Aqueous and non-aqueous capillary electrophoresis (CE) systems were employe
d for the separation of basic and acidic polar drugs using capillary zone e
lectrophoresis (CZE) and micellar electrokinetic chromatography (MECC) tech
niques. This work was performed to determine the differences in selectivity
, after chemical adjustment of the media, of the separation of closely rela
ted drugs (by measurement of separation efficiency, resolution and detectio
n) in aqueous and non-aqueous solvents. Various electrolytes were tested in
aqueous and organic solvent media. The best separation in aqueous CZE was
obtained in 25 mM phosphate solution at pH 7.3. In aqueous MECC, the best p
erformance was obtained in pH 10.5 buffer containing glycine and dodecyl su
lfate. Non-aqueous CE separations were performed in electrolyte mixtures co
ntaining methanol-acetonitrile, ethanol-acetonitrile and propan-2-ol-aceton
itrile (50:49, v/v) modified by ammonium acetate and water-free glacial ace
tic acid. Acetone was also used instead of acetonitrile in the separation m
edia. In non-aqueous CE systems, the effect of water in the non-aqueous sam
ple and as part of the electrolyte solution played a significant role in th
e separation of polar anionic drugs.