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Abstract: Cyclodextrins have been used extensively in separation science because they have been shown to discriminate between positional isomers, functional groups, homologues and enantiomers. This property makes them one of the most useful agents for a wide variety of separations. The main goal of this review is a discussion of somewhat more exotic applications of cyclodextrins to separation methods. Techniques examined in detail include gel electrophoresis, isotachophoresis, isoelectric focusing, preparative scale electrophoretic techniques, thin-layer chromatography, electrochemically modulated liquid chromatography, use of monolithic media in liquid chromatography, microdialysis, separation on hollow fibers, foam flotation enrichment, solid- and liquid-phase extractions, countercurrent chromatography, separation through liquid and composite membranes, and cyclodextrin applications in molecularly imprinted polymers. Since a lot of attention has been paid to use of cyclodextrins in capillary electrophoresis, liquid, gas and supercritical fluid chromatography, these techniques will be only briefly discussed. The second goal of this review is a discussion of a scaling-up the analytical separations to semi-preparative or preparative techniques. It was found that despite a need for large scale separations in the industry, development of these techniques has been somewhat lagging behind development of miniaturized analytical separations. It is hoped that the focus on areas outside more traditional separation applications might stimulate further research. (C) 2000 Elsevier Science B.V. All rights reserved