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Small peptides and peptidomimetics represent an important class of pharmacologically active therapeutics as well as synthetic chiral building blocks, thus, requiring effective analytical techniques for the determination of their chiral purity. Because these analytes are often hydrophilic and ionogenic, capillary electrophoresis (CE) is a suitable technique for this purpose. CE offers several advantages including the thigh resolution power, the low consumption of analytes and chemicals as well as the high flexibility and ease of changing the chiral selector.