Design and Functions of Fluorous Nanospaces with Microgel Star Polymers and Amphiphilic Random Copolymers

This comprehensive article summarizes our recent efforts to create fluorous nanospaces with microgel-core star polymers and amphiphilic random copolymers via living radical polymerization for molecular encapsulation and bioapplication. Fluorous microgel star polymers were obtained in high yield from ruthenium-catalyzed crosslinking reactions of hydrophobic poly(methyl methacrylate) or hydrophilic poly(ethylene glycol) (PEG) arms with perfluorinated methacrylates; the star polymers serve as homogeneously-soluble fluorous nanocapsules to selectively encapsulate and release perfluorinated compounds in organic solvents or water. Fluorous star polymers with PEG arms and the star polymer gels were particularly effective for the removal of potentially toxic perfluorinated surfactants in water. In contrast, amphiphilic/fluorous random copolymers gave dynamic fluorous nanospaces via single-chain folding and/or multi-chain aggregation in water. The fluorous core aggregates were non-cytotoxic and afforded protein conjugation. Thus, fluorous nanocapsules consisting of microgel star polymers and amphiphilic random copolymers would open new vistas in molecular encapsulation/separation technologies and biochemical and biomedical applications.