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.

Polymer coatings with features of differing hydrophilicity, mobility, and topography, distributed across a substrate in microscopic and nanoscopic patches were designed as complex materials equipped with sufficient variability in composition, structure, and dynamics to inhibit interactions associated with biomacromolecular fouling. These complex polymer coatings were prepared by the in situ phase separation and crosslinking of mixtures of hyperbranched fluoropolymer (HBFP) and diamino‐terminated poly(ethylene glycol) (PEG), for which the degree of crosslinking, compositions, topographies, and morphologies were varied by alteration of the PEG/HBFP stoichiometries (14, 29, 45, and 55 wt % PEG). This article examines the physicochemical details of HBFP–PEG network coatings prepared on glass substrates, functionalized by 3‐aminopropyltriethoxysilane, as characterized by atomic force microscopy (AFM), contact‐angle measurements, X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetric analysis. Upon incubation in water or artificial seawater, the surfaces underwent reconstruction, which was believed to be driven by the swelling of the PEG domains and the energetic favorability offered by the segregation of PEG to the solid–water interface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6193–6208, 2004

Amphiphilic diblock copolymers of polystyrene (PS) and poly(N-vinylpyrrolidone) (PNVP) were prepared by a combination of ATRP and MADIX. Well-defined PS with bromine end group was synthesized by ATRP in bulk at 110 8C using (1-bromoethyl) benzene as an initiator. The Br-end group was then converted to xanthate as verified by 1 H NMR spectroscopy, elemental analysis, and UV-spectroscopy. PS-b-PNVP copolymers were produced by MADIX of NVP in bulk at 60 8C using PS-xanthate as a macro-chain transfer agent and the kinetics of polymerization were investigated. The structures of PS-b-PNVP were characterized using GPC and 1 H NMR. Amphiphilic PS-b-PNVP could form spherical micelles with PS cores and PNVP shells in aqueous solution as confirmed by 1 H NMR and laser light scattering (LLS). The values of critical micelle concentration of PS-b-PNVP and the average aggregation number of PS-b-PNVP in the micelles were measured using pyrene as a probe and static LLS, respectively. The aggregation number increases concomitantly with temperature (10-50 8C), but the hydrodynamic radius of the micelles remains almost constant over the same temperature range, which may indicate shell dehydration at a higher temperature. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: [5604][5605][5606][5607][5608][5609][5610][5611][5612][5613][5614][5615] 2008

Methacrylate-functionalized cubic silsesquioxane homopolymers [p(MA-CSSQ)] were synthesized by reversible addition-fragmentation chain transfer (RAFT)-mediated living radical polymerization in the presence of dodecyl(dimethylacetic acid)trithiocarbonate (DDTA) chain transfer agent, and their polymerization kinetics were studied. The DDTA-terminated p(MA-CSSQ) was then employed as a macro-RAFT agent in the polymerization of methylmethacrylate (MMA) for the synthesis of a brushlike p(MA-CSSQ)-b-PMMA block copolymer. The kinetics study of p(MA-CSSQ) showed that the monomer to polymer conversion, evaluated by (1)H NMR, was found to be approximately 80% with the maximum number average molecular weight (M(n)) of 24000 and 32300 Da, for the [MA-CSSQ]/[DDTA] ratios of 100 and 200, respectively, as determined by gel permeation chromatography (GPC). The broadening of molecular weight distributions in p(MA-CSSQ) homopolymer GPC traces was observed, presumably due to the presence of the radical-radical termination products. The resultant homopolymer and block copolymer exhibited excellent thermal stability as evidenced by thermogravimetric and differential scanning calorimetric analyses. The surface properties of p(MA-CSSQ) homopolymer and p(MA-CSSQ)-b-PMMA block copolymer, determined by water contact angle and atomic force microscopy (AFM) measurements, strongly indicated the surface enrichment of the hydrophobic silsesquioxane groups. The AFM images showed the microsized granular domains of p(MA-CSSQ) homopolymer, whereas the islandlike phase-separated domains were observed in p(MA-CSSQ)-b-PMMA block copolymer.