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MALDI-TOF/TOF CID study of 4-alkyl-substituted polystyrene fragmentation reactions

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Abstract

MALDI-TOF/TOF CID experiments were conducted on a variety of hydrogen-terminated poly(4-methylstyrene), hydroxylated poly(t-butylstyrene), and polystyrene precursor ions: n = 10, 15, 20, 25, and 30, where the number of repeat units n corresponds to the oligomer mass number. The influences of structure, molecular weight, and effective collision kinetic energy on degradation mechanisms were examined to test the generality of our multi-chain fragmentation model developed for polystyrene. Each depolymerization mechanism is presented in detail with experimental and computational data to justify/rationalize its occurrence and effective kinetic energy dependence. These processes show the complex interrelationship between the various pathways along with preferred production of secondary radicals, which suppresses the appearance of primary radicals. Additionally, Py-GC/MS experimental data are presented, for 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 and Kevin L. Schey for use of his ABI 4800 MALDI-TOF/TOF instrument.

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Authors and Affiliations

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

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

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

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Gies, A.P., Vergne, M.J., Orndorff, R.L. et al. MALDI-TOF/TOF CID study of 4-alkyl-substituted polystyrene fragmentation reactions. Anal Bioanal Chem 392, 609–626 (2008). https://doi.org/10.1007/s00216-008-2139-0

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  • DOI: https://doi.org/10.1007/s00216-008-2139-0

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