Enantioselectivity of vesicle-forming chiral surfactants in capillary electrophoresis: Role of the surfactant headgroup structure

Abstract

Two vesicle-forming single-tailed amino acid derivatized surfactants sodium N-[4- n-dodecyloxybenzoyl]- l-leucinate (SDLL) and sodium N-[4- n-dodecyloxybenzoyl]- l-isoleucinate (SDLIL) have been synthesized and used as pseudo-stationary phase in micellar electrokinetic chromatography to evaluate the role of steric factor of amino acid headgroup and hydrophobic/hydrophilic interactions for enantiomeric separations. The aggregation behavior of the surfactants has been studied in aqueous buffered solution using surface tension and fluorescence probe techniques. Results of these studies have suggested formation of vesicles in aqueous solutions. Microenvironment of the vesicle, which determines the depth of penetration of the analytes into vesicle was determined by fluorescence probe technique using pyrene, N-phenyl-1-naphthylamine (NPN), and 1,6-diphenyl-1,3,5-hexatriene (DPH) as probe molecules. Atropisomeric compounds (±)-1,1′-bi-2-naphthol (BOH), (±)-1,1′-binaphthyl-2,2′-diamine (BDA), (±)-1,1′-binaphthyl-2,2′-diylhydrogen phosphate (BNP) and Tröger's base (TB) and chiral compound benzoin (BZN) has been enantioseparated. The separations were optimized with respect to surfactant concentration, pH, and borate buffer concentration. SDLL was found to provide better resolution for BOH, BNP, and BZN. On the other hand, SDLIL offers better resolution for BDA. The chromatographic results have been discussed in the light of the aggregation behavior of the surfactants and the interaction of the solutes with the vesicles.