Stochastic Particle Approach Electrochemistry (SPAE): Estimating Size, Drift Velocity, and Electric Force of...

Stochastic particle impact electrochemistry (SPIE) is considered one of the most important electro-analytical methods to understand the physicochemical properties of single entities. SPIE of individual insulating particles (IPs) has been particularly crucial for analyses of bioparticles. In this article, we introduce stochastic particle approach electrochemistry (SPAE) for electrochemical analyses of IPs, which is the advanced version of SPIE; SPAE is analogous to SPIE but focuses on deciphering a sudden current drop (SCD) by an IP-approach toward the edge of an ultramicroelectrode (UME). Polystyrene particles (PSPs) with and without different surface functionalities (-COOH and - NH₃) as well as fixed human platelets (F-HPs) were used as model IPs. From theory based on finite element analysis, a sudden current drop (SCD) induced by an IP during electro-oxidation (or reduction) of a redox mediator on a UME can represent the rapid approach of an IP toward an edge of a UME, where a strong electric field is generated. It is also found that the amount of current drop, i_drop, of an SCD depends strongly on both the size of an IP and the concentration of redox electrolyte. From simulations based on the SPAE model that fit the experimentally obtained SCDs of three types of PSPs or F-HP dispersed in solutions with two redox electrolytes, their size distribution histograms are estimated, from which their average radii determined by SPAE are compared to those from scanning electron microscopic images. In addition, the drift velocity and corresponding electric force of the PSPs and F-HPs during their approach toward an edge of a Pt UME are estimated, which cannot be addressed currently with SPIE. We further learned that the estimated drift velocity and the corresponding electric force could provide a relative order of the number of excess surface charges on the IPs.