Universal Bioinert Control of Polystyrene Interfaces via Hydrophobic-Driven Self-Assembled Surface PEGylation with a Well-Defined Block Sequence

This work proposes a new molecular insight of interfacial design in the control of antifouling performance for the versatile biofoulants, including proteins, blood cells, tissue cells, and bacteria. A self-assembled bioinert interface with universal fouling resistance to general biofoulants via hydrophobic-driven surface PEGylation is presented. The study systematically discriminates the optimum PEGylated block polymer configuration and hydrophobic/hydrophilic segmental ratio enabling to optimize the surface coverage by the bioinert moieties, thus ensuring the best resistance to biofouling. For similar copolymer molecular weights and similar polystyrene (PS)/poly(ethylene glycol) methacrylate (PEGMA), the coating density obtainable is the highest if a random copolymer is used, while it is the lowest with a triblock copolymer. That measured with a diblock copolymer lies in between. Random copolymers offer more numerous anchoring possibilities than diblock copolymers, while they are importantly fewer if triblock copolymers are used. For similar total number of hydrophilic blocks, the diblock copolymer is more efficient to resist larger cells (leukocytes, fibroblasts) while the triblock is better to promote mitigate biofouling by smaller molecules or cells (proteins, platelets, red blood cells). The length of the hydrophilic PEGylated block seems to dominate fouling resistance of large biofoulants.