Transient Plastic Spin Labeling with Chlorine Dioxide

TL;DR

This study demonstrates a novel method using chlorine dioxide radicals and electron spin resonance spectroscopy to identify and analyze plastic waste, revealing molecular immobilization and diffusion properties within polymers.

Contribution

We introduce a spin-labeling technique with chlorine dioxide radicals for detecting and characterizing plastics, providing new insights into molecular dynamics within polymer matrices.

Findings

Radicals are immobilized at low temperatures with distinct ESR spectra.

Some molecular mobility persists above water's melting point.

Diffusion coefficient of radicals in polymer measured at room temperature.

Abstract

Plastic waste, being one of the most important problems for humankind, poses severe threats to ecosystems, wildlife, and human health. Tracing, quantifying, and identifying types of plastic waste is of crucial importance to understand its environmental pathways and develop targeted strategies for reduction, recycling, and remediation. To contribute to addressing this global issue, we investigated the spin-labeling capabilities of aqueous chlorine dioxide (ClO$_2$) radicals upon introduction into poly(ethylene terephthalate) and utilized electron spin resonance spectroscopy for detection. The technique is capable of identifying plastic species as the unpaired electron of the radical molecule is strongly sensitive to its local environment through its coupling parameters. Temperature-dependent measurements revealed that the molecules are immobilized at low temperatures and exhibit well-resolved anisotropic and hyperfine spectra that are quantitatively described by a model spin Hamiltonian. Even above the melting point of water, some degrees of freedom remain blocked as a result of the polymer matrix. Furthermore, employing a time-series measurement at room temperature enabled us to determine the diffusion coefficient of the molecule in the polymer.