Polydopamine Generates Hydroxyl Free Radicals under Ultraviolet-Light Illumination

Polydopamine (PDA) generally demonstrates as an efficient free-radical scavenger. However, its free-radical chemistry under illumination is unclear, which becomes important in view of growing studies of polydopamine applications in photoprotector and photothermal therapy. In this study, for the first time, we reported an experimental investigation of the generation of hydroxyl free radicals from ultraviolet (UV)-illuminated polydopamine in an aqueous environment. By using terephthalic acid as fluorescent probe, we measured hydroxyl radicals generated from UV-illuminated polydopamine with different shapes and sizes. The morphology of PDA shows significant influence on its productions of hydroxyl free radicals. Through characterizations of UV-vis absorption spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectrometry, mass spectrometry, and thermogravimetric analysis, we demonstrated the change of PDA nanomaterials brought by UV-light illumination in composition and thermal stability. We proposed a tentative mechanism for interpreting the relationship between morphology and photostability of PDA nanomaterials. These results reveal underlying complexity of polydopamine chemistry under light illumination that will deepen our understanding and benefit its further application.