Enhanced solid-liquid synergistic microextraction of nine bisphenols in serum using polyaniline functionalized metal-organic framework nanocomposites/methyl tert-butyl ether.

Bisphenols, as a new class of environmental endocrine disruptors (EED), can interfere with the endocrine system of the human body and lead to various diseases. In this study, a novel polyaniline functionalized metal-organic framework (PANI@MIL-101@HF) was synthesized by utilizing hollow fibers (HF) as the the immobilization carrier, and combined with methyl tert-butyl ether (MTBE) for solid-liquid cooperative adsorption to determine bisphenols (BPs) in serum samples. The immobilized adsorbent exhibited excellent high stability and hydrophobicity. Furthermore, the inclusion of amino and benzene rings in PANI enhanced the adsorption efficiency of BPs through π-π and hydrogen bond interactions. Surprisingly, owing to the synergies of size exclusion effect of the MIL-101 and HF, the exclusion rate of protein reached as high as 99.2-99.9%. Based on its excellent adsorption properties and protein exclusion effect, the immobilized adsorbent PANI@MIL-101@HF was successfully used as a new restricted material for the high extraction performance with solid-liquid synergy of nine bisphenols (BPs) in serum samples. The operation process has also become more convenient without centrifuging. Integrated with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), the nine BPs in serum samples have a wide linear range (2-200 ng mL) with low quantitative limits of 0.02 ng mL, and the recoveries ranged from 84.65 to 112.56%. The proposed method could be widely applied in convenient, green, and sensitive detection of endocrine disruptors from serum samples.