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 FRANÇ OIS MAVRÉ

Bipolar electrode (BPE) focusing locally enriches charged analytes in a microchannel along an electric field gradient that opposes a counter-flow. This electric field gradient forms at the boundary of an ion depletion zone generated by the BPE. Here, we demonstrate concentration enrichment of a fluorescent tracer by up to 500,000-fold. The use of a dual-channel microfluidic configuration, composed of two microchannels electrochemically connected by a BPE, enhances the rate of enrichment (up to 71-fold/s). Faradaic reactions at the ends of the BPE generate ion depletion and enrichment zones in the two, separated channels. This type of device is equivalent to previously reported micro/nanochannel junction arrangements used for ion concentration polarization, but it is experimentally more flexible and much simpler to construct.

We demonstrate continuous high-throughput selective capture of circulating tumor cells by dielectrophoresis at arrays of wireless electrodes (bipolar electrodes, BPEs). The use of BPEs removes the requirement of ohmic contact to individual array elements, thus enabling otherwise unattainable device formats. Capacitive charging of the electrical double layer at opposing ends of each BPE allows an AC electric field to be transmitted across the entire device. Here, two such designs are described and evaluated. In the first design, BPEs interconnect parallel microchannels. Pockets extruding from either side of the microchannels volumetrically control the number of cells captured at each BPE tip and enhance trapping. High-fidelity single-cell capture was achieved when the pocket dimensions were matched to those of the cells. A second, open design allows many non-targeted cells to pass through. These devices enable high-throughput capture of rare cells and single-cell analysis.

Bipolar electrode (BPE) focusing is a developing technique for enrichment and separation of charged analytes in a microfluidic channel. The technique employs a bipolar electrode that initiates faradaic processes that subsequently lead to formation of an ion depletion zone. The electric field gradient resulting from this depletion zone focuses ions on the basis of their individual electrophoretic mobilities. The nature of the gradient is of primary importance to the performance of the technique. Here, we report dynamic measurements of the electric field gradient showing that it is stable over time and that its axial position in the microchannel is directly correlated to the location of an enriched tracer band. The position of the gradient can be tuned with pressure-driven flow. We also show that a steeper electric field gradient decreases the breadth of the enriched tracer band and therefore enhances the enrichment process. The slope of the gradient can be tuned by altering the buffer concentration: higher concentrations result in a steeper gradient. Coating the channel with the neutral block co-polymer Pluronic also results in enhanced enrichment.

Membraneless desalination: A simple power supply is used to apply a 3.0 V potential bias across a microelectrochemical cell comprising two microchannels spanned by a single bipolar electrode (BPE) to drive chloride oxidation and water electrolysis at the BPE poles. The resulting ion depletion zone and associated electric field gradient direct ions into a branching microchannel, consequently producing desalted water. Gnd=ground.