The preconditions are outlined for enantioselective separations in cap
illary electrophoresis (CE) with chiral selectors as additives to the
background electrolyte. Free solution capillary electrophoresis condit
ions are characterised by a single solution phase. Chiral separations
are reviewed by selector type (chiral ligand exchange, cyclodextrins,
crown ethers, glycoproteins) with the extensive studies on cyclodextri
ns grouped into sections on amino acids, pharmaceuticals, and speciali
ty chemicals, optimisation, biological fluids, and quantitative aspect
s. In micellar electrokinetic capillary chromatography, enantioselecti
ve discrimination occurs by partition in a two-phase system, with a ch
iral micellar phase as selector. Optimum separation conditions can be
readily predicted for a given selector-selectand combination, and abso
lute values of binding constants determined by CE. Advantages of CE in
comparison with HPLC using a chiral stationary phase include robust,
rapid assays and the use of small volumes of aqueous solutions; disadv
antages include less favourable detection limits. (C) 1994 Wiley-Liss,
Inc.