Polymer Brushes Exhibiting Versatile Supramolecular Interactions Grown by Nitroxide-Mediated Polymerization and Structured via Microcontact Chemistry

Functionalization of metal, glass, and semiconductor substrates with polymers and nanoparticles is a key challenge for surface-based material science. Such substrates have the potential to find widespread application in optical and electronic devices, microarrays, and materials for information storage. We report site-specific immobilization of nitroxide-mediated polymerization initiators via microcontact chemistry employing thiol–ene click chemistry on glass-supported alkene-terminated self-assembled monolayers. The polymer initiator covered substrates are used for preparation of poly(styrene) and poly(acrylate) brushes with defined and tunable brush thicknesses. Brush thickness dependent site-specific protein adsorption of streptavidin and concanavalin A on structured polystyrene brushes is reported. Poly(styrene) brushes with a thickness of 40 nm or larger showed protein repellence whereas brushes below 15 nm thickness reveal protein adhesive properties. We also disclose the site selective host–guest assisted immobilization of β-cyclodextrin-coated silica nanoparticles and the tethering of liposomes modified with amphiphilic β-cyclodextrin onto adamantane-functionalized poly(acrylate) brushes. Selective immobilization of these supramolecular colloids via the multivalent hydrophobic inclusion complex of β-cyclodextrin and adamantane can be readily verified by fluorescence microscopy imaging, atomic force microscopy, and quartz crystal microbalance with dissipation monitoring.