Electrokinetic control of fluid flow in native poly(dimethylsiloxane) capillary electrophoresis devices

Capillary zone electrophoresis (CZE) devices fabricated in poly(dimethylsil oxane) (PDMS) require continuous voltage control of all intersecting channe ls in the fluidic network in order to avoid catastrophic leakage at the int ersections. This contrasts with the behavior of similar flow channel design s fabricated in glass substrates. When the injection plugs are shaped by vo ltage control and leakage from side channels is controlled by the applicati on 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 i n the direction of the cathode for the buffer systems studied (phosphate, p H 3-10.5), in the presence or absence of hydrophobic ions such as tetrabuty lammonium or dodecyl sulfate. Electroosmotic mobilities of 1.49 x 10(-5) an d 5.84 x 10(-4) cm(2)/Vs were observed on average at pH 3 and 10.5, respect ively, 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(R) 493/503 adsorbed strongly to the PDMS, indic ating the hydrophobicity of the channel walls is clearly problematic for CZ E analysis of hydrophobic analytes. A method to stack multiple channel laye rs in PDMS is also described.