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Capillary electrokinetic separation techniques offer high efficiency and peak capacity, and can be very useful for the analysis of samples containing a large variety of (unknown) compounds. Such samples are frequently met in impurity profiling of drugs (detection of potential impurities in a pharmaceutical substance or product) and in general sample profiling (determination of differences or similarities between samples). In this paper, the potential, merits, and limitations of electrokinetic separation techniques for profiling purposes are evaluated using examples from literature. A distinction is made between impurity profiling, forensic profiling and profiling of natural products, and the application of capillary zone electrophoresis, micellar electrokinetic chromatography, and capillary electrochromatography in these fields is discussed. Attention is devoted to important aspects such as selectivity, resolution enhancement, applicability, detection, and compound confirmation and quantification. The specific properties of the various electrokinetic techniques are discussed and compared with more conventional techniques as liquid chromatography.

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