Melanin-Inspired Maleimide Coatings on Various Substrates for Rapid Thiol Functionalization.

Abstract

In this study, a substrate-independent maleimide film is developed that can be formed under mild aqueous conditions (pH 7.4), and which allows rapid and efficient external thiol immobilization onto the coated surfaces. For the coating block, tyrosine-conjugated maleimide (Tyr-Mal) containing a phenolic amine moiety is prepared as a substrate-independent dormant coating precursor, wherein the maleimide component permits a rapid Michael addition reaction with the thiol moiety of interest. By mimicking natural melanogenesis, Tyr-Mal acts as a substrate for tyrosinase under physiological conditions (pH 7.4) to form a melanin-inspired maleimide (Mel-Mal) film on various substrates, including living cell surfaces. The resulting film undergoes a rapid surface reaction (< 30 min) with external thiol groups under mild aqueous conditions. Considering that a typical polydopamine film requires a long reaction time (≈3 h) under alkaline conditions (pH 8.5) to achieve thiol functionalization with low efficiency, the current surface platform demonstrates significant improvements in terms of its reaction kinetics and usability. Moreover, considering that thiol functionalization and surface coating are performed under mild aqueous conditions, it is expected that the developed Mel-Mal film will be a useful tool in the fields of cell surface engineering, microarrays, and high-throughput screening.