Ferritin–Polymer Conjugates: Grafting Chemistry and Integration into Nanoscale Assemblies

Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer‐to‐initiator feed ratio. PolyMPC and polyPEGMA‐grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA‐coated ferritin in organic solvents enables its processing with polystyrene‐block‐poly(ethylene oxide) copolymers, and selective integration into the PEO domains of microphase‐separated copolymer structures.