Chiral selector complex

Fig. 4. A ligand-exchange chiral selector complexed with a chiral analyte.

From the method development and robustness point of view, the temperature is a parameter that controls equilibria such as pK and enantiomer—chiral selector complexation, or induces structural changes in, e.g., proteins.For chiral separations, generally a lower temperature results in better enantioseparation, but even the opposite has been observed. Sometimes a raise in temperature does not so much affect the enantiomeric separation, but increases the resolution between an enantiomer and a matrix component. ... 

At equilibrium, the effective mobility of an enantiomer in the presence of a chiral selector in capillary electrophoresis is the sum of the electrophoretic mobility of each species containing the enantiomer, weighted by the mole fraction of each species. Assuming for a given separation the enantiomers exist as either the free enantiomer with a mobility, ixr, or the enantiomer-chiral selector complex, p,c,R, then the effective mobility for the enantiomer is given by... 

Many ionic poly(saccharides), such as heparin, chondroitin sulfates, dextran sulfate, and natural poly(saccharides), such as dextran, dextrin, pullulan, and their charged derivatives have been used as mobile phase additives for the separation of different enantiomers. Figure 10.10 [191,192,205,206]. Dextrins were found to have a wide application range, thought to be due in part to their helical structures. Enantiomer-chiral selector complexes seem to be weaker than for cyclodextrins, and it has not been demonstrated that enantiomer separations obtained by the poly(saccharide) chiral selectors cannot be obtained using cyclodextrins. Natural poly(saccharides) are typically complex mixtures of homologues and isomers, with a composition that can vary for different sources, resulting in differences in enantioselectivity. 

Y. Ma, Y. Ito, and A. Berthod, A chromatographic method for measuring of enantiomer-chiral selector complexes, J. Liquid Chromatogr. 22(19) 2945 (1999). 

At the first glance a small number of enantioseparations based on the mobility difference between the noncovalent analyte-chiral selector complexes in CE may appear to be based on true electrophoretic principles. However, this is not the case because the analyte-chiral selector interaction is a necessary prerequisite for the formation of transient diastereomeric complexes [2-7]. 

It should be borne in mind that chiral chromatography is a dynamic process of forming transient noncovalent diastereomeric complexes between chiral solutes and immobilized chiral selectors. Enantioselectivity (a) is a measurement of the thermodynamic stability (A AG) of the two diastereomeric enantiomer/chiral selector complexes. The A AG parameter is the Gibbs free energy difference of the two complex selector-selectand formation. It includes both an enthalpic AAH) and an entropic (TAAS) contributions (Eq. (1)) ... 

Chapter 7 is devoted to important physicochemical —basically mechanistic — aspects of the direct enantioseparations, carried out by using either CSP or mobile phase. In such cases, the diversity of the involved separation mechanisms is much greater than the most of other chromatographic modes (and, particularly, when compared with the relatively simple physicochemical rules governing adsorption or partition liquid chromatography). Thus, the author of this chapter discusses enantioseparation in terms of the solute-chiral selector complexation constants, stoichiometry and selectivity of complexation, the nature of the binding sites on the stationary phase surface, and, finally, the supramolecular mechanisms of complexation. 

Most chiral chromatographic separations are accompHshed using chromatographic stationary phases that incorporate a chiral selector. The chiral separation mechanisms are generally thought to involve the formation of transient diastereomeric complexes between the enantiomers and the stationary phase chiral ligand. Differences in the stabiHties of these complexes account for the differences in the retention observed for the two enantiomers. Often, the use of a... 

The chiral recognition mechanism for these types of phases was attributed primarily to hydrogen bonding and dipole—dipole interactions between the analyte and the chiral selector in the stationary phase. It was postulated that chiral recognition involved the formation of transient five- and seven-membered association complexes between the analyte and the chiral selector (117). 

Catechin and epicatechin are two flavanols of the catechin family. They are enantiomers. The capillary zone electrophoresis (CE) methods with UV-detection were developed for quantitative determination of this flavanols in green tea extracts. For this purpose following conditions were varied mnning buffers, pH and concentration of chiral additive (P-cyclodextrin was chosen as a chiral selector). Borate buffers improve selectivity of separation because borate can make complexes with ortho-dihydroxy groups on the flavanoid nucleus. 

Addition of a chiral carrier can improve the enantioselective transport through the membrane by preferentially forming a complex with one enantiomer. Typically, chiral selectors such as cyclodextrins (e.g. (4)) and crown ethers (e.g. (5) [21]) are applied. Due to the apolar character of the inner surface and the hydrophilic external surface of cyclodextrins, these molecules are able to transport apolar compounds through an aqueous phase to an organic phase, whereas the opposite mechanism is valid for crown ethers. 

This relatively new class of CSPs incorporates glycopeptides attached covalently to silica gel. These CSPs can be used in the normal phase, reversed phase, and polar organic modes in LC [62]. Various functional groups on the macrocyclic antibiotic molecule provide opportunities for tt-tt complexation, hydrogen bonding, and steric interactions between the analyte and the chiral selector. Association of the analyte... 

Many chiral compounds can be used as selectors, for example, chiral metal complexes, native and modified cyclodextrins, crown ethers, macrocyclic antibiotics, noncyclic oligosaccharides, and polysaccharides all have been shown to be useful for efficient separation of different types of compounds. 

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