A simple capillary electrophoresis system in the planar format that uses a new, hydrodynamic injection principle is described. The system was realized with poly(dimethylsiloxane)-glass chips and microdisk electrodes for amperometric detection. Using a double-tee injector, no precise voltage control of the electrolyte reservoirs was needed, thus making the microchip CE system more user-friendly. The analytical characteristics of chip-based CE-EC were evaluated using ascorbic acid as the model analyte. The reproducibility of migration time and signal height was expressed by relative standard deviations of 1.2% and 5.1%, respectively (n = 5). The limit of detection for ascorbic acid was ~5 μM at a signal-to-noise ratio of 3. Practical application concerning the determination of physiologically relevant compounds such as noradrena-line and L-dopa are discussed.In recent years, there has been a significant interest in miniaturized analytical systems. The downscale in electrophoresis results in a decrease in analysis time and a potential increase in efficiency while the instrument becomes more compact due to integration of essential parts onto a single substrate.1,2 Another attractive feature is the possibility of parallel analysis using multiple separation systems residing on one chip. Capillary electrophoresis (CE) in the planar format has been applied to a variety of analytes, e.g., DNA,3,4 neurotransmitters,5,6 explosives,7 and the bioassay of clinically relevant compounds.8 Fabrication of microfluidic devices in poly(dimethylsiloxane) (PDMS) by soft lithography provides a fast, inexpensive route to devices that can handle aqueous solutions.9 These soft lithographic methods are based on rapid prototyping and replica molding and are easily accessible to chemists and biologists working under benchtop conditions. Crucial in chip-based CE is the reproducible introduction of well-defined sample zones in the separation channel and the detection of narrow bands. While detection schemes, such as electrochemical detection (EC) or laser-induced fluorescence (LIF), can be adapted from conventional CE, sample introduction requires a completely new approach.In microchip CE, injection is usually performed by electro-kinetic methods. The introduction of a well-defined sample plug is achieved through the channel network, i.e., a sample-guiding channel that intersects the separation channel. The first CE chips employed a tee-injector design.10 Due to difficulties in the control of the sample plug, other injector layouts were developed. Improved control of the sample plug can be gained by using a cross11 or double-tee injector,12 which works well for the analysis of DNA using polymer sieving media.3,4 For injection, an electric field is applied across the sample reservoir and the sample waste reservoir. The resulting analyte stream is perpendicular to the separation channel. In the separation phase, an electric field is applied across the separation channel. The sample plug, residing in the channel intersection, is transpor...