A new example of reversal of the order of migration of enantiomers, as a function of cyclodextrin concentration and pH, by cyclodextrin-modified capillary zone electrophoresis: enantioseparation of 6,6'-dibromo-1,1'-binaphthyl-2,2'-diol.

ABSTRACT

Enantioseparation of 6,6'-dibromo-1,1'-binaphthyl-2,2'-diol (DBBD) by cyclodextrin-modified capillary zone electrophoresis (CD-CZE) was studied using the three native alpha, beta, and gamma cyclodextrins, the three hydroxypropylated cyclodextrins (2-hydroxypropyl-alpha, beta, and gamma), heptakis-2,6-di-O-methyl-beta-CD (DM-beta-CD), and heptakis-2,3,6-tri-O-methyl-beta-cyclodextrin (TM-beta-CD). First, the acidity constants of DBBD were determined using capillary electrophoresis, before performing enantioseparation. The influence of the concentrations of the studied cyclodextrins on the enantioseparation was explored and the experimental optimal concentrations were determined and compared to the theoretical optimal concentrations. Moreover, the apparent complexation constants between each studied cyclodextrin and the two DBBD enantiomers were evaluated using a non-linear curve fitting method and three linear plotting methods (x-reciprocal, y-reciprocal and double reciprocal). For TM-beta-CD, the order of migration of the enantiomers of DBBD reversed as a function of TM-beta-CD concentration. The influence of the nature of methylated cyclodextrin derivatives (methyl-beta-CD (M-beta-CD) and DM-beta-CD) was then studied. Inversion of the order of migration of the enantiomers of DBBD was observed for DM-beta-CD, whereas the S enantiomer of DBBD always migrated first for M-beta-CD.