Bioactive surfaces with well-defined amphiphilic copolymers containing a natural terpene-based monomer

New amphiphilic cationic copolymers based on poly((methacryloyloxy) ethyl trimethylammonium chloride) (PMETAC) and bio-based poly(thymol methacrylate) (PTMA) were prepared by atom transfer radical polymerization (ATRP) methods, using low concentration of metal catalyst and a bio-based eutectic mixture (EM), composed of L-menthol and thymol. The antimicrobial activity of the polymers was evaluated against Grampositive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) bacteria.The results in solution showed that increasing the terpenic segment (PTMA) in the copolymers resulted in lower antimicrobial activity against S. aureus (as the MIC increases from 3.1 to 100 & mu;M) and higher activity against E. coli (as the MIC decreases from 400 to 200 & mu;M).Scanning electron microscopy (SEM) analysis suggests that polymers affected the bacterial viability by damaging the cell structure. The synthesized biocidal polymers were used as additives in polyurethane-based varnish formulations to produce bioactive coated surfaces that were found to be more active against E. coli. Coatings containing either PTMA or PMETAC homopolymers were more efficient than those containing PMETAC-co-PTMA copolymers. A dramatic improvement in the antimicrobial activity of PMETAC-containing varnish against both S. aureus (3 orders of magnitude) and E. coli (4 orders of magnitude) was observed when an aqueous solution of the homopolymer was applied to the dried varnish instead of being incorporated into the varnish formulation. The strategy presented here is simple and opens the door for the preparation of customized bioactive surfaces to prevent bacterial infections.