The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (Mw = 350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS8 K-b-P(E/B)25 K-b-PI10 K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (Mw = 550 g mol(-1)) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings.

Here, a new procedure and method are presented for the production of highly grafted polymer brushes. Thiol-terminated polyethylene oxide (PEO-SH) of molecular weight (M(w)) 20,000 (20k) is grafted to a gold surface from highly concentrated aqueous solutions of nonthiolated polyethylene oxide homopolymer. The M(w) and volume fraction of the homopolymer solution are varied in order to control the grafting density of the resulting PEO-SH brush. As a result, 20k M(w) PEO-SH brushes with grafting densities up to 0.3 chains/nm(2) are achieved, as determined by ellipsometry. Highly concentrated homopolymer solutions of volume fraction greater than approximately 12% and M(w) greater than approximately 938 produce near-ideal solvent conditions for the 20k M(w) PEO-SH chains; we have found that this facilitates the achievement of higher grafting densities of end-functionalized polymer brushes than would be possible from simple solutions. We propose this as a suitable method for applications where the grafting density of a brush surface must be accurately varied and controlled consistently. The effect of chemisorption time and cleaning procedure on the resulting brush grafting density are also explored.

The adsorption of lysozyme protein was measured ex situ on well-characterized gold surfaces coated by end-tethered polyethylene oxide brushes of various molecular weights and controlled grafting densities. The adsorbed amount of protein for different molecular weight brushes was found to collapse onto one master curve when plotted against brush coverage. We interpret this relationship in terms of a model involving site-blocking of the adsorption of proteins at the substrate and discuss the role of the physical attraction of PEO segments to gold. We account for our observation of a simple exponential relationship between protein adsorption and normalized brush coverage with a simple protein adsorption model. In contrast to other studies in similar systems, we do not observe protein adsorption on brushes at high grafting density, and we suggest that this discrepancy may be due to the solubility effects of salt upon the brushes, influencing their protein binding affinity, in the limit of high grafting density and high brush volume fraction.

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