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Enantioselective analysis of chiral drugs plays a significant role in chemistry, biology and pharmacology. Baclofen, an antispasmodic chiral drug, has been widely studied due to the obvious differences in toxicity and medical activity between enantiomers. This service provides a simple and efficient method for separation of baclofen enantiomers by capillary electrophoresis without complicated sample derivatization and expensive instruments. Then, the molecular modeling and density functional theory are used to simulate and investigate the chiral resolution mechanism of electrophoresis, the calculated intermolecular forces are directly presented by visualization softwares.