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 (SBET = 408.91 ± 6.72 m2 g-1) 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-1. The limits of detection (LODs) were 0.045, 0.036 and 0.033 μg g-1 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.

中文翻译：

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通过Pickering乳液聚合制备的虚拟分子印迹微球，用于从鱼样品中基质固相分散体中提取三种唑类杀菌剂。

通过Pickering乳液聚合合成了虚拟的分子印迹微球（DMIM），并将其用作基质固相分散萃取（MSPD）吸附剂，用于鱼样品中的唑类杀菌剂的样品预处理。使用α-（2,4-二氯苯基）-1H-咪唑-1-乙醇（DCE）作为片段假模板，用于烙印Campzazole（CBZ），clotrimazole（CMZ）和miconazole（MNZ）的印迹。通过扫描电子显微镜（SEM）和氮吸附测量来表征微球的形态，获得具有规则球形和高表面积（SBET = 408.91±6.72 m2 g-1）的窄直径分布（20-50μm）。通过静态吸附实验发现，对于CBZ，CMZ和MNZ，DMIM具有良好的类选择性。然后评估压印的微球作为MSPD吸附剂对鱼样品中CBZ，CMZ和MNZ的提取和纯化。通过HPLC-DAD分析在225nm处检测提取的唑类杀真菌剂。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方法对加标为0.5、2.5和12.5μgg-1的鱼样品具有良好的回收率（89.2-101.5％）和重现性（RSDs 1.6-4.8％，n = 5）。CBZ，CMZ和MNZ的检出限（LOD）分别为0.045、0.036和0.033μgg-1。结果表明，该方法在鱼样品中唑类杀菌剂的预处理方面具有良好的应用前景。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方法对加标为0.5、2.5和12.5μgg-1的鱼样品具有良好的回收率（89.2-101.5％）和重现性（RSDs 1.6-4.8％，n = 5）。CBZ，CMZ和MNZ的检出限（LOD）分别为0.045、0.036和0.033μgg-1。结果表明，该方法在鱼样品中唑类杀菌剂的预处理中具有良好的应用前景。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方法对加标为0.5、2.5和12.5μgg-1的鱼样品具有良好的回收率（89.2-101.5％）和重现性（RSDs 1.6-4.8％，n = 5）。CBZ，CMZ和MNZ的检出限（LOD）分别为0.045、0.036和0.033μgg-1。结果表明，该方法在鱼样品中唑类杀菌剂的预处理中具有良好的应用前景。