Utilizing the Oxygen Reduction Reaction in Particle Impact Electrochemistry: A Step toward Mediator-Free Digital...

The current blockade particle impact method opens a route toward highly parallelized single-entity electrochemical assays. An important limitation is, however, that a redox mediator must be present in the sample, which can detrimentally interfere with molecular recognition processes. Dissolved O₂ that is naturally present in aqueous solutions under ambient conditions can in principle serve as a suitable mediator via the oxygen reduction reaction (ORR). Here, we demonstrate the validity of this concept by performing current blockade experiments to capture and detect individual microparticles at Pt microelectrodes using solely the ORR. The readout modality is independent of the absolute O₂ concentration, allowing operation under varying conditions. We further determine how the trajectories of individual microparticles are influenced by the combination of electrophoresis and electroosmotic flows and how these can be utilized to provide continuous detection of cationic particles in water for environmental monitoring.