Capillary zone electrophoresis (CZE) devices fabricated in poly(dimethylsiloxane) (PDMS) require continuous voltage control of all intersecting channels in the fluidic network in order to avoid catastrophic leakage at the intersections. This contrasts with the behavior of similar flow channel designs fabricated in glass substrates. When the injection plugs are shaped by voltage control and leakage from side channels is controlled by the application of pushback voltages during separation, fluorescein samples give 64 200 theoretical plates (7000 V separation voltage, E = 1340 V/cm). Native PDMS devices exhibit stable retention times (± 8.6% RSD) over a period of five days when filled with water. Contact angles were unchanged (± 1.9% RSD) over a period of 16 weeks of dry storage, in contrast to the known behavior of plasma‐oxidized PDMS surfaces. Electroosmotic flow (EOF) was observed in the direction of the cathode for the buffer systems studied (phosphate, pH 3—10.5), in the presence or absence of hydrophobic ions such as tetrabutylammonium or dodecyl sulfate. Electroosmotic mobilities of 1.49 × 10—5 and 5.84 × 10—4 cm2/Vs were observed on average at pH 3 and 10.5, respectively, the variation strongly suggesting that silica fillers in the polymer dominate the zeta potential of the material. Hydrophobic compounds such as dodecyl sulfate and BODIPY® 493/503 adsorbed strongly to the PDMS, indicating the hydrophobicity of the channel walls is clearly problematic for CZE analysis of hydrophobic analytes. A method to stack multiple channel layers in PDMS is also described.

A micromachined absorbance and fluorescence detection cell for application to capillary electrophoresis within planar glass substrates (chips) is described. A microfabricated U-cell for absorbance provides a longitudinal path 120-140 µm long parallel to the flow direction and gives at least a 10-fold increase in absorbance compared to an absorbance path transverse to the flow direction. Absorbance detection limits of 0.003 AU gave ∼6 µM detection limits for hydrolyzed fluorescein isothiocyanate dye. The same device can be used for longitudinal fluorescence excitation with a 20-fold improvement in signal-tobackground levels due to reduced scattering, utilizing a form of sheath flow. Fluorescence detection limits of ∼20 000 molecules and 3 nM were obtained for fluorescein.

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