Biodegradable Polymer with Hydrolysis-Induced Zwitterions for Antibiofouling

Abstract

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.

Exploring the Long-Term Hydrolytic Behavior of Zwitterionic Polymethacrylates and Polymethacrylamides

“…Although occasionally concerns are expressed, they are mostly discussed on the basis of common wisdom rather than of experimental facts. Accordingly, polymers with all-carbon backbones are preferred, avoiding the risk of backbone hydrolysis [15,16,17]. For such vinyl and vinylidene polymers, it is generally assumed that polymers connecting the functional side groups by ester moieties to the backbone (such as poly((meth)acrylates)) are considerably more sensitive to hydrolysis than analogs bearing amide moieties (such as poly((meth)acrylamides)), and much more than derivatives of polystyrene or poly(diallylammonium) compounds [18,19,20,21].…”

Advanced functional polymer materials

“…For example, copolymer carrying the tertiary carboxybetaine (TCB) ester can be hydrolyzed in seawater to generate zwitterions with resistance to nonspecific protein and bacteria (both marine bacteria and clinically related bacteria). 478 Moreover, these zwitterions were renewed by main-chain degradation, which was favorable to maintain both mechanical robustness and fouling resistance.…”

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

“…[10] Ther ing-opening polymerization of cyclic ketene acetals (CKAs) by free radical or controlled radical mechanisms has attracted considerable interest since it presents an alternative route for the synthesis of functionalized aliphatic polyesters [12][13][14][15] and is ap owerful tool for imparting degradability to vinyl polymers [16][17][18][19][20] by introducing ester linkages into their backbone (Scheme 1b). [9,10] Indeed, the copolymerization of vinyl-based monomers and CKAs has been used to prepare (bio)degradable polyethylene, [21] fluoropolymers, [22] polymethyl methacrylate materials, [18] marine anti-biofouling coatings, [23,24] etc.,o ffering ap romising route to reduce plastic pollution. This approach has also been used to confer (bio)degradability to many vinyl-based biomaterials such as polymer prodrugs, [25] nanoparticles, [26,27] thermo-responsive materials, [20,28,29] icerecrystallization inhibitors, [30] etc.…”