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The impact of the orientation of zwitterionic groups, with respect to the polymer backbone, on the antifouling performance of thin hydrogel films made of polyzwitterions is explored. In an extension of the recent discussion about differences in the behavior of polymeric phosphatidylcholines and choline phosphates, a quasi-isomeric set of three poly(sulfobetaine methacrylate)s is designed for this purpose. The design is based on the established monomer 3-[N-2-(methacryloyloxy)ethyl-N,N-dimethyl]ammonio-propane-1-sulfonate and two novel sulfobetaine methacrylates, in which the positions of the cationic and the ionic groups relative to the polymerizable group, and thus also to the polymer backbone, are altered. The effect of the varied segmental dipole orientation on their water solubility, wetting behavior by water, and fouling resistance is compared. As model systems, the adsorption of the model proteins bovine serum albumin (BSA), fibrinogen, and lysozyme onto films of the various polyzwitterion surfaces is studied, as well as the settlement of a diatom (Navicula perminuta) and barnacle cyprids (Balanus improvisus) as representatives of typical marine fouling communities. The results demonstrate the important role of the zwitterionic group's orientation on the polymer behavior and fouling resistance.
Although zwitterionic chemistries are among the most promising materials for producing nonfouling surfaces, their structural diversity has been low until now. Here, we compare the in vitro fouling behavior of a set of four systematically varied sulfa-/sulfobetaine-containing zwitterionic hydrogel coatings against a series of proteins and nonmotile as well as motile marine organisms as model foulers. The coatings are prepared by simultaneous photoinduced cross-linking and surface anchoring to elucidate the effect of the molecular structure of the zwitterionic moieties on their antifouling activity. Analogously prepared coatings of poly(butyl methacrylate) and poly(oligoethylene glycol methacrylate) serve as references. Photoreactive polymers are synthesized by the statistical copolymerization of sulfobetaine or sulfabetaine methacrylates and methacrylamides with a benzophenone derivative of 2-hydroxyethyl methacrylate and are applied as a thin film coating. While keeping the density of the zwitterionic and cross-linker groups constant, the molecular structure of the zwitterionic side chains is varied systematically, as is the arrangement of the ion pairs in the side chain by changing the classical linear geometry to a novel Y-shaped geometry. All of the polyzwitterions strongly reduce fouling compared to poly(butyl methacrylate). Overall, the sulfabetaine polyzwitterion coatings studied matches the high antifouling effectiveness of oligo(ethylene glycol)-based ones used as a control. Nevertheless, performances varied individually for a given pair of polymer and fouler. The case of the polysulfobetaines exemplifies that minor chemical changes in the polymer structure affect the antifouling performance markedly. Accordingly, the antifouling performance of such polymers cannot be correlated simply to the type of zwitterion used (which could be generally ranked as better performing or poorer performing) but is a result of the polymer’s precise chemical structure. Our findings underline the need to enlarge the existing structural diversity of polyzwitterions for antifouling purposes to optimize the potential of their chemical structure.