Over the past decade, bipolar electrochemistry has emerged from relative obscurity to provide a promising new means for integrating electrochemistry into lab-ona-chip systems. This article describes the fundamental operating principles of bipolar electrodes, as well as several interesting applications.A bipolar electrode (BPE) is an electronic conductor in contact with an ionically conductive phase. When a sufficiently high electric field is applied across the ionic phase, faradaic reactions occur at the ends of the BPE even though there is no direct electrical connection between it and an external power supply. In this article, we describe the fundamental principles and some electroanalytical applications of BPEs for array-based sensing, separations, and concentration enrichment in microelectrochemical systems. Specifically, we show how the latter three operations, which are normally thought of as arising from different phenomena, are linked by processes occurring on and near BPEs confined within a convenient, miniaturized microfluidic format. The results presented here demonstrate that under a particular set of conditions, up to 1000 well-defined BPEs can be simultaneously activated and interrogated using just a single pair of driving electrodes. Furthermore, a slight change to the resistance of the buffer solution within the microfluidic channel leads to the separation and concentration enrichment of charged analytes.
OVERVIEW OF BIPOLAR ELECTROCHEMISTRYA traditional three-electrode electrochemical cell, which consists of a working electrode, an auxiliary electrode, and a reference electrode, is illustrated in Scheme 1a. In this configuration, the potential of the working electrode, which is related to the energy of the electrons in the electrode, is controlled (versus a reference electrode) using a potentiostat. The potential of the solution is not directly controlled; in other words, it is at a floating potential that (in the absence of an externally applied electric field) depends on the composition of the solution. When the potential of the working electrode is set to a value more negative than that of an electroactive molecule in the solution, electrons may (depending upon kinetics) transfer from the electrode to reduce species in solution (Scheme 1b; note that positive potentials are up in this diagram to make it consistent with Scheme 1c). Similarly, oxidation reactions occur when the electron transfer is in the opposite direction. The faradaic current measured in the circuit connecting the working and auxiliary electrodes is a direct FRANĂ OIS MAVRĂ