Delayed voltammetric with respect to amperometric electrochemical detection of concentration changes in microchannels

The time response of an electrode incorporated into a fluidic channel to variations in analyte concentration of the outer-sphere redox probe ferrocenemethanol was investigated both for amperometry (AMP) and cyclic voltammetry (CV). The experimental data show that the temporal resolution of CV is not as good as that of AMP, as CV cannot properly detect fast concentration transients. The delayed response of CV was previously reported, for neurotransmitters, and mostly attributed to the adsorption of the analyte on the electrode surface. By using an outer-sphere redox couple, we show that mass transport also significantly delays the response of CV. The experimental delay time in CV was understood from mass transfer limitations due to the relaxation of the diffusion layer during repeated potential scanning. Furthermore, a robust protocol for the analysis of fast concentration transients was established, using the impulse and modulation transfer functions of the system. This method was found to be more precise than the mere analysis of undifferentiated traces in the time domain. As a proof of concept, the effect of increased viscosity was investigated, showing that AMP was more sensitive than CV to these variations. Overall, this analysis underlines further the enhanced temporal sensitivity of AMP over CV, at the expense of decreased chemical resolution, potentially having implications for in situ electrochemical detection of biologically relevant molecules.