Kinetic Effects on Self‐Assembly and Function of Protein–Polymer Bioconjugates in Thin Films Prepared by Flow Coating

The self‐assembly of nanostructured globular protein arrays in thin films is demonstrated using protein–polymer block copolymers based on a model protein mCherry and the polymer poly(oligoethylene glycol acrylate) (POEGA). Conjugates are flow coated into thin films on a poly(ethylene oxide) grafted Si surface, forming self‐assembled cylindrical nanostructures with POEGA domains selectively segregating to the air–film interface. Long‐range order and preferential arrangement of parallel cylinders templated by selective surfaces are demonstrated by controlling relative humidity. Long‐range order increases with coating speed when the film thicknesses are kept constant, due to reduced nucleation per unit area of drying film. Fluorescence emission spectra of mCherry in films prepared at <25% relative humidity shows a small shift suggesting that proteins are more perturbed at low humidity than high humidity or the solution state.