Humidity-Responsive Antimicrobial Membranes Based on Cross-Linked Copolymers Functionalized with Ionic Liquid Moieties.

Abstract

Humidity-responsive materials have attracted increasing attention for their potential use in various applications, e.g., sensors, soft robotics, and human-machine interfaces. Much effort has been focused on the use of ionic liquids for the construction of humidity-responsive sensors; yet, not enough attention has been paid on the susceptibility of the used poly(ionic liquid)s to microorganisms. This is especially relevant to the wide use of the polymers for biomedical applications, e.g., wearable body-condition sensors or healthcare control systems. We herein describe the development of dual functional, self-standing, monolayer antimicrobial membranes derived from cross-linked copolymers functionalized with ionic liquids. In a first step, random copolymers of poly(4-vinylbenzyl N-alkyl imidazolium chloride-co-acrylic acid), P(VBCImCn-co-AA20), were synthesized bearing aliphatic chains of different lengths (where n = 1, 4, 8, 12, 16 carbon atoms) to investigate the effect of hydrophobicity/hydrophilicity on the humidity-responsive properties of the copolymer and its antimicrobial activity. The aforementioned copolymers were later blended with the complementary reactive copolymers of poly(cetyl trimethylammonium 4-styrene sulfonate-co-glycidyl methacrylate), P(SSAmC16-co-GMA20), to provide highly stable films and coatings through thermal cross-linking. The membrane P(VBCImC12-co-AA20)/P(SSAmC16-co-GMA20) with a molar ratio of 3:1 (mol AA/mol GMA) exhibited immediate and high response to moisture through folding or flipping motions when placed on a wet filter paper or on the palm of a hand. The inhibition of growth for selected bacterial species (Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus) on the copolymer membranes was dependent on the length of the imidazolium alkyl chain and the species. Additionally, in the case of the cross-linked P(VBCImCn-co-AA20)/P(SSAmC16-co-GMA20) membranes, the overall efficacy was very high against all microorganisms tested, which, combined with their high humidity responsiveness, enables their potential application.