Microchip electrophoresis with wall-jet electrochemical detector: Influence of detection potential upon resolution of solutes

This report studies the electrochemical response of wall-jet detector for microchip electrophoresis (μCE). It shows that in wall-jet configuration, the electrochemical detector operates in coulometric mode and that there is an influence of detection potential upon peak width and therefore upon the resolution of solutes. Upon raising the detection potential from +0.3 to +0.9 V, the resolution between model analytes, dopamine and catechol, increases from 0.63 to 2.90. The reasons for this behavior originate in wall-jet detector design and in its typically significant higher detector volume than the volume of injected sample. The conversion efficiency of the wall-jet electrochemical detection cell was found to be 97.4% for dopamine and 98.0% for catechol. The paper brings deeper understanding of operations of wall-jet electrochemical detectors for microchip devices, and it explains previously reported significantly sharper peaks when electrocatalytic electrodes (i.e., palladium and carbon nanotube) were used in μCE-electrochemistry wall-jet detector. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.