Electrografted nanostructured platforms for click chemistry

We report on the combination of nanosphere lithography, electrodeposition and click chemistry to produce nanostructured surfaces with improved number of anchored molecules. Our strategy was developed here for the immobilization of ferrocene at glassy carbon electrode, both used as models. The nanostructuration of the surface was obtained by adsorption of 900 nm-diameter polystyrene nanosphere followed either by electropolymerization of N-(10-azidodecyl)pyrrole or by electrografting of 4-azidobenzenediazonium. In the case of poly-N-(10-azidodecyl)pyrrole, the AFM analysis of the surface after electropolymerization and removal of the nanospheres show the formation of a patterned film with holes separated of ≈ 900 nm. In the case of 4-azidobenzenediazonium, the electrografting proceeds similarly to bare surfaces, but with a decrease of reduction peak intensity due to the partial coverage of the electrode surface with insulating nanospheres. For both modified surfaces, the immobilization of ferrocene by copper(I) catalyzed azide-alkyne cycloaddition was clearly evidenced by cyclic voltammetry. The evaluation of the surface coverage shows that the nanostructuration leads to larger specific area for the chemical anchorage of ferrocene. Finally this procedure produces versatile functionalization of conductive materials used in various applications.