Encapsulated electrodes for microchip devices: Microarrays and platinized electrodes for signal enhancement

In this paper, we present two new methodologies of improving the performance of microchip‐based electrochemical detection in microfluidic devices. The first part describes the fabrication and characterization of epoxy‐embedded gold microelectrode arrays that are evenly spaced and easily modified. Electrodepositions using a gold plating solution can be performed on the electrodes to result in a 3D pillar array that, when used with microchip‐based flow injection analysis, leads to an eightfold increase in signal (when compared to a single electrode), with the LOD for catechol being 4 nM. For detecting analytically challenging molecules such as nitric oxide (NO), platinization of electrodes is commonly used to increase the sensitivity. It is shown here that microchip devices containing either the pillar arrays or more traditional glassy carbon electrodes can be modified with platinum black (Pt‐black) for NO detection. In the case of using glassy carbon electrodes for NO detection, integration of the resulting platinized electrode with microchip‐based flow analysis resulted in a ten times signal increase relative to use of a bare glassy carbon electrode. In addition, it is demonstrated that these electrodes can be coated with Nafion to impart selectivity toward NO over interfering species such as nitrite. The LOD for NO when using the Pt‐black /Nafion‐coated glassy carbon electrode was 9 nM. These electrodes can also be embedded in a polystyrene substrate, with the applicability of these sensitive and selective electrodes being demonstrated by monitoring the adenosine triphosphate‐mediated release of NO from endothelial cells immobilized in a microfluidic network without any adhesion factor.