A capillary electrophoretic method with low ultraviolet (185 nm) detection is presented for the analysis of both artesunate, a hemisuccinate ester analogue of artemisinin, and succinic acid without prior derivatization. Artesunate is easily separated from its ester hydrolysis products, succinic acid and dihydroartemisinin, with the use of phosphate electrolytes at neutral pH, and this makes the method suitable for ester stability monitoring or quality control purposes. Sensitivity is shown to be strongly influenced by electrolyte and sample matrix ionic concentration ratio, which illustrates the need for careful selection of the electrolyte when direct injection of isotonic sample solutions is considered. Alkaline derivatization, which is known to generate charged compounds, is found to be useful for the analysis of neutral artemisinin derivatives, as exemplified by experiments with dihydroartemisinin.
Abstract Capillary electrophoresis (CE) represents a decisive step forward in stereoselective analysis. The present paper deals with the theoretical aspects of the quantitation of peak separation in chiral CE. Because peak shape is very different in CE with respect to high performance liquid chromatography (HPLC), the resolution factor R s , commonly used to describe the extent of separation between enantiomers as well as unrelated compounds, is demonstrated to be of limited value for the assessment of chiral separations in CE. Instead, the conjunct use of a relative chiral separation factor (RCS) and the percent chiral separation (%CS) is advocated. An array of examples is given to illustrate this. The practical aspects of method development using maltodextrins – which have been proposed previously as a major innovation in chiral selectors applicable in CE – are documented with the stereoselective analysis of coumarinic anticoagulant drugs. The possibilities of quantitation using CE were explored under two extreme conditions. Using ibuprofen, it has been demonstrated that enantiomeric excess determinations are possible down to a 1% level of optical contamination and stereoselective determinations are still possible with a good precision near the detection limit, increasing sample load by very long injection times. The theoretical aspects of this possibility are addressed in the discussion.