Open Tubular Capillary Electrochromatography-Mass Spectrometry for Analysis of Underivatized Amino Acid Enantiomers with a Porous Layer-Gold Nanoparticle-Modified Chiral Column

By developing a novel chiral column, we integrate open tubular capillary electrochromatography into sheathless mass spectrometry (MS) for efficient analysis of underivatized amino acid enantiomers. The chiral column is easily fabricated by modifying the inner surface of a capillary with a three-dimensional porous layer (PL, thickness ∼ 90 nm, pore size ∼ 30 nm) and gold nanoparticles and by introducing a chiral selector, thiol β-cyclodextrin (SH-β-CD), onto the modified surface via Au–S bonds. This approach greatly enhances the specific surface area and thus the ratio of the stationary phase to mobile phase and interaction between the stationary phase and analytes. The proposed PLOT@Au@CD column is coupled to the sheathless CE-ESI-MS system for chiral analysis of amino acid enantiomers. No derivatization of amino acids is required for chiral analysis, and baseline separation of a total of 15 pairs of amino acid enantiomers is achieved within 17 min with high column efficiencies of 5.60 × 104 to 1.82 × 106 N/m, high resolutions of 1.51–10.0, and low limits of detection between 0.02 and 0.09 μg/mL. The separation efficiency and MS intensity are only slightly decreased over 60 runs or after usage for 15 days, showing excellent repeatability and stability of the PLOT@Au@CD column. The proposed method is successfully applied to the determination of amino acid enantiomers in vinegar samples with satisfactory accuracy. Our study provides a new approach for developing a chiral stationary phase in the chromatographic separation technique, which can be easily coupled to sensitive MS detection, thus it would be of value for various applications in the fields of chiral analysis.