College of Chemistry and Chemical Engineering, Xingtai University, Xingtai 054001, China.
Functional Polymer Materials R&D and Engineering Application Technology Innovation Center of Hebei, Xingtai 054001, China.
Molecules. 2024 May 14;29(10):2311. doi: 10.3390/molecules29102311.
Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO@FeO as an adsorbent. COF-SiO@FeO was prepared by a straightforward solvothermal method, using FeO as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO@FeO could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 μg·kg (1.00-100 μg·kg for bifenthrin and 2.5-100 μg·kg for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 μg·kg, and the limits of quantification (LOQs) were 0.9-4.5 μg·kg. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO@FeO, NH-SiO@FeO and FeO were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO@FeO was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.
拟除虫菊酯（PYRs）在农业中被广泛用于保护水果和蔬菜作物。然而，过量使用或不当应用可能会导致残留物超过安全限制，从而对消费者安全构成威胁。因此，迫切需要开发从蔬菜中消除或痕量检测 PYRs 的高效技术。在这里，开发了一种简单高效的磁性固相萃取（MSPE）策略，使用磁性共价有机骨架纳米材料 COF-SiO@FeO 作为吸附剂，同时对蔬菜中的五种 PYRs 进行净化和富集。COF-SiO@FeO 通过使用 FeO 作为磁性核和联苯二胺和 3,3,5,5-四醛联苯作为两个构建单元的简单溶剂热方法制备。COF-SiO@FeO 可以通过其丰富的π电子系统和羟基有效地捕获目标 PYRs。研究了各种实验参数对萃取效率的影响，以优化 MSPE 条件，包括吸附剂用量、萃取时间、洗脱溶剂类型和洗脱时间。随后，在最佳条件下结合气相色谱-质谱（GC-MS）进行方法验证。在 5.00-100 μg·kg（1.00-100 μg·kg 用于溴氰菊酯和 2.5-100 μg·kg 用于氯氟氰菊酯）范围内，五种 PYRs 表现出很强的线性关系，决定系数范围为 0.9990 至 0.9997。检出限（LODs）为 0.3-1.5 μg·kg，定量限（LOQs）为 0.9-4.5 μg·kg。回收率为 80.2-116.7%，相对标准偏差（RSDs）低于 7.0%。最后，将 COF-SiO@FeO、NH-SiO@FeO 和 FeO 进行比较，作为用于 PYRs 的 MSPE 吸附剂。结果表明，COF-SiO@FeO 是一种高效快速的 PYRs 选择性吸附剂。该方法有望用于实际样品中 PYRs 的测定。
