A Guide to Recognizing Your Electrochemical Impedance Spectra: Revisions of the Randles Circuit in (Bio)sensing

Electrochemical impedance spectroscopy (EIS) is a highly versatile electrochemical technique capable of discretizing each electrochemical parameter in complex systems by employing a broad frequency spectrum. When EIS is employed in (bio)sensing applications, the electrochemical parameters are usually fitted into a relatively limited equivalent circuit model regardless of the system at hand. This work thoroughly discusses the meaning of each physical parameter in the Randles circuit, the most common equivalent circuit to model (bio)sensing systems based on EIS transduction. Additionally, it pinpoints the most suitable modifications to the Randles circuit for modern-day electrodes, where coatings of non-biological and/or biological materials can radically impact the measured impedance compared to that of unmodified electrodes. The discussion is supported by simulations that clearly exhibit the effect of each examined parameter, providing guidance for experimentalists to improve the accuracy of their work.