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An EKC method for the determination of ornithine (Orn) enantiomers has been developed after a fast pre-capillary derivatization with FITC. The derivatization step was needed to provide a chemical moiety to the Orn molecule, enabling a sensitive UV detection and the interaction with the CDs used as chiral selectors. To accelerate the derivatization reaction, an ultrasound probe was used. For the development of the chiral method, the influence of different experimental conditions (type and concentration of the chiral selector, temperature, and separation voltage) was investigated. Due to the anionic nature of the analyte (FITC-Orn), five neutral CDs were employed as chiral selectors. The native gamma-CD showed the highest chiral separation power, observing that a low concentration of this CD (1 mM), using a working temperature of 25 degrees C and a separation voltage of 20 kV, enabled to obtain the highest enantioresolution for Orn and its separation from other amino acids usually present in food supplements. After optimizing the method for the preconditioning of the capillary, the analytical characteristics of the chiral method were established. Linearity, LOD and LOQ, precision, and accuracy were evaluated previously to the determination of Orn enantiomers contained in ten commercial food supplements. No interferences from other amino acids present in these samples were observed.

A fast in-capillary derivatization method by CE with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate was developed for the first time for the determination of amino acid enantiomers (arginine, lysine, and ornithine) in dietary supplements and wines. Because of the initial current problems due to the formation of precipitates into the capillary during the derivatization reaction, a washing step with an organic solvent as DMSO between injections was necessary. Different approaches were also investigated to enhance the sensitivity of detection. A derivatization procedure, where plugs of ACN, derivatizing agent (10 mM 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate), and sample in borate (1:1 v/v) were injected in tandem (2, 3, and 6 s, respectively, at 50 mbar), was selected because it enabled to obtain the most sensitive and reproducible results. Appropriate analytical characteristics (linearity, LOD and LOQ, precision, absence of matrix interferences, and accuracy) were obtained for this method. Finally, the optimized method was successfully applied to the determination of the enantiomers of arginine, lysine, and ornithine in food samples of different complexities (dietary supplements and wines).