Dual functionalized brush copolymers as versatile antifouling coatings

Polymer coatings containing both fouling-resistant and fouling-release components have been reported to show synergistic antifouling properties. However, it remains unclear how the polymer composition influences the antifouling performance, particularly regarding foulants of different sizes and biological natures. Herein, we prepare dual functionalized brush copolymers containing fouling-resistant poly(ethylene glycol) (PEG) and fouling-release polydimethylsiloxane (PDMS) and examine their antifouling performances against different biofoulants. We utilize poly(pentafluorophenyl acrylate) (PPFPA) as a reactive precursor polymer and graft amine-functionalized PEG and PDMS side chains to create PPFPA-g-PEG-g-PDMS brush copolymers of systematically varying compositions. The copolymer films spin-coated on silicon wafers exhibit surface heterogeneity that can be correlated well with the bulk composition of the copolymer. When the copolymer-coated surfaces are examined against protein (human serum albumin and bovine serum albumin) adsorption and cell (lung cancer cells and microalgae) adhesion, they are found to perform better than the homopolymers. The enhanced antifouling properties are attributed to the copolymers having a PEG-rich top layer and a PEG/PDMS mixed bottom layer that work synergistically to resist biofoulant attachment. Furthermore, the composition of the best-performing copolymer is different for different foulants, with PPFPA-g-PEG₃₉-g-PDMS₄₆ exhibiting the best antifouling properties against proteins and PPFPA-g-PEG₅₄-g-PDMS₃₀ exhibiting the best antifouling properties against cells. We explain this difference by considering the changes in the length scale of the surface heterogeneity in relation to the foulant sizes.