Oxidation of Cysteine by Electrogenerated Hexacyanoferrate(III) in Microliter Droplets

Chemical reactivity in droplets is often assumed to mimic reactivity in bulk, continuous water. Here, we study the catalytic oxidation of cysteine by electrogenerated hexacyanoferrate(III) in microliter droplets. These droplets are adsorbed onto glassy carbon macroelectrodes and placed into an immiscible 1,2-dichloroethane phase. We combined cyclic voltammetry, optical microscopy, and finite element simulations to quantify the apparent bimolecular rate constant, k(c,app), in microdroplets and bulk water. Statistical analyses reveal that the apparent bimolecular rate constant (k(c,app)) values formicrodroplets are larger than those in the continuous phase. Reactant adsorption to the droplet boundary has previously been implicated as the cause of such rate accelerations. Finite element modeling of this system suggests that molecular adsorption to the liquid|liquid interface cannot alone account for our observations, implicating kinetics of the bimolecular reaction either at the boundary or throughout the microliter volume. Our results indicate that cysteine oxidation by electrogenerated hexacyanoferrate(III) can be accelerated within a microenvironment, which may have profound implications on understanding biological processes within a cell.

Automated summary

Chemical reactivity in microdroplets differs from that in bulk water, with a higher apparent bimolecular rate constant observed in microdroplets. The cause of this rate acceleration is not solely attributed to the adsorption of reactants at the liquid|liquid interface, indicating the involvement of kinetics of the bimolecular reaction throughout the microdroplet volume or at the boundary. These findings have significant implications for understanding biological processes within cells.