Evaluating important analytical figures of merit for PILSNER: particle-into-liquid sampling for nanoliter electrochemical reactions.

Recently introduced as a method for aerosol electroanalysis, particle-into-liquid sampling for nanoliter electrochemical reactions (PILSNER) has shown promise as a versatile, highly sensitive analytical technique. To further validate the analytical figures of merit, we present correlated fluorescence microscopy and electrochemical data. The results show excellent agreement as to the detected concentration of a common redox mediator, ferrocyanide. Experimental data also suggest that PILSNER's unconventional two-electrode system is not a contributing source of error when appropriate controls are established. Finally, we address the concern that arises from two electrodes operating within such close proximity. COMSOL Multiphysics simulations confirm that with the present parameters, positive feedback is not a contributing source of error in voltammetric experiments. The simulations also show at what distances feedback could become a source of concern, which will be a factor in future investigations. Thus, this paper provides validation of PILSNER's analytical figures of merit, as well as voltammetric controls and COMSOL Multiphysics simulations to address possible confounding factors that could arise from PILSNER's experimental setup.