F. Lelievre et al., SELECTIVITY IN CAPILLARY ELECTROPHORESIS - APPLICATION TO CHIRAL SEPARATIONS WITH CYCLODEXTRINS, Analytical chemistry, 69(3), 1997, pp. 385-392
In order to accurately evaluate the performances of any electrolyte me
dium, a clear concept of selectivity in capillary electrophoresis and
related electroseparation techniques is proposed. Selectivity is defin
ed as the ratio of the affinity factors of both analytes for a separat
ing agent (phase, pseudophase, or complexing agent present in the back
ground electrolyte). When in the presence of a complexing agent and if
only 1:1 complexation occurs, selectivity corresponds to the ratio of
the apparent binding constants and is independent of the concentratio
n of the complexing agent. This concept is illustrated through the sep
arations of neutral and anionic enantiomers in the presence of a catio
nic cyclodextrin, the mono(6-amino-6-deoxy)-beta-cyclodextrin, as a ch
iral complexing agent. The values obtained for different pairs of enan
tiomers are discussed with regard to the functional groups that distin
guish them. When the analytes have the same mobilities in free solutio
n and in their complexed form, then the resolution equation developed
in micellar electrokinetic chromatography may be applied and optimum c
onditions (affinity factors, chiral agent concentration) can be predic
ted.