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离子液体增强:磁性分子印迹聚合物-磁性固相萃取-超高效液相色谱-紫外检测法用于多种食品基质中苯并咪唑的灵敏检测

Enhanced by ionic liquids: Magnetic molecularly imprinted polymers-magnetic solid-phase extraction-UHPLC-UV for sensitive detection of benzimidazoles in multiple food matrices.

作者信息

Xue Tianyi, Yuan Yue, Yuan Yiyang, Song Zhexue, Xiong Zhili, Wang Honggang

机构信息

School of Pharmacy, Shenyang Pharmaceutical University, Benxi 117004, Liaoning Province, PR China.

School of Pharmacy, Shenyang Pharmaceutical University, Benxi 117004, Liaoning Province, PR China.

出版信息

J Chromatogr A. 2025 Sep 27;1759:466237. doi: 10.1016/j.chroma.2025.466237. Epub 2025 Jul 21.

DOI:10.1016/j.chroma.2025.466237
PMID:40706266
Abstract

Benzimidazoles (BZDs) as fungicides and veterinary drugs may remain in various food matrices, posing potential risks to human health. It is challenging to detect trace BZDs under complex matrix interferences. In this study, ion liquid magnetic molecularly imprinted polymers (IL-MMIPs) for the selective extraction of six BZDs from complex matrices were synthesized via surface imprinting technology with vinyl-functionalized Fe₃O₄@SiO₂ as magnetic carriers. Importantly, the synthesized 1-vinyl-3-amidomethylimidazolium chloride ([VAFMIM]Cl-IL) was used as the functional monomer, which could form π-π, hydrogen bonds, electrostatic interactions, ion exchange, and hydrophobic interactions with BZDs. A series of adsorption test results demonstrated that IL-MMIPs exhibited superior selectivity, with high imprinting factors (3.77-4.41) and excellent adsorption capacities (18.26 mg/g). Furthermore, coupling with ultra-high performance liquid chromatography (UHPLC) analysis, an effective, sensitive and selective analysis method based on IL-MMIPs-MSPE-UHPLC integrated technology was established and validated for the quantification of 6 BZDs from multiple food matrices. The results showed remarkable sensitivity with limits of quantification 1.5-10.0 μg/kg and expected recoveries (85.1 %-103.6 %). The method satisfied the detection standards of China and the European Union (EU) and had been applied to food matrices including pork, milk, eggs, drinking water, grapes, cucumbers samples. Finally, trace amounts of thiabendazole were detected only in grapes (533 μg/kg) and eggs (79 μg/kg), demonstrating practical significance for detecting trace BZDs in complex matrices.

摘要

苯并咪唑类化合物(BZDs)作为杀菌剂和兽药可能残留在各种食品基质中,对人类健康构成潜在风险。在复杂基质干扰下检测痕量BZDs具有挑战性。本研究以乙烯基功能化的Fe₃O₄@SiO₂为磁性载体,通过表面印迹技术合成了用于从复杂基质中选择性萃取6种BZDs的离子液体磁性分子印迹聚合物(IL-MMIPs)。重要的是,所合成的1-乙烯基-3-酰胺甲基咪唑氯盐([VAFMIM]Cl-IL)用作功能单体,其可与BZDs形成π-π键、氢键、静电相互作用、离子交换和疏水相互作用。一系列吸附测试结果表明,IL-MMIPs表现出优异的选择性,具有高印迹因子(3.77 - 4.41)和出色的吸附容量(18.26 mg/g)。此外,结合超高效液相色谱(UHPLC)分析,建立并验证了一种基于IL-MMIPs-MSPE-UHPLC集成技术的有效、灵敏且选择性的分析方法,用于定量多种食品基质中的6种BZDs。结果显示出显著的灵敏度,定量限为1.5 - 10.0 μg/kg,预期回收率为85.1% - 103.6%。该方法满足中国和欧盟的检测标准,并已应用于包括猪肉、牛奶、鸡蛋、饮用水、葡萄、黄瓜样品在内的食品基质。最后,仅在葡萄(533 μg/kg)和鸡蛋(79 μg/kg)中检测到痕量噻苯达唑,证明了该方法在检测复杂基质中痕量BZDs方面的实际意义。

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