Department of Chemistry, Lishui University, Lishui 323000, China.
Department of Chemistry, Lishui University, Lishui 323000, China.
J Chromatogr A. 2020 Jun 7;1620:461013. doi: 10.1016/j.chroma.2020.461013. Epub 2020 Mar 6.
Dummy molecularly imprinted microspheres (DMIMs) were synthesized by Pickering emulsion polymerization and used as the matrix solid-phase dispersion extraction (MSPD) sorbent for sample pre-treatment of azole fungicides in fish samples. Alpha-(2,4-Dichlorophenyl)-1H-imidazole-1-ethanol (DCE) was used as the fragment dummy template for the imprinting of climbazole (CBZ), clotrimazole (CMZ) and miconazole (MNZ). The morphology of the microspheres were characterized by scanning electron microscopy (SEM) and nitrogen adsorption measurements, narrow diameter distribution (20-50 μm) with regular spherical shape and high surface area (S = 408.91 ± 6.72 m g) were achieved. Good class-selectivity of the DMIMs was found for CBZ, CMZ and MNZ by static adsorption experiments. The imprinted microspheres as MSPD sorbent was then evaluated for the extraction and purification of CBZ, CMZ and MNZ in fish samples. The extracted azole fungicides were detected by HPLC-DAD analysis at 225 nm. MSPD conditions including elution, mass ratio of sample/sorbent and washing were carefully evaluated. The optimized MSPD method have good recoveries (89.2-101.5%) and reproducibility (RSDs 1.6-4.8%, n = 5) for fish samples spiked at 0.5, 2.5 and 12.5 μg g. The limits of detection (LODs) were 0.045, 0.036 and 0.033 μg g for CBZ, CMZ and MNZ, respectively. The results show that this method has a good application prospect for the pretreatment of azole fungicides in fish samples.
空白分子印迹微球（DMIMs）通过 Pickering 乳液聚合合成，并用作鱼样中唑类杀菌剂样品前处理的基质固相分散萃取（MSPD）吸附剂。α-（2,4-二氯苯基）-1H-咪唑-1-乙醇（DCE）被用作印迹咪康唑（CBZ）、克霉唑（CMZ）和咪康唑（MNZ）的片段虚拟模板。微球的形态通过扫描电子显微镜（SEM）和氮气吸附测量进行了表征，实现了窄粒径分布（20-50μm）、规则球形和高表面积（S=408.91±6.72m²/g）。静态吸附实验发现，DMIMs 对 CBZ、CMZ 和 MNZ 具有良好的类选择性。然后，将印迹微球作为 MSPD 吸附剂用于鱼样中 CBZ、CMZ 和 MNZ 的提取和纯化。用 HPLC-DAD 分析在 225nm 处检测提取的唑类杀菌剂。仔细评估了 MSPD 条件，包括洗脱、样品/吸附剂的质量比和洗涤。优化的 MSPD 方法对鱼样中 0.5、2.5 和 12.5μg/g 加标 CBZ、CMZ 和 MNZ 的回收率（89.2-101.5%）和重现性（RSDs 为 1.6-4.8%，n=5）均较好。CBZ、CMZ 和 MNZ 的检出限（LODs）分别为 0.045、0.036 和 0.033μg/g。结果表明，该方法在鱼样中唑类杀菌剂的预处理方面具有良好的应用前景。
