Persistent protein resistance is critical for marine antibiofouling. We have prepared copolymer of 2-methylene-1,3-dioxepane (MDO), tertiary carboxybetaine ester (TCB), and 7-methacryloyloxy-4-methylcoumarin (MAMC) via radical ring-opening polymerization, where MDO, TCB, and MAMC make the polymer degradable, protein resistible, and photo-cross-linkable, respectively. Our study shows that the polymer can well adhere to the substrate with controlled degradation and water adsorption rate in artificial seawater (ASW). Particularly, the polymer film can generate zwitterions via surface hydrolysis in ASW. Quartz crystal microbalance with dissipation measurements reveal that such hydrolysis-induced zwitterionic surface can effectively resist nonspecific protein adsorption. Moreover, the surface can inhibit the adhesion of marine bacteria Pseudomonas sp. and Vibrio alginolyticus as well as clinical bacterium Escherichia coli.

Degradable polymers with protein resistance can find applications in antibiofouling. We have prepared copolymer of 2-methylene-1,3-dioxepane (MDO), 2-(dimethylamino) ethyl methacrylate (DEM) and 3-(methacryloxypropyl) trimethoxysilane (KH570) via radical ring-opening polymerization, where MDO, DEM, and KH570 make the polymer degradable, protein resistant and self-cross-linkable, respectively. Our studies demonstrate that the self-cross-linking significantly improves the coating ability of the polymer with controlled biodegradation in seawater. We have investigated the adsorption of fibrinogen, bovine serum albumin and lysozyme on the self-cross-linking polymer surface as a function of its composition by use of quartz crystal microbalance with dissipation (QCM-D). It shows the polymer network can resist the adsorption of proteins in seawater. The antibacterial adhesion of the polymer network was evaluated by using Micrococcus luteus (M. luteus) and Pseudomonas sp., revealing that the polymer network can effectively inhibit the settlement of marine bacteria.