Thermoresponsive poly(glycidyl ether) brushes can be grafted to applied tissue culture substrates and used for the fabrication of primary human cell sheets. The self-assembly of such brushes is achieved via the directed physical adsorption and subsequent UV immobilization of block copolymers equipped with a short, photo-reactive benzophenone-based anchor block. Depending on the chemistry and hydrophobicity of the benzophenone anchor, we demonstrate that such block copolymers exhibit distinct thermoresponsive properties and aggregation behaviors in water. Independent on the block copolymer composition, we developed a versatile grafting-to process which allows the fabrication of poly(glycidyl ether) brushes on various tissue culture substrates from dilute aqueous-ethanolic solution. The viability of this process crucially depends on the chemistry and hydrophobicity of, both, benzophenone-based anchor block and substrate material. Utilizing these insights, we were able to manufacture thermoresponsive poly(glycidyl ether) brushes on moderately hydrophobic polystyrene and polycarbonate as well as on rather hydrophilic polyethylene terephthalate and tissue culture-treated polystyrene substrates. We further show that the temperature-dependent switchability of the brush coatings is not only dependent on the cloud point temperature of the block copolymers, but also markedly governed by the hydrophobicity of the surface-bound benzophenone anchor and the subjacent substrate material. Our findings demonstrate that the design of amphiphilic thermoresponsive block copolymers is crucial for their phase transition characteristics in solution and on surfaces.
