Open-channel electrochromatography in combination with solvent program
ming is demonstrated using a microchip device. Channel walls were coat
ed with octadecylsilanes at ambient temperatures, yielding stationary
phases for chromatographic separations of neutral dyes. The electroosm
otic now after coating was sufficient to ensure transport of all speci
es and on-chip mixing of isocratic and gradient elution conditions wit
h acetonitrile-buffer mixtures. Chips having different channel depths
between 10.2 and 2.9 mu m were evaluated for performance, and van Deem
ter plots were established. Channel depths of about 5 mu m were found
to be a good compromise between efficiency and ease of operation. Isoc
ratic and gradient elution conditions were easily established and mani
pulated by computer-controlled application of voltages to the terminal
s of the microchip. Linear gradients with different slopes, start time
s, duration times, and start percentages of organic modifier proved to
be powerful tools to tune selectivity and analysis time for the separ
ation of a test mixture. Even very steep gradients still produced exce
llent efficiencies. Together with fast reconditioning times, complete
runs could be finished in under 60 s.