A silica-based three-dimensional molecularly imprinted coating for the selective solid-phase microextraction of...

In this work, a selective silica-based molecular imprinted solid-phase microextraction (SPME) sorbent was prepared through the sol-gel process. Difenoconazole was used as a template to prepare imprinted materials on the surface of mesoporous silica. The SPME fiber followed by gas chromatography-electron capture detection was applied for the extraction and determination of difenoconazole. Fourier transform infrared spectrometry, field emission scanning electron microscopy, X-ray diffraction, and thermal gravimetry were used to characterize the imprinted SPME fiber. Two different procedures were presented to prepare MCM-41@SiO₂-difenoconazole. Also, a non-MCM molecularly imprinted polymer was synthesized to investigate the effect of MCM-41 on the selectivity and extraction efficiency of the sorbent. The important parameters (i.e., desorption time and temperature, ionic strength, stirring rate, pH, extraction temperature and time) affecting the extraction performance of the method were optimized. Under optimum conditions, the limits of detection and quantification were found to be 0.002 and 0.005 ng mL^-1, respectively. Linear dynamic range was in the range of 0.01-1 ng mL^-1. The intra- and inter-day relative standard deviations and fiber-to-fiber reproducibility were in the range of 4.3-7.5, 3.3-8.2 and 7.4-9.7%, respectively. The fiber was successfully applied for the selective extraction of difenoconazole from wheat and fruit samples and satisfactory results with extraction recoveries >73% were obtained.