Nano MIPs (Molecularly Imprinted Polymers) Prepared From a “Frustrated” Gold Nanoparticle‐Based Pre‐Imprinting Matrix: Enhancing Binding Affinity and Selectivity

ABSTRACT Molecularly imprinted polymers have broad applications in chemistry and biology. Nanomaterials differ substantially from analogous materials on the macroscopic scale. In this work, ligand‐stabilized gold nanoparticles and two micelles with different surfactant structures are used as nanoplatforms for molecular imprinting. Each platform due to its unique structure strongly impacts the imprinting, to the point that the best template molecule on one platform could become the worst on another. Ligand‐stabilized gold nanoparticles can be engineered to contain unsatisfied or ‘frustrated’ hydrophobic and hydrogen‐bonding interactions within the monolayer, causing molecular imprinting on these particles to strongly favor templates that satisfy these interactions and to penalize those that do not, dramatically improving binding affinity and selectivity as a result. In contrast, with freely moving surfactants that rapidly optimize their interactions with the templates, micelles give more predictable results during imprinting, governed by the hydrogen‐bonding abilities and hydrophobicity of the surfactant molecules. These results indicate that the unique features of each nanoplatform can be exploited to improve molecular imprinting on the nanoscale and facilitate the preparation of advanced nanomaterials with tailored molecular recognition properties.