MALDI-TOF/TOF CID study of 4-alkyl-substituted polystyrene fragmentation reactions |
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Authors: | Anthony P Gies Matthew J Vergne Rebecca L Orndorff David M Hercules |
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Institution: | (1) Department of Chemistry, Vanderbilt University, 7330 Stevenson Center, Nashville, TN 37235, USA |
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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.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. |
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Keywords: | MALDI-TOF/TOF CID mass spectrometry Polymers Modeling MS/MS Poly(t-butylstyrene) Poly(4-methylstyrene) |
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