Dummy molecularly imprinted polymer-based solid-phase extraction method for the determination of some phthalate monoesters in urine by gas chromatography-mass spectrometry analysis

A dummy molecularly imprinted polymer-based solid-phase extraction (SPE) sorbent was used for the selective extraction of some phthalate monoesters, monoethyl phthalate (MEP), monobutyl phthalate (MnBP) and mono-(2-ethylhexyl) phthalate (MEHP) in urine prior to gas-chromatography-mass spectrometry (GC-MS) analysis. Diethyl phthalate (DEP), a phthalate ester, was successfully used as a dummy template to prepare selective sorbent for MEP, MnBP, and MEHP extraction. DEP-imprinted poly(ethylene glycol dimethacrylate N-methacryloyl-l-tryptophan methyl ester) (DPEMT) microbeads were synthesized by suspension polymerization and characterized by Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and Brunauer Emmet Teller (BET) analysis. The critical parameters (i.e., pH, sorbent amount, ionic strength, sample volume, elution solvent) affecting the extraction performance of the DPEMT-SPE sorbent were optimized. Under optimum conditions, good linearities were obtained in the concentration range of 4 to 60 ng/mL with determination coefficients (R ) of greater than 0.9959. The developed SPE method provided low limits of detection (LOD) of 0.05-1.20 ng/mL and limits of quantification (LOQ) of 0.18-4.01 ng/mL with relative standard deviations (RSDs) of less than 8.95 % for intra- and inter-day analyses. The proposed SPE method was used to analyze phthalate monoesters in spiked urine samples, and recoveries of 97.45-109.26 % were obtained. DPEMT-SPE sorbent was reused for 15 times without any losses of performance. Consequently, a highly selective and sensitive SPE method based on a dummy molecularly imprinted polymer combined with GC-MS was successfully developed to monitor human phthalate exposure via urine samples.