In situ observation of single-molecule surface reactions from low to high affinities

Abstract

Understanding reactions occurring between ligand molecules and nanomaterial surfaces is essential in the field of nanoscience. The conventional methods for characterizing such surface-based reactions allow only for the analysis of the end product of a reaction, although the reaction path proceeds through the transient interaction of reactants and with kinetics dependent on environmental parameters. Here we study single molecule reaction kinetics associated with gold nanoparticle surfaces in an aqueous medium by utilizing whispering-gallery-mode microcavity sensors. Our approach resolves transient as well as permanent interaction kinetics of ligand molecules at the nanoparticle interface in situ, over a broad range of affinities and even under conditions where no net product is formed. This enables us to monitor and characterize reactions during the entire procedure of a bottom-up surface modification, ranging from the deposition of ligands to the confirmation of their functionality. We demonstrate this prospect by studying surface reaction kinetics with respect to the species of ligand head groups, tethered molecules, and inhibitors in addition to subsequent bio-specific reactions between tethered molecules and analytes.