The work in this thesis has demonstrated the chiral recognition through the adaptation of chromatographically derived chiral recognition systems by electrospray ionization mass spectrometry (ESI-MS). Mass-labeled, pseudoenantiomeric chiral selectors (where each pseudoenantiomer had the opposite stereochemistry, but was slightly different in mass due to labeling of one enantiomer) were prepared as soluble analogues of Pirkle type chiral stationary phases. When mixed with a chiral analyte, solutions containing these pseudoenantiomeric selectors afforded selector-analyte complexes in the ESI-MS, and the relative peak intensities of the complexes could be related back to the enantiomeric composition of the analyte. In each case of this study, the complex intensity fraction for either of the selector-analyte complexes in the ESI-MS varies linearly with the enantiomeric composition of the analyte. This linear relationship provides a measure of the extent of enantioselectivity and allows quantitative analysis of the enantiomeric composition of analyte.

Chiral separation systems in capillary electrophoresis are in the scope of interest of many research groups all over the world. Therefore, the need to develop reliable theoretical models, which would help to explain phenomena connected with chiral separations or optimization of separation conditions, is obvious. In this thesis several mathematical models and approaches that can fulfill these requirements are presented. First part of the thesis deals with the determination of rate constants of interconversion of enantiomers by means of dynamic capillary electrophoresis. We focused on mixtures of chiral selectors and formulated a mathematical model, which enables to determine rate constants of interconversion in such systems. Mixtures of chiral selectors are very popular in separation practice due to their enhanced enantioselectivity. The theoretical model established in the thesis is able to explain the separation mechanisms of multi-chiral selector systems and to propose and verify possible ways of their optimization. In addition, the separation mechanism in systems with simultaneous cyclodextrin and borate complexation was revealed. Finally we present the complete mathematical model of electromigration in systems with complexation agents. The model is implemented into our simulation tool Simul 5...