F.J. Parra-Velandia

Sulfobetaine-based polymer brushes in marine environment: Is there an effect of the polymerizable group on the antifouling performance?

Three different zwitterionic polymer brush coatings for marine biofouling control were prepared by surface-initiated atom transfer radical polymerization (ATRP) of sulfobetaine-based monomers including methacrylamide (SBMAm), vinylbenzene (SBVB) and vinylimidazolium (SBVI). None of these brush systems have been assessed regarding marine antifouling performance. Antifouling tests performed indicate that surfaces featuring these three brush systems substantially reduce the adhesion of the marine microalgae, Amphora coffeaeformis, and the settlement of cyprid larvae of the barnacle, Amphibalanus amphitrite, in a similar way, displaying comparable performance. Thus, it appears that the chemical structure of the polymerizable group has no substantial influence on marine antifouling performance.

Polyion multilayers with precise surface charge control for antifouling

We report on a molecular fabrication approach to precisely control surface ζ potentials of polymeric thin layers constructed by electrostatic layer-by-layer (LbL) assembly methods. The protocol established allows us to achieve surface isoelectric points (IEP) in the pH range of 6-10. Poly(acrylic acid) (PAA, a weak polyanion) and poly(diallyldimethylammonium chloride) (PDADMAC, a strong polycation) were chosen to build up the bulk films. The weak polycation polyethylenimine (PEI) was applied as a top layer. A unique feature of this approach is that the chemical composition of the top layer is not affected by the manipulation of the ζ potential of the films. Surface charge tuning is achieved by controlling the degree of ionization of the weak polyelectrolytes at various pH values and subsequent manipulation of the amount of polyelectrolyte deposited in the penultimate and last layers, respectively. Following assembly and characterization, the films were used as candidates for antifouling surfaces. The fouling behavior of barnacle cyprids and bacteria on the LbL films with similar hydrophilicity and roughness but different surface charge densities were studied. We found that more cyprids of Amphibalanus amphitrite settled on the negatively charged LbL film compared to the neutral or positively charged LbL film. In bacterial adhesion tests employing Pseudomonas, Escherichia coli, and Staphylococcus aureus, more bacteria were observed on the positively charged LbL film compared with the neutral and negatively charged LbL films, possibly as a result of the negative potential of the bacterial cell wall. The procedures proposed allow one to adjust surface isoelectric points of LbL architectures to achieve optimal antifouling performance of a given material taking into account specific pH values of the environment and the character of the fouler.

Biomimicking micropatterned surfaces and their effect on marine biofouling.

When synthetic materials are submerged in marine environments, dissolved matter and marine organisms attach to their surfaces by a process known as marine fouling. This phenomenon may lead to diminished material performance with detrimental consequences. Bioinspired surface patterning and chemical surface modifications present promising approaches to the design of novel functional surfaces that can prevent biofouling phenomena. In this study, we report the synergistic effects of surface patterns, inspired by the marine decapod crab Myomenippe hardwickii in combination with chemical surface modifications toward suppressing marine fouling. M. hardwickii is known to maintain a relatively clean carapace although the species occurs in biofouling communities of tropical shallow subtidal coastal waters. Following the surface analysis of selected specimens, we designed hierarchical surface microtopographies that replicate the critical features observed on the crustacean surface. The micropatterned surfaces were modified with zwitterionic polymer brushes or with layer-by-layer deposited polyelectrolyte multilayers to enhance their antifouling and/or fouling-release potential. Chemically modified and unmodified micropatterned surfaces were subjected to extensive fouling tests, including laboratory assays against barnacle settlement and algae adhesion, and field static immersion tests. The results show a statistically significant reduction in settlement on the micropatterned surfaces as well as a synergistic effect when the microtopographies are combined with grafted polymer chains.

Multilayers of Fluorinated Amphiphilic Polyions for Marine Fouling Prevention

Sequential layer-by-layer (LbL) deposition of polyelectrolytes followed by chemical cross-linking was investigated as a method to fabricate functional amphiphilic surfaces for marine biofouling prevention applications. A novel polyanion, grafted with amphiphilic perfluoroalkyl polyethylene glycol (fPEG) side chains, was synthesized and subsequently used to introduce amphiphilic character to the LbL film. The structure of the polyanion was confirmed by FTIR and NMR. Amphiphilicity of the film assembly was demonstrated by both water and hexadecane static contact angles. XPS studies of the cross-linked and annealed amphiphilic LbL films revealed the increased concentration of fPEG content at the film interface. In antifouling assays, the amphiphilic LbL films effectively prevented the adhesion of the marine bacterium Pseudomonas (NCIMB 2021).