Residual Monomer Content Affects the Interpretation of Plastic Degradation.

Plastic degradation rates in the marine environment are essential to understand. This study demonstrates that in plastic-microbial interaction experiments, residual monomeric and oligomeric content of PA6 significantly influences the development of dissolved organic carbon. While it is well recognized that additives in plastics should be considered during the inception of plastic-exposure experiments, residual monomers have yet to be prominently considered in the same light. As such, in degradation studies where residual contents of monomers and/or oligomers are not considered, degradation of synthetic polymers could be significantly overestimated. The substantial conversion of these monomeric and oligomeric leachates also has implications for plastic-biofilm development studies and microplastic-biota-based ingestion experiments.

Electron and hydrogen self-exchange of free radicals of sterically hindered tertiary aliphatic amines investigated by photo-CIDNP.

The photoreactions of diazabicyclo[2,2,2]octane (DABCO) and triisopropylamine (TIPA) with the sensitizers anthraquinone (AQ) and xanthone (XA) or benzophenone (BP) were investigated by time-resolved photo-CIDNP (photochemically induced dynamic nuclear polarization) experiments. By varying the radical-pair concentration, it was ensured that these measurements respond only to self-exchange reactions of the free amine-derived radicals (radical cations DH (•) (+) or α-amino alkyl radicals D (•) ) with the parent amine DH; the acid-base equilibrium between DH (•) (+) and D (•) also plays no role. Although the sensitizer does not at all participate in the observed processes, it has a pronounced influence on the CIDNP kinetics because the reaction occurs through successive radical pairs. With AQ, the polarizations stem from the initially formed radical-ion pairs, and escaping DH (•) (+) then undergoes electron self-exchange with DH. In the reaction sensitized with XA (or BP), the polarizations arise in a secondary pair of neutral radicals that is rapidly produced by in-cage proton transfer, and the CIDNP kinetics are due to hydrogen self-exchange between escaping D (•) and DH. For TIPA, the activation parameters of both self-exchange reactions were determined. Outer-sphere reorganization energies obtained with the Marcus theory gave very good agreement between experimental and calculated values of ∆G (‡) 298.