We fabricated composite membranes containing inorganic nanosheets (NSs) and polymers and demonstrated their outstanding antibacterial performance against several opportunistic pathogens. Layered α-zirconium phosphate [Zr(HPO4)2, α-ZrP] as a pristine compound of NS was exfoliated by ion-exchanging protons in the interlayer space of α-ZrP with bulky tetraalkylammonium ions (TRA+: R = butyl, hexyl, and octyl). During the exfoliation process, TRA+ was electrostatically adsorbed onto α-ZrP NS with a negative surface charge (ZrP-TRA-NS). The produced PMMA membrane including α-ZrP NS (PM-ZrP-TRA-NS) was optically transparent and prohibited bacterial growth, and the effect was stronger for Gram-positive Staphylococcus aureus than Gram-negative Escherichia coli. The antibacterial activity of PM-ZrP-TRA-NS was based on physical damage induced by both 2D ceramic NSs and sharp alkyl chains of TRA+. Despite the inherent flexibility of alkyl chains, when adsorbed onto the NSs, they can act in a manner that effectively pierces the bacterial cell wall. The piercing force of TRA+ was greater for the longer alkyl chains (TBA+ < THA+ < TOA+). Focusing on the difference in the cell wall structure between these bacteria, the growth of Gram-positive S. aureus with loose peptidoglycan layers as an outer membrane could be easily inhibited by contact with the composite film. In contrast, Gram-negative bacteria E. coli, surrounded by a relatively dense outer cell wall composed of peptidoglycan and lipopolysaccharide layers, could not be damaged easily. In this study, the antibacterial mechanism of PM-ZrP-TRA-NS membranes was elucidated, and their usefulness as antimicrobial coatings for existing solid surfaces was demonstrated.
Keywords: antibacterial polymer membrane; ceramic nanosheets; inorganic/polymer hybrid; tetraalkylammonium ions; zirconium phosphate.