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    Environmental Polymer Degradation: Using the Distonic Radical Ion Approach to Study the Gas-Phase Reactions of Model Polyester Radicals

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    Author
    Taggert, BI; O'Hair, RAJ; Wille, U
    Date
    2017-07-20
    Source Title
    The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory
    Publisher
    AMER CHEMICAL SOC
    University of Melbourne Author/s
    Wille, Uta; O'Hair, Richard; Taggert, Bethany
    Affiliation
    School of Chemistry
    Metadata
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    Document Type
    Journal Article
    Citations
    Taggert, B. I., O'Hair, R. A. J. & Wille, U. (2017). Environmental Polymer Degradation: Using the Distonic Radical Ion Approach to Study the Gas-Phase Reactions of Model Polyester Radicals. JOURNAL OF PHYSICAL CHEMISTRY A, 121 (28), pp.5290-5300. https://doi.org/10.1021/acs.jpca.7b04217.
    Access Status
    Open Access
    URI
    http://hdl.handle.net/11343/252776
    DOI
    10.1021/acs.jpca.7b04217
    Abstract
    A novel precursor to the distonic O- and C-centered radical cations Oxo+O• and Oxo+C• was designed and synthesized, which represents model systems for radicals produced during polyester degradation. The precursor is equipped with a nitrate functional group, which serves as a masked site for these alkoxyl and carbon radicals that are unleashed through collision-induced dissociation (CID). Oxo+O• and Oxo+C• feature a cyclic carboxonium ion as permanent charge tag to enable monitoring their ion-molecule reactions on the millisecond to second time scale in the ion trap of the mass spectrometer. The reactions of Oxo+O• and Oxo+C• with cyclohexene, cyclohexadiene, ethyl acetate, 1,1-dimethoxyethane, and 1,2-dimethoxyethane, which exhibit structural features present in both intact and defective polyesters, were explored through product and kinetic studies to identify "hot spots" for radical-induced damage in polyesters. All reactions with Oxo+O• were extremely fast and proceeded predominantly through HAT. Oxo+C• was about two orders of magnitude less reactive and did not noticeably damage aliphatic ester moieties through hydrogen abstraction on the time scale of our experiments. Radical addition to alkene π systems was identified as an important pathway for C-radicals, which needs to be included in polymer degradation mechanisms.

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