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

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-dimethoxyethan..