MOE Key Lab Environment and Health, Institute of Environmental Medicine, School of Public Health, Tongji Medical College, Huazhong University of Science and Technology, Wuhan, Hubei 430030, China; Zhejiang Provincial Key Laboratory of Watershed Science and Health, College of Public Health and Management, Wenzhou Medical University, Wenzhou, Zhejiang 325035, China.
Suzhou Center for Disease Prevention and Control, Suzhou, Jiangsu 215004, China.
Talanta. 2019 Apr 1;195:785-795. doi: 10.1016/j.talanta.2018.11.106. Epub 2018 Nov 30.
Herein, a novel method, magnetic effervescent tablet-assisted ionic liquid-based dispersive liquid-liquid microextraction (META-IL-DLLME), was pioneered for extraction and preconcentration of polybrominated diphenyl ethers (PBDEs) in liquid matrix samples. In this proposed method, a magnetic effervescent tablet, containing CO sources, ionic liquids and FeS magnetic nanoparticles (MNPs), combines extractant dispersion and magnetic recovery into one-step. FeS was synthesized, characterized and applied it for the first time to the newly developed method, and its extraction recoveries (ERs) for PBDEs were 20.8-32.0% higher than those of conventional FeO MNPs. The increased ERs of FeS resulted from its larger specific surface area and pore size. Some important parameters were rigorously optimized, such as kinds of magnetic nanoparticles, effervescent agents, extraction solvents and their volumes, elution solvents, extraction temperature and salt addition. Under the optimized conditions, the META-IL-DLLME method combined with HPLC-DAD analysis gave the linear ranges of 0.1-0.5-100 µg L with correlation coefficients of > 0.9990. The ERs ranged from 80.7% to 99.3%, and the limits of detection and quantitation were 0.012-0.078 µg L and 0.04-0.26 µg L, respectively. The intra- and inter-day precisions, expressed as relative standard deviations (RSD, n = 6), were 1.32-4.83% and 1.99-4.25%, respectively. To evaluate its matrix effect, the relative recoveries of PBDEs from tap and river water, skim and whole milk, pregnant women and women serum samples at three fortification levels (2.0, 5.0 and 20.0 µg L) were in the range of 77.3-106.7%. Overall, the commercial FeO MNPs can only be used for magnetic separation in microextraction procedures, while FeS MNPs gave the higher adsorption and extraction efficiency for organic analytes besides the convenient magnetic separation. Therefore, the results obtained in this study provide a superior alternative for the conventional magnetic separation and adsorbent material. Also, this newly developed method has a great potential in routine monitoring of liquid matrix samples.
本文开创性地提出了一种新方法，即磁膨化片剂辅助离子液体分散液液微萃取（META-IL-DLLME），用于萃取和预浓缩液体基质样品中的多溴二苯醚（PBDEs）。在该方法中，一种包含 CO 源、离子液体和 FeS 磁性纳米粒子（MNPs）的磁膨化片剂将萃取剂分散和磁性回收合二为一。FeS 被合成、表征并首次应用于新开发的方法中，其对 PBDEs 的萃取回收率（ER）比传统的 FeO MNPs 高 20.8-32.0%。FeS 较高的 ER 归因于其更大的比表面积和孔径。还严格优化了一些重要参数，例如磁性纳米粒子、膨化剂、萃取溶剂及其体积、洗脱溶剂、萃取温度和加盐量。在优化条件下，结合 HPLC-DAD 分析，META-IL-DLLME 方法的线性范围为 0.1-0.5-100µg L，相关系数均大于 0.9990。ER 范围为 80.7%-99.3%，检出限和定量限分别为 0.012-0.078µg L 和 0.04-0.26µg L。日内和日间精密度分别表示为相对标准偏差（RSD，n=6），为 1.32-4.83%和 1.99-4.25%。为了评估其基质效应，从自来水和河水、脱脂奶和全脂奶、孕妇和妇女血清样品中以三个加标水平（2.0、5.0 和 20.0µg L）对 PBDEs 的相对回收率在 77.3%-106.7%范围内。总的来说，商用 FeO MNPs 只能用于微萃取过程中的磁性分离，而 FeS MNPs 除了方便的磁性分离外，还对有机分析物具有更高的吸附和萃取效率。因此，本研究结果为传统磁性分离和吸附材料提供了更好的选择。此外，该新开发的方法在液体基质样品的常规监测中具有很大的潜力。
