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MALDI-TOF/TOF CID Study of 4-alkyl-substituted Polystyrene Fragmentation Reactions

MALDI-TOF/TOF CID Study of 4-alkyl-substituted Polystyrene Fragmentation Reactions

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

Anal Bioanal Chem. 2008 Oct;392(4):609-26.

PMID: 18537031

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP24936412	Poly(4-methylstyrene)		24936-41-2	Price

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