Separation high voltage field driven on-chip amperometric detection in capillary electrophoresis

A new potentiostatless detection scheme for amperometric detection in capillary electrophoresis is presented based on the use of microband array electrodes positioned in the capillary electrophoresis electric field. In the present study, the spatial potential difference in the CE separation high-voltage field was measured using two gold microband electrodes positioned in the proximity of the capillary outlet. The induced potential difference between the two electrodes was recorded as a function of the applied separation high voltage and the dependence of the electrochemically generated current on the high-voltage field, and the concentration of a redox couple (Fe(CN)(6)(4-)/Fe(CN)(6)(3-)) was investigated. The results show that plots of the generated current versus the CE separation voltage have the same shape as cyclic voltammograms obtained with the same electrodes in a traditional potentiostatic setup and that the current is proportional to the concentration of the redox couple. As a decoupling device is not needed, the described potentiostatless approach significantly simplifies the instrumental setup for amperometric detection. This approach consequently holds great promise for application in inexpensive portable chip-based CE devices.