Emerging progress of the Particle Impact Electrochemistry (PIE) technique has opened a novel field of detection and characterization of many analyte particles. 1 PIE comprises detection of changes in current when collisions of individual micro or nanoparticles are linked with an electrochemical event at the surface of an ultramicroelectrode (UME). 2 Being a rapid, low cost, and analyzing of one analyte at a time, PIE is widely used to characterize the shape, size distribution, and catalytic activity of nanoparticles. 2-5 To explore the scope of PIE for the detection of soft microparticles (absence of crystalline structure), ferrocene (Fc) trapped toluene-in-water emulsion droplets was used as a model with ultramicroelectrode. Droplets were analyzed by tracking the oxidation of Fc inside the droplet in the presence of an ionic liquid acting as emulsifier and conductivity enhancer. The droplet diameter was determined electrochemically using Faraday’s law. PIE was able to characterize the polydisperse size distribution of the droplets successfully. A 3D lattice random walk simulation indicated the stochastic nature of the droplet motion. Unlike nanoparticles, the droplets have slow kinetics and the collision dynamics associated with adsorption on the electrode surface. The adsorbing droplet generated similar spike-like electrical signals in real-time experiments that follow the bulk electrolysis model. These findings will facilitate the characterization of polydisperse microparticles including bacteria, which also adsorb and have similar size and density as the droplets in this work. Finally, because electrolysis time spans from hundreds of milliseconds to a second, single events of such duration are detectable with present-day instrumentation in contrast to non-adsorbing nanoparticles that have nanosecond collisions.
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