Single-Entity Electrochemistry in the Agarose Hydrogel: Observation of Enhanced Signal Uniformity and Signal-to-Noise Ratio.

For the first time, single-entity electrochemistry (SEE) was demonstrated in a hydrogel matrix. SEE involves the investigation of the electrochemical characteristics of individual nanoparticles (NPs) by observing the signal generated when a single NP, suspended in an aqueous solution, collides with an electrode and triggers catalytic reactions. Challenges associated with SEE in electrolyte-containing solutions such as signal variation due to NP aggregation and noise fluctuation caused by convection phenomena can be addressed by employing a hydrogel matrix. The polymeric hydrogel matrix acts as a molecular sieve, effectively filtering out unexpected signals generated by aggregated NPs, resulting in more uniform signal observations compared to the case in a solution. Additionally, the hydrogel environment can reduce the background current fluctuations caused by natural convection and other factors such as impurities, facilitating easier signal analysis. Specifically, we performed SEE of platinum (Pt) NPs for hydrazine oxidation within the agarose hydrogel to observe the electrocatalytic reaction at a single NP level. The consistent porous structure of the agarose hydrogel leads to differential diffusion rates between individual NPs and reactants, resulting in variations in signal magnitude, shape, and frequency. The changes in the signal were analyzed in response to gel concentration variations.