An Artificial Enzyme: How Nanoconfinement Allows the Selective Electrochemical Detection of Glucose Directly in Whole Blood

Abstract Nanoparticles that catalyze biochemically relevant reactions are promoted as alternative enzymes. The application of such artificial enzymes is severely restricted by poor selectivity in biological fluids; mainly because the reactions occur at active sites on the exterior surface of the nanoparticle. Enzymes in contrast typically have their active sites down a nanoconfined substrate channel where the reaction occurs in different solution conditions to bulk solution which aids in achieving selectivity for the substrate. Herein the same 3D structure of enzymes is mimicked in nanoparticles to allow selective reactions in biological fluids. This is achieved using a gold nanoparticle coated in a conducting mesoporous carbon shell where isolated nanochannels lead to the gold surface. It can detect glucose in whole blood with no interference from other species. This is achieved by electrochemically pulsing the artificial enzymes to generate the locally required alkalinity for an effective electrocatalytic reaction in the nanochannels, as well as expelling fouling agents that will otherwise passivate the electrocatalytic reaction. The artificial enzymes are shown to be capable of detecting glucose in biological fluids, without loss of signal, for several months. This study shows how nanoconfinement in nanoparticles can be exploited to potentially allow a broad range of species to be selectively detected in biological fluids with stability that can exceed that of enzymes.