, J.; Critchley, G. Relationship between in-source and post-source fragment ions in the matrix-assisted laser desorption (ionization) mass spectra of carbohydrates recorded with reflectron time-of-flight mass spectrometers. Int. J. Mass Spectrom. Ion Processes 1999, 188, 131–146.

    CAS  Google Scholar 

  19. Van Benthem, R. A. T. M.; Muscat, D.; Stanssens, D. A. W. New commercially available hyperbranched polymers for tailor made solutions, ACS Preprints, PMSE, Anaheim, 1999, 72–73.

    Google Scholar 

  20. Wicks, Z. W., Jr.; Chiang, N. C. Esterification of N-(2-hydroxyalkyl)amides. J. Coat. Technol. 1982, 54, 27–31.

    CAS  Google Scholar 

  21. Stanssens, D.; Hermanns, R.; Wories, H. On the mechanisms of the esterification of beta-hydroxy alkylamides with a carboxylic acid. Progress Organic Coatings 1993, 22, 379–391.

    Article  CAS  Google Scholar 

  22. Vestal, M. L.; Juhasz, P.; Martin, S. A. Delayed extraction matrix-assisted laser desorption time-of-flight mass spectrometry. Rapid Commun. Mass Spectrom. 1995, 9, 1044–1050.

    Article  CAS  Google Scholar 

  23. De Koster, C. G.; Duursma, M. C.; van Rooij, G. J.; Heeren, R. M. A.; Boon, J. J. End-group analysis of polyethylene glycol polymers by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry. Rapid Commun. Mass Spectrom. 1995, 9, 957–962.

    Article  Google Scholar 

  24. Van Rooij, G. J.; Duursma, M. C.; Heeren, R. M. A.; Boon de Koster, C. G. High resolution end-group determination of low molecular weight polymers by matrix-assisted laser desorption ionization on an external ion source Fourier transform ion cyclotron resonance mass spectrometer. J. Am. Soc. Mass Spectrom. 1996, 7, 449–457.

    Article  Google Scholar 

  25. Jacobson, H.; Stockmayer, W. H. Intramolecular reactions in polycondensations. I. The theory of linear systems. J. Chem. Phys. 1950, 18, 1600–1606.

    Article  CAS  Google Scholar 

  26. Gooden, J. K.; Gross, M. L.; Mueller, A.; Stefanescu, A. D.; Wooley, K. L. Cyclization in hyperbranched syntheses: Characterization by MALDI-TOF mass spectrometry. J. Am. Chem. Soc. 1998, 120, 10180–10186.

    Article  CAS  Google Scholar 

  27. Brown, R. S.; Lennon, J. J. Sequence-specific fragmentation of matrix-assisted laser-desorbed protein/peptide ions. Anal. Chem. 1995, 67, 3990–3999.

    Article  CAS  Google Scholar 

  28. Harrison, A. G. The gas-phase basicities and proton affinities of amino acids and peptides. Mass Spectrom. Rev. 1997, 16, 201–217.

    Article  CAS  Google Scholar 

  29. Aue, D. H.; Bowers, M. T. Stabilities of positive ions from equilibrium gas-phase basicity measurements. In Gas Phase Ion Chemistry; Bowers, M. T., Ed.; Academic: New York, 1979.

    Google Scholar 

  30. Van Dongen, W. D.; Heerma, W.; Haverkamp, J.; de Koster, C. G. The B1-fragment ion from protonated glycine is an electrostatically-bound ion/molecule complex of CH2=NH +2 and CO. Rapid Commun. Mass Spectrom. 1996, 10, 1237–1239.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Chris G. de Koster.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Muscat, D., Henderickx, H., Kwakkenbos, G. et al. In-source decay of hyperbranched polyesteramides in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. J Am Soc Mass Spectrom 11, 218–227 (2000). https://doi.org/10.1016/S1044-0305(99)00141-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1016/S1044-0305(99)00141-5

Keywords

Navigation