Chiral separation of hydroxyflavanones in cyclodextrin-modified capillary zone electrophoresis using sulfated cyclodextrins as chiral selectors

Abstract

Chiral separations of three hydroxyflavanone aglycones, including 2′-, 3′-, and 4′-hydroxyflavanone, in capillary zone electrophoresis (CZE) using randomly sulfate-substituted β-cyclodextrin (S-β-CD) or dual cyclodextrin (CD) systems consisting of S-β-CD and a neutral CD at low pH were investigated. The results indicate that S-β-CD is an excellent chiral selector for enantioseparation of 2′-hydroxyflavanone and is a good chiral selector for 3′-hydroxyflavanone. Depending on the concentration of S-β-CD ranging from 2.0 to 0.75% (w/v), the enantioresolution values were 10.5–19.5 and 1.8–3.4 for 2′- and 3′-hydroxyflavanone, respectively. The enantiomers of 4′-hydroxyflavanone could be effectively separated with S-β-CD at a concentration of 2.0% (w/v) within 20 min. The enantioselectivity and enantioresolution follow the order 2′-hydroxyflavanone ≫ 3′-hydroxyflavanone > 4′-hydroxyflavanone. Alternatively, with the addition of sodium dodecyl sulfate (SDS) monomers at low concentrations in the electrophoretic system, enantioselectivity of these hydroxyflavanone aglycones could be enhanced with dual CD systems. In this case, SDS monomer acted as a complexing agent probably first with S-β-CD and then subsequently with the analytes for increasing the effective electrophoretic mobility of the analytes towards the anode and as a selectivity controller for affecting the selectivity of hydroxyflavanones. Better enantioseparation between 2′-hydroxyflavanone and 3′-hydroxyflavanone could be achieved with a dual CD system consisting of S-β-CD and γ-CD than that with S-β-CD and β-CD. In addition, possible chiral recognition mechanisms of hydroxyflavanones are discussed.