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MALDI-TOF/TOF CID study of poly(α-methylstyrene) fragmentation reactions

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Abstract

MALDI-TOF/TOF CID experiments are reported for hydroxylated poly(α-methylstyrene) precursor ions (PAMS: m/z 1,445.9 (n = 10), 2,036.3 (n = 15), 2,626.7 (n = 20), 3,217.1 (n = 25), and 3,807.5 (n = 30), where the number of repeat units n corresponds to the oligomer mass numbers). The influences of structure, molecular weight, and kinetic energy on degradation mechanisms were examined to test the generality of our multi-chain fragmentation model developed for polystyrene. Our results indicate that poly(α-methylstyrene) free radicals are formed initially through multiple chain breaks and subsequently undergo a variety of depolymerization reactions to yield predominantly monomer and dimer species; the intensity of each species depends on the effective kinetic energy selected for the CID process. Each depolymerization mechanism is presented in detail with experimental and computational data to justify/rationalize the process and its kinetic energy dependence. These processes show the complex interrelationships between the various pathways along with preferred production of tertiary radicals, which suppresses the appearance of primary radicals. Additionally, Py-GC/MS experimental data are presented to allow a comparison of the multimolecular free radical reactions in pyrolysis with the unimolecular fragmentation reactions of MS/MS.

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Acknowledgments

We would like to thank William K. Nonidez for use of his Py-GC/MS instrument, Kevin L. Schey for use of his ABI 4800 MALDI-TOF/TOF MS instrument, and Jimmy W. Mays for helpful synthesis advice.

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Authors and Affiliations

  1. Department of Chemistry, Vanderbilt University, 7330 Stevenson Center, Nashville, TN, 37235, USA

    Anthony P. Gies, Sparkle T. Ellison, Matthew J. Vergne, Rebecca L. Orndorff & David M. Hercules

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  1. Anthony P. Gies
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  2. Sparkle T. Ellison
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  3. Matthew J. Vergne
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  4. Rebecca L. Orndorff
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  5. David M. Hercules
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Correspondence to Anthony P. Gies.

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Gies, A.P., Ellison, S.T., Vergne, M.J. et al. MALDI-TOF/TOF CID study of poly(α-methylstyrene) fragmentation reactions. Anal Bioanal Chem 392, 627–642 (2008). https://doi.org/10.1007/s00216-008-2310-7

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  • DOI: https://doi.org/10.1007/s00216-008-2310-7

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