Rewritable Surface on a Plastic Substrate Using Fluorous Affinity

Fluorous chemistry has unique features and high potential applicability, which are distinct from those of nonfluorinated organic compounds. However, there are limited reports detailing the applications of fluorous–fluorous interactions (fluorophilicity or fluorous affinity), likely because these interactions are not found in nature. In the present study, we describe the rewritable surface functionalization of a plastic substrate based on fluorous affinity. Plastic substrates were dip-coated with a series of methacrylate-based fluoropolymers to generate fluorous surfaces. Fluorous-tagged small molecules [perfluoroalkyl (Rf) amines] were immobilized on the fluorous surfaces via fluorous–fluorous interactions, thereby introducing reactive functional groups (amino moieties) on the surface. The amino groups displayed on the surface (accessible by a reactant) were successfully quantified using a reactive fluorophore, which enabled quantitative analysis of the Rf-amines immobilized on the fluorous surface that were available for the subsequent reaction. The effects of the molecular structures of the fluoropolymers and Rf-amines on the surface immobilization of Rf-amines were also investigated quantitatively. The surface coated with a fluoropolymer containing −C₈F₁₇ most effectively immobilized an Rf-amine comprising two −C₆F₁₃ chains. The adhered Rf-amines were easily removed by washing the surface with methanol, and then, they could successfully be re-immobilized on the surface. Finally, the presented approach enabled the rewritable micropatterning of an Rf-tagged biomolecule on a plastic surface through microcontact printing.