The Antifouling and Fouling-Release Perfomance of Hyperbranched Fluoropolymer (HBFP)−Poly(ethylene glycol) (PEG) Composite Coatings Evaluated by Adsorption of Biomacromolecules and the Green Fouling Alga Ulva

Abstract

Cross-linked hyperbranched fluoropolymer (HBFP) and poly(ethylene glycol) (PEG) amphiphilic networks with PEG weight percentages of 14% (HBFP-PEG14), 29% (HBFP-PEG29), 45% (HBFP-PEG45), and 55% (HBFP-PEG55) were prepared on 3-aminopropyl)triethoxysilane (3-APS) functionalized microscope glass slides for marine antifouling and fouling-release applications. The surface-free energies (gamma(s)), polar (gamma(s)(p) and gamma(s)(AB)), and dispersion (gamma(s)(d) and gamma(s)(LW)) components were evaluated using advancing contact angles by two-liquid geometric-mean and three-liquid Lifshitz-van der Waals acid-base approaches. The HBFP coating exhibited a low surface energy of 22 mJ/m(2), while the gamma(s) and gamma(s)(p) of the cross-linked HBFP-PEG coatings increased proportionally with the PEG weight percentages in the networks. The adsorption of bovine serum albumin (BSA), lectin from Codium fragile (CFL), lipopolysaccharides from Escherichia coli (LPSE) and Salmonella minnesota (LPSS) upon glass, APS-glass, HBFP, PEG, and the cross-linked HBFP-PEG network coatings were investigated by fluorescence microscopy. The marine antifouling and fouling-release properties of the cross-linked HBFP-PEG coatings were evaluated by settlement and release assays involving zoospores of green fouling alga Ulva (syn. Enteromorpha; Hayden, H. S.; Blomster, J.; Maggs, C. A.; Silva, P. C.; Stanhope, M. J.; Waaland, J. R. Eur. J. Phycol. 2003, 38, 277). The growth and release of Ulva sporelings were also investigated upon the HBFP-PEG45 coating in comparison to a poly(dimethylsiloxane) elastomer (PDMSE) standard material. Of the heterogeneous cross-linked network coatings, the maximum resistances to protein, lipopolysaccharide, and Ulva zoospore adhesion, as well as the best zoospore and sporeling release properties, were recorded for the HBFP-PEG45 coating. This material also exhibited better performance than did a standard PDMSE coating, suggesting its unique applicability in fouling-resistance applications.

Effect of contact angle hysteresis on the removal of the sporelings of the green alga Ulva from the fouling-release coatings synthesized from polyolefin polymers

“…6. This is in agreement with the results of Gudipati et al 26 and Krishnan et al 27 where the strength of attachment of sporelings was typically lower on the hydrophobic surfaces.…”

“…This finding was also supported with the results of some recent reports. 24,26,27,47 Only a weak inverse relationship between ␥ S tot of the polyolefinic films and Ulva removal was found showing that contact angle hysteresis results are the more important parameter than the surface free energy of the films in order to correlate with the Ulva foul-release properties from these surfaces.…”

“…Yarbrough et al 24 reported that the removal of Ulva sporelings from poly ͑MMA-co-GMA-g-PFPED͒ terpolymer having a CAH of 24°was larger than the poly ͑MMA-co-GMA-g-PFPEM͒ terpolymer having a CAH of 20°. Gudipati et al 26 reported that for their samples synthesized from cross-linked hyperbranched fluoropolymer ͑HBFP͒ and poly͑ethylene glycol͒ ͑PEG͒ amphiphilic networks, their sample coded as HBFP-PEG45 having a CAH value of 30°Ϯ 6°resulted in the 40% removal, whereas sample HBFP-PEG55 having a CAH value of 25°Ϯ 10°re-sulted in 10% removal, showing that the higher the mean CAH, the higher the spore removal for these chemically heterogeneous samples. HBFP-PEG45 sample surface also resulted in the largest removal of 8 days old sporelings.…”

Surface Sensing and Settlement Strategies of Marine Biofouling Organisms

“…Such inert coatings have been identified for a number of well-defined surfaces in short term, single species assays. Especially ethylene glycol (EG) x -containing coatings have been used in the biomedical area [21][22][23][24] and have recently been investigated with respect to their marine anti-fouling potential [25][26][27][28][29][30][31][32][33]. However, the degradation of the ethylene-glycol-containing chemistries makes them unsuitable for long-term antifouling applications [34,35].…”

“…However, the degradation of the ethylene-glycol-containing chemistries makes them unsuitable for long-term antifouling applications [34,35]. Other promising approaches involve the use of amphiphilic [26,27,29,36] or zwitterionic chemistries [37][38][39][40]. Even though fouling inhibition is the most desirable way of avoiding biofouling, the development of such inert, non-toxic, and long-term stable coatings remains to be the most challenging of the three approaches.…”