Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy

Abstract

Advances in liquid phase transmission electron microscopy (LP‐TEM) have enabled the monitoring of polymer dynamics in solution at the nanoscale, but radiolytic damage during LP‐TEM imaging limits its routine use in polymer science. This study focuses on understanding, mimicking, and mitigating radiolytic damage observed in functional polymers in LP‐TEM. It is quantitatively demonstrated how polymer damage occurs across all conceivable (LP‐)TEM environments, and the key characteristics and differences between polymer degradation in water vapor and liquid water are elucidated. Importantly, it is shown that the hydroxyl radical‐rich environment in LP‐TEM can be approximated by UV light irradiation in the presence of hydrogen peroxide, allowing the use of bulk techniques to probe damage at the polymer chain level. Finally, the protective effects of commonly used hydroxyl radical scavengers are compared, revealing that the effectiveness of graphene's protection is distance‐dependent. The work provides detailed methodological guidance and establishes a baseline for polymer degradation in LP‐TEM, paving the way for future research on nanoscale tracking of shape transitions and drug encapsulation of polymer assemblies in solution.