Introduction: Micellar Electrokinetic Chromatography, sometimes referred as Affinity Capillary Electrophoresis, is a useful tool to the characterization of the drug partitioning in different vehicle systems such as micelles and microemulsions using the capacity factor as hydrophobicity parameter. Bile acids, because of their important role in biological systems, are applied widely in ACE method to characterization of partition properties of solutes. In this paper the interaction of some hydrophilic and lipophilic vitamins with micellar systems consisted of bile salts and phospholipids was considered using ACE. Material and Methods: Three mixed micelles and one microemulsion were employed. The samples were filtered through a 0.45 μm filter. 13 vitamins, consist of 4 lipophilic and 9 hydrophilic vitamins were investigated. Each vitamin was solved in different micellar systems (0.1 mg/ml). Then, using ACE, the electropherogram of samples was obtained under certain run conditions. The capacity factor for each sample was calculated according the migration times in the electropherogram. DMSO and Sudan red were used as EOF tracer and micelle tracer respectively. All experiments were carried out with certain instrumental conditions. Results and Discussion: The results show that the migration times of lipophilic vitamins are equal to migration time of micellar tracer and consequently the capacity factor of all of them tends to infinity. In fact these vitamins, concerning the hydrocarbonic chain in their chemical structure, are incorporated in the inner oil core of mixed micelle or microemulsion and moved with it. Four hydrophilic vitamins (niacinamid, pyridoxine, D-panthenol and cyanocobalamin) have different affinity to Micellar systems. But for each vitamin the affinity to different system is almost same. K′ zero means that vitamin has not any affinity to micelle, remains in aqueous phase and moves with EOF. Five hydrophilic vitamins (ascorbic acid, folic acid, riboflavin, biotin and thiamin) had charged behavior. The electrophoretic mobility of all these vitamins was negative, except thiamin which has positive mobility. Two important parameters that may influence these migration behaviors of charged solutes are pH and micelle concentration. Distribution properties of molecules mostly change depending to pH value of the media because of the effect of pH on the chemical interaction. In the other hand, it might be that the negative charge of bile salt's micelle increases by mixing with phospholipids, and causes to stronger repulsion between negative charged micelle and anion analyte. So the electrophoretic mobility of anionic vitamins in presence of micelle would be reduced. Conclusion: The MEKC technique as a method of ACE was employed to determination partitioning pattern of various kinds of vitamins in a micellar solutions. The affinity of both hydrophilic and lypophilic vitamins to micellar system was investigated by calculation the capacity factor. This value for lypophilic vitamins is infinite, because they incorporate with micelle compositions and moved with them. In contrast hydrophilic vitamins exhibited different partitioning behaviour in micellar solution. The negative value obtained for anionic hydrophilic vitamins can be corrected by change some condition like micellar concentration and the pH of media.
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