Phosphonate/zwitterionic/cationic terpolymers as high-efficiency bactericidal and antifouling coatings for metallic substrates

Bacteria associated infection is a critical challenge for metallic implants and devices in biomedical applications. Here, we report phosphonate/zwitterionic/quaternary amine terpolymers as a new type of antifouling and bactericidal coating for metallic substrates. Through reversible-addition fragmentation chain transfer polymerization (RAFT) and quaternization, well-controlled phosphonate/zwitterionic/cationic terpolymers with identical phosphonate segments (repeat units of 15) and varied zwitterionic and cationic components (nSBMA : nTMAEMA = 64 : 0, 54 : 18, 18 : 32, 9 : 52, and 0 : 70) were precisely prepared. The polymers can be coated on TC4 substrates based on the strong coordination between phosphonate groups and metallic substrates, as evidenced by water contact angle and XPS tests. Bactericidal evaluation revealed that the antibacterial efficiency was enhanced with the increase of cationic content in the coating polymers. TC4 substrates coated with the polymer coating with a cationic segment of 70 repeat units were able to kill 97.5 and 94.0% of S. aureus and E. coli, respectively. By virtue of the antifouling ability of the zwitterionic component and the bactericidal ability of the cationic component, the antibacterial efficiency was increased to 99.5% without significant compromising of the cytocompatibility. Meanwhile, the dual functional terpolymers could be easily applied on other metallic substrates, such as titanium, stainless steel, and Ni/Cr alloy, which were able to kill up to 97.9% of S. aureus and 99.9% of E. coli, respectively, endowing the excellent antibacterial properties to general bio-metals. The high-efficiency antibacterial modification strategy demonstrated here may find many applications on metallic implants and devices to combat bacterial associated infections.