Abstract:

Fluorinated covalent organic polymers (F-COPs) constitute a new class of porous materials with a topological structure, large surface area, and potential superiority over other types of polymers in sample preparation. In this study, a F-COP was rapidly synthesized by a simple Schiff-based reaction using 2,3,5,6-tetrafluoroterephthalaldehyde (TFA) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) as monomers, and by adding scandium (Ⅲ) triflate (Sc(OTf)₃) as the metal catalyst at room temperature. The prepared F-COP was applied as a coating adsorbent for solid phase microextraction (SPME) to enrich three kinds of eugenol anesthetics in aquatic products. The extraction performance of an enrichment medium is an important factor for practical application in real analytical projects. This F-COP adsorbent with rich π-stacking electrons contained abundant phenyl rings and imine (-C=N) groups throughout the molecular framework. The adsorption mechanism was explored and discussed based on the π-π affinity and hydrogen bonding interaction, which contributed to its strong recognition affinity to targets. The F-COP was characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), nitrogen adsorption-desorption isotherms, and scanning electron microscopy (SEM). The results indicated that the novel F-COP-SPME bar exhibited a rough and porous surface structure, good preparation reproducibility, and high stability. High performance liquid chromatography (HPLC) was performed with an ultraviolet-visible (UV-vis) wavelength detector. A Diamonsil plus C18 column (250 mm×4.6 mm, 5 μm) was used as the analytical column. The mobile phase comprised 60% methanol and 40% ultrapure water, and was flowed at 0.800 mL/min. The injected volume of the sample was 20.0 μL. The column temperature was maintained at 30 ℃ and the detection wavelength was set to 280 nm. Further, the SPME conditions (including extraction time, stirring rate, desorption solvent, and desorption time) that influenced the extraction efficiencies of the eugenol anesthetics were investigated in detail. Thus, the optimized F-COP-SPME bar conditions were established as follows: extraction time: 30 min; stirring rate: 700 r/min; desorption solvent: acetonitrile; desorption time: 10 min. By combining F-COP-based SPME with HPLC-UV analysis, an effective method was developed for the extraction and determination of eugenol, eugenyl acetate, and methyl eugenol residues in aquatic products. The method demonstrated good linearity in the range of 10-1000 μg/L for eugenol and eugenyl acetate, and 10-1500 μg/L for methyl eugenol, with correlation coefficients (r²) greater than 0.9961, low limits of detection (2.9-4.5 μg/kg, S/N=3), and excellent precision (relative standard deviations lower than 8.7%, n=5). Finally, the method was applied for the effective extraction of three kinds of eugenol anesthetics from tilapia and shrimp samples. The obtained recoveries were in the range of 76.7%-98.7% and 80.3%-104% with relative standard deviations of 8.5%-11.8% and 8.6%-12.4% (n=5), respectively. These results demonstrated that the F-COP is promising for use as an adsorbent in SPME for the determination of eugenol anesthetics in aquatic products. The developed method was suitable for the qualitative and quantitative determination of three kinds of eugenol anesthetics in aquatic products, yielding a satisfactory purification effect and sensitivity.

Key words: high performance liquid chromatography (HPLC), solid phase microextraction (SPME), eugenol, aquatic products, fluorinated covalent organic polymer (F-COP)