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Deep eutectic solvent functionalized graphene oxide composite adsorbent for miniaturized pipette-tip solid-phase extraction of toluene and xylene exposure biomarkers in urine prior to their determination with HPLC-UV

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Abstract

A deep eutectic solvent functionalized graphene oxide composite adsorbent (DFG) was synthesized through reversible-addition fragmentation chain-transfer polymerization. The synthesized DFG had multiple adsorption interactions after covalent modification with a deep eutectic solvent (allyltriethylammonium bromide/ethylene glycol). Adsorption isotherms and kinetics studies of DFG indicate that the adsorption of hippuric acid (HA) and methylhippuric acid (MHA) was monolayer chemical adsorption. The comparison of DFG with commercial adsorbents demonstrates that the adsorption ability of DFG was superior. This was due to the multiple adsorption interactions of DFG for the three analytes (mainly π-interaction, hydrogen bonding, electrostatic adsorption, and hydrophobic interaction). The DFG adsorbent was applied to miniaturized pipette-tip solid-phase extraction (MPT-SPE), followed by high-performance liquid chromatography (HPLC) to determine biomarkers in urine for toluene and xylene exposure. The DFG-MPT-SPE-HPLC method required only 2.00 mg of DFG as adsorbent, 0.50 mL of washing solvent, and 0.40 mL of elution solvent to achieve a wide linear range (0.200–200 μg mL−1), high recoveries (90.9–99.1%), and high precision (RSD ≤ 6.3%). The proposed method was applied to determine HA and MHA in urine samples from occupational workers.

Deep eutectic solvent functionalized graphene oxide composite adsorbent for miniaturized pipette-tip solid-phase extraction of toluene and xylene exposure biomarkers in urine prior to their determination with HPLC-UV.

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Acknowledgments

This work is supported by the National Natural Science Foundation of China (81803287), the Natural Science Foundation of Hebei Province (B2018201270, H2019201288), the Talent Engineering Training Foundation of Hebei Province (A201802002), and the Outstanding Doctoral Cultivation Project of Hebei University (YB201703).

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Authors and Affiliations

  1. Key Laboratory of Medicinal Chemistry and Molecular Diagnosis, College of Public Health, Institute of Life Science and Green Development, Hebei University, Baoding, 071002, China

    Yanan Yuan, Yehong Han, Chunliu Yang, Dandan Han & Hongyuan Yan

  2. Affiliated Hospital of Hebei University, Baoding, 071002, China

    Yanan Yuan & Hongyuan Yan

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  1. Yanan Yuan
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  2. Yehong Han
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Correspondence to Hongyuan Yan.

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Yuan, Y., Han, Y., Yang, C. et al. Deep eutectic solvent functionalized graphene oxide composite adsorbent for miniaturized pipette-tip solid-phase extraction of toluene and xylene exposure biomarkers in urine prior to their determination with HPLC-UV. Microchim Acta 187, 387 (2020). https://doi.org/10.1007/s00604-020-04370-z

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