Microchimica Acta

, 186:135 | Cite as

Extraction of the toluene exposure biomarkers hippuric acid and methylhippuric acid using a magnetic molecularly imprinted polymer, and their quantitation by LC-MS/MS

  • Cong Hu
  • Zhen Yang
  • Fuhua Yan
  • Biancheng SunEmail author
Original Paper


A magnetic polymer was molecularly imprinted with hippuric acid (HA) to obtain a nanomaterial with an architecture of type Fe3O4@SiO2@MIP. It was used as a sorbent for magnetic solid phase extraction of HA and methylhippuric acids (2-MHA, 3-MHA, 4-MHA) from urine samples. The respective imprinting factor are 4.6, 2.7, 2.0 and 1.8, respectively, and the selectivity coefficients are 1.7, 2.3 and 2.6. The effects of adsorbent amount, extraction time, pH value, ionic strength, desorption solvent and desorption time on the extraction of HA and MHA were investigated. Following elution with 1 mM NaOH solution, the 4 HAs were quantified by ultra-performance liquid chromatography with mass spectrometric detection. Under the optimal experimental conditions, the limits of detection (at S/N = 3) range between 89 ng·L−1 (for HA) and 170 ng·L−1 (for 4-MHA), the limits of quantification (at S/N = 10) range between 300 ng·L−1 (for HA) and 570 ng·L−1 (for 4-MHA), the linear range extends from 500 ng·L−1 to 10 mg·L−1, the relative standard deviations of intra-day range between 6.4 and 9.6% (for n = 6 at 10 μg·L−1) and inter-day range between 9.2 and 11.5% (for n = 6 at 10 μg·L−1). The method was successfully applied to the analysis of HA and MHA in (spiked) urine, and good recoveries were obtained.

Graphical abstract

Schematic presentation of a method for the determination of hippuric acid (HA) and methylhippuric acid (MHA) in urine sample. The preparation of Fe3O4@SiO2@MIP includes three steps: (1) Preparation of Fe3O4 nanoparticles (NPs), (2) Preparation of Fe3O4@SiO2 and (3) Preparation of a molecular imprint in the surface of the nanoparticles (Fe3O4@SiO2@MIP). The MIP was used as a sorbent for magnetic solid phase extraction (MSPE) of the toluene exposure biomarkers.


Magnetic solid phase extraction Vortex-assisted extraction Ultrasonic liquid desorption Fourier transform infrared spectrometry Transmission electron microscopy X-ray photoelectron spectroscopy Urine analysis 



This project was supported by the National Nature Science Foundation for Young Scholars of China (No. 21505007), and Changsha science and technology project (No. kq1701023).

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2019_3239_MOESM1_ESM.doc (228 kb)
ESM 1 (DOC 228 kb)


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Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Changsha Center for Diseases Prevention and ControlChangshaPeople’s Republic of China

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