Squish and CuAAC: Additive-Free Covalent Monolayers of Discrete Molecules in Seconds

A terminal alkyne is immobilized rapidly into a full monolayer by squishing a small volume of a solution of the alkyne between an azide-modified surface and a copper plate. The monolayer is covalently attached to the surface through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction, and the coverages of the immobilized electroactive alkyne species are quantified by cyclic voltammetry. A reaction time of less than 20 s is possible with no other reagents required. The procedure is effective under aerobic conditions using either an aqueous or aprotic organic solution of the alkyne (1-100 mM).