Role of polydopamine’s redox-activity on its pro-oxidant, radical-scavenging, and antimicrobial activities

Polydopamine (PDA) is a bioinspired material and coating that offers diverse functional activities (e.g., photothermal, antioxidant, and antimicrobial) for a broad range of applications. Although PDA is reported to be redox active, the association between PDA’s redox state and its functional performance has been difficult to discern because of PDA’s complex structure and limitations in methods to characterize redox-based functions. Here, we use an electrochemical reverse engineering approach to confirm that PDA is redox-active and can repeatedly accept and donate electrons. We observed that the electron-donating ability of PDA offers the detrimental pro-oxidant effect of donating electrons to O2 to generate reactive oxygen species (ROS) or, alternatively, the beneficial antioxidant effect of quenching oxidative free radicals. Importantly, PDA’s electron-donating ability depends on its redox state and is strongly influenced by external factors including metal ion binding as well as near-infrared (NIR) irradiation. Furthermore, we demonstrated that PDA possesses redox state-dependent antimicrobial properties in vitro and in vivo. We envision that clarification of PDA’s redox activity will enable better understanding of PDA’s context-dependent properties (e.g., antioxidant and pro-oxidant) and provide new insights for further applications of PDA. We believe this is the first report to characterize the redox activities of polydopamine (PDA) and to relate these redox activities to functional properties important for various proposed applications of PDA. We observed that polydopamine nanoparticles 1) are redox-active; 2) can repeatedly donate and accept electrons; 3) can accept electrons from reducing agents (e.g., ascorbate), donate electrons to O2 to generate ROS, and donate electrons to free radicals to quench them; 4) have redox state-dependent electron-donating abilities that are strongly influenced by metal ion binding as well as NIR irradiation; and 5) have redox state-dependent antimicrobial activities.