TY - JOUR

T1 - Thermoresponsive poly(glycidyl ether) brush coatings on various tissue culture substrates

T2 - How block copolymer design and substrate material govern self-assembly and phase transition

AU - Stöbener, Daniel David

AU - Weinhart, Marie

N1 - Funding Information: Funding: This research was funded by the Federal Ministry of Education and Research Germany (BMBF) through Grant FKZ: 13N13523. Acknowledgments: D.D.S. is grateful to Simon Rackow for his contributions in polymer synthesis, surface preparation and surface characterization. D.D.S. would further like to thank Alexander Schweigerdt for his support in surface preparation and characterization. The publication of this article was funded by Freie Universität Berlin.

PY - 2020/9

Y1 - 2020/9

N2 - 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.

AB - 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.

KW - Brush conformation

KW - C,H-insertion crosslinking

KW - Coil-to-globule transition

KW - Critical aggregation concentration

KW - Grafting density

KW - Mesoglobules

KW - Physical adsorption

KW - Temperature-dependent wettability

KW - Thermal hysteresis

KW - Volume phase transition

UR - http://www.scopus.com/inward/record.url?scp=85090564331&partnerID=8YFLogxK

U2 - 10.3390/POLYM12091899

DO - 10.3390/POLYM12091899

M3 - Article

AN - SCOPUS:85090564331

VL - 12

JO - Polymers

JF - Polymers

SN - 2073-4360

IS - 9

M1 - 1899

ER -