Antimicrobial Hybrid Coatings Combining Enhanced Biocidal Activity under Visible-Light Irradiation with Stimuli-Renewable Properties.

Hybrid, organic-inorganic, biocidal films exhibiting polishing properties were developed as effective long-lasting antimicrobial surface coatings. The films were prepared using cationically modified chitosan, synthesized by the reaction with 3-bromo-,,-trimethylpropan-1-aminium bromide, to introduce permanent biocidal quaternary ammonium salt (QAS) groups along the polymer backbone and were cross-linked by a novel, pH-cleavable acetal cross-linker, which allowed polishing the hybrid coatings with the solution pH. TiO nanoparticles, modified with reduced graphene oxide (rGO) sheets, to narrow their band gap energy value and shift their photocatalytic activity in the visible light regime, were introduced within the polymer film to enhance its antibacterial activity. The hybrid coatings exhibited an effective biocidal activity in the dark (∼2 Log and ∼3 Log reduction for Gram-negative and Gram-positive bacteria, respectively), when only the QAS sites interacted with the bacteria membrane, and an excellent biocidal action upon visible-light irradiation (∼5 Log and ∼6 Log reduction for Gram-negative and Gram-positive bacteria, respectively) due to the synergistic antimicrobial effect of the QAS moieties and the rGO-modified TiO nanoparticles. The gradual decrease in the film thickness, upon immersion of the coatings in mildly basic (pH 8), neutral (pH 7), and acidic (pH 6) media, reaching 10, 20, and 70% reduction, respectively, after 60 days of immersion time, confirmed the polishing behavior of the films, whereas their effective antimicrobial action was retained. The biocompatibility of the hybrid films was verified in human cell culture studies. The proposed approach enables the facile development of highly functional coatings, combining biocompatibility and bactericidal action with a "kill and self-clean" mechanism that allows the regeneration of the outer surface of the coating leading to a strong and prolonged antimicrobial action.