Although bile acids (BAs) have been suggested as important biomarkers for endocrine diseases, the identification and quantification of different BAs are still challenges due to their enormous species and wide range concentrations. Herein, a copolymer probe based on β-cyclodextrin (β-CD) is fabricated through a simple in-mold photopolymerization for the selective extraction of BAs. Through the unique stereochemical affinity between BAs and the cavity of β-CD, the custom probe shows superior enriching capacities to series BAs. Moreover, the outstanding extraction ability is proved to be consistent in various interfering conditions, including pH changing and the addition of complex matrix. Further comparison shows that the stereostructure of the nucleus of BAs plays a vital role during the formation of the β-CD/BA complex, indicating the potential for efficient extraction of other BAs, including their structural analogues or some unknown ones. The developed probe is used for solid phase microextraction, and the limits of detection are lower than 0.075 ng mL-1 by coupling to high performance liquid chromatography-tandem mass analysis. The results in this study highlight the potential for effective improvement of immediate detection and profiling of BAs in real samples, which will make a tremendous impact in the analytical field or clinical diagnosis.
Keywords: bile acid; host–guest interactions; matrix interference‐free; solid phase microextraction; β‐cyclodextrin.