色谱 ›› 2021, Vol. 39 ›› Issue (9): 1012-1020.DOI: 10.3724/SP.J.1123.2021.06027

• 研究论文 • 上一篇    下一篇


王兴益1,2, 陈彦龙1,*(), 李攻科1,*()   

  1. 1.中山大学化学学院, 广东 广州 510275
    2.兴义民族师范学院生物与化学学院, 贵州 兴义 562400
  • 收稿日期:2021-06-15 出版日期:2021-09-08 发布日期:2021-09-06
  • 通讯作者: 陈彦龙,李攻科
  • 作者简介:E-mail: chenyl8909@163.com(陈彦龙).
    * E-mail: cesgkl@mail.sysu.edu.cn(李攻科);
  • 基金资助:

Solid phase microextraction-high performance liquid chromatography of fluorinated covalent organic polymer to determine eugenol anesthetics in aquatic products

WANG Xingyi1,2, CHEN Yanlong1,*(), LI Gongke1,*()   

  1. 1. School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China
    2. School of Biology and Chemistry, Xingyi Normal University for Nationalities, Xingyi 562400, China
  • Received:2021-06-15 Online:2021-09-08 Published:2021-09-06
  • Contact: CHEN Yanlong,LI Gongke
  • Supported by:
    Research and Development Plan for Key Areas of Food Safety in Guangdong Province of China(2019B020211001);National Key Research and Development Program of China(2019YFC1606101);National Natural Science Foundation of China(21976213);Science and Technology for Youth Talent Growth Project of the Guizhou Provincial Education Department (No. KY[2020]216)


氟化共价有机聚合物(F-COP)具有较大的比表面积和吸附容量,对丁香酚类化合物具有特异性吸附。该文以2,3,5,6-四氟对二苯甲醛(TFA)和1,3,5-三(4-氨苯基)苯(TAPB)为单体,三氟甲磺酸钪(Sc(OTf)3)为催化剂在室温下快速合成F-COP,并将其作为固相微萃取(SPME)吸附剂,结合高效液相色谱-紫外检测法(HPLC-UV),建立了测定水产品中丁香酚、乙酸丁香酚酯和甲基丁香酚麻醉剂的分析方法。通过傅里叶红外光谱、X射线衍射、N2吸附-解吸等温线和扫描电子显微镜等手段对F-COP材料进行表征。考察了萃取时间、搅拌速度、解吸溶剂及解吸时间对丁香酚类麻醉剂萃取量的影响,在萃取时间为30 min、搅拌速度为700 r/min、解吸溶剂为乙腈、解吸时间为10 min时,丁香酚类麻醉剂获得了最佳的萃取效果。在Diamonsil Plus C18-B色谱柱(250 mm×4.6 mm, 5 μm)上,以甲醇-水(60∶40, v/v)为流动相,流速0.800 mL/min,进样量20.0 μL,紫外检测波长280 nm,柱温30 ℃条件下,丁香酚和乙酸丁香酚酯在10~1000 μg/L,甲基丁香酚在10~1500 μg/L范围内呈现出良好的线性关系,相关系数(r2)大于0.9961,方法检出限为2.9~4.5 μg/kg(S/N=3),精密度小于8.7%(n=5)。最后,将该分析方法用于罗非鱼和基围虾样品的3种麻醉剂残留分析中,得到了满意的回收率(76.7%~104%)。结果表明,F-COP-SPME-HPLC-UV可满足水产品中丁香酚类麻醉剂的分析检测。

关键词: 高效液相色谱, 固相微萃取, 丁香酚, 水产品, 氟化共价有机聚合物


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)