Functionalization of Polydopamine via the Aza-Michael Reaction for Antimicrobial Interfaces.

Abstract

Polydopamine (pDA) coatings afford tremendous versatility due to their capabilities to provide substrate-independent functionalization with a wide range of amine- and thiol-containing molecules. In this work, we developed a new and facile conjugation approach to the formation of β-amino carbonyl linkages between pDA and acrylate/acrylamide molecules via the aza-Michael reaction. Sulfobetaine acrylamide (SBAA), sulfobetaine methacrylate (SBMA), and poly(ethylene glycol) methacrylate (PEGMA) were employed to graft onto pDA films, giving rise to formation of antifouling coatings. Because of the universal adhesive property of pDA, the coating strategy was applied to different substrates, including TiO2, gold, SiO2, Nitinol alloy, polystyrene, and poly(dimethylsiloxane). The variation of surface chemistry and surface wettability upon pDA modification and subsequent conjugation was monitored with X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. Antifouling properties of coatings were challenged by three common Gram-negative and Gram-positive bacteria. Cytocompatibility of the coatings with NIH-3T3 fibroblasts was accessed using MTT assay. The results showed that pDA coatings grafted with SBAA exhibited superhydrophilicity and excellent fouling resistance likely due to the high chemical reactivity of acrylamide, leading to high grafting density. In addition, dual functional coatings containing passive and active antibacterial components were constructed through the in situ deposition of antimicrobial agent, silver nanoparticles, in pDA, followed by the grafting of SBAA for bacterial repellence. The composite coatings allowed reducing adsorption of E.coli by >95%, while killing attached bacteria by up to 98% upon the releasing of Ag(+) ions as measured by inductively coupled plasma mass spectrometry. Consequently, this work paves a new avenue to the grafting strategy to engineer pDA and to the functional bioinspired antifouling interfaces in a substrate-independent fashion.