SupramolecularPolymer Brushes Grafted via Atom TransferRadical Polymerization from Surfaces Presenting Non-covalent, Host–GuestComplex-Based Initiators

This paper describes the synthesis of supramolecular polymer brushes via surface-initiated polymerization from adamantane-functionalized initiators that are noncovalently bound to β-cyclodextrin- or cucurbit[7]uril-modified substrates. Surface-initiated atom transfer radical polymerization in aqueous media allowed the growth of various hydrophilic polymer brushes with film thicknesses of up to 40 nm from β-cyclodextrin functionalized surfaces. The adamantane moiety not only forms a host–guest complex with β-cyclodextrin, but also with cucurbit[7]uril, which provides opportunities to study the effect of the binding strength of these supramolecular motifs on the film thickness and grafting density of the resulting polymer brushes. Comparison of supramolecular polymer brushes grown from β-cyclodextrin and cucurbit[7]uril-based noncovalent initiators reveals differences in grafting density that are much smaller than expected based on the differences in the solution binding constant of the corresponding host–guest complexes. Both the β-cyclodextrin as well as the cucurbit[7]uril-anchored supramolecular brushes were remarkably robust toward detachment of the polymer grafts. These observations are attributed to the fact that the rates of formation and dissociation of the host–guest complexes are much faster as compared to diffusion of free, detached polymer chains through the polymer brush film. As a result, the surface-grafted polymer brush presents a steric barrier that prevents detachment of individual chains, and also allows surface-initiated polymerization from substrates to which initiators are bound via putatively weak β-cyclodextrin-based host–guest complexes.