Development of Universal and Clickable Film by Mimicking Melanogenesis: On-Demand Oxidation of Tyrosine-Based Azido Derivative by Tyrosinase.

Abstract

A tyrosine-based azido derivative (TBAD) that permits both substrate-independent surface coating and clickable film functionalization by mimicking natural melanogenesis is synthesized here. In contrast to catechol derivatives, which are generally susceptible to oxidation by air under ambient conditions, the monophenol-based TBAD remains stable under alkaline and neutral conditions and is activated to oxidized quinone in situ by tyrosinase to initiate melanin-like polymerization. The resulting poly(TBAD) film can be formed on various substrates including noble metals, metal oxides, and synthetic polymers, which can undergo click reaction with terminal alkyne moieties on the entire surface or a specific region through Cu(I)-catalyzed azide-alkyne cycloaddition. The enzyme-mediated coating can rapidly form thin films (≈10nm) and produce a uniform film morphology, which are important aspects in surface chemistry. This on-demand, clickable coating may become a significant tool for bioconjugation, soft lithography, and labeling techniques.