Xie Lijun, Liu Shuqin, Han Zhubing, Jiang Ruifen, Zhu Fang, Xu Weiqin, Su Chengyong, Ouyang Gangfeng
Department of Chemistry, Guangdong University of Education, Guangzhou, 510303, China.
MOE Key Laboratory of Aquatic Product Safety/KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, 510275, China.
Anal Bioanal Chem. 2017 Sep;409(22):5239-5247. doi: 10.1007/s00216-017-0472-x. Epub 2017 Jul 6.
The fiber coating is the key part of the solid-phase microextraction (SPME) technique, and it determines the sensitivity, selectivity, and repeatability of the analytical method. In this work, amine (NH)-functionalized material of Institute Lavoisier (MIL)-53(Al) nanoparticles were successfully synthesized, characterized, and applied as the SPME fiber coating for efficient sample pretreatment owing to their unique structures and excellent adsorption properties. Under optimized conditions, the NH-MIL-53(Al)-coated fiber showed good precision, low limits of detection (LODs) [0.025-0.83 ng L for synthetic musks (SMs) and 0.051-0.97 ng L for organochlorine pesticides (OCPs)], and good linearity. Experimental results showed that the NH-MIL-53(Al) SPME coating was solvent resistant and thermostable. In addition, the extraction efficiencies of the NH-MIL-53(Al) coating for SMs and OCPs were higher than those of commercially available SPME fiber coatings such as polydimethylsiloxane, polydimethylsiloxane-divinylbenzene, and polyacrylate. The reasons may be that the analytes are adsorbed on NH-MIL-53(Al) primarily through π-π interactions, electron donor-electron acceptor interactions, and hydrogen bonds between the analytes and organic linkers of the material. Direct immersion (DI) SPME-gas chromatography-mass spectrometry methods based on NH-MIL-53(Al) were successfully applied for the analysis of tap and river water samples. The recoveries were 80.3-115% for SMs and 77.4-117% for OCPs. These results indicate that the NH-MIL-53(Al) coating may be a promising alternative to SPME coatings for the enrichment of SMs and OCPs.
纤维涂层是固相微萃取（SPME）技术的关键部分，它决定了分析方法的灵敏度、选择性和重复性。在本工作中，成功合成、表征了拉瓦锡研究所（MIL）-53（Al）纳米颗粒的胺（NH）功能化材料，并将其用作SPME纤维涂层用于高效样品预处理，这归因于其独特的结构和优异的吸附性能。在优化条件下，涂覆NH-MIL-53（Al）的纤维表现出良好的精密度、低检测限[合成麝香（SMs）为0.025 - 0.83 ng/L，有机氯农药（OCPs）为0.051 - 0.97 ng/L]以及良好的线性。实验结果表明，NH-MIL-53（Al）SPME涂层具有耐溶剂性和热稳定性。此外，NH-MIL-53（Al）涂层对SMs和OCPs的萃取效率高于市售的SPME纤维涂层，如聚二甲基硅氧烷、聚二甲基硅氧烷 - 二乙烯基苯和聚丙烯酸酯。原因可能是分析物主要通过π-π相互作用、电子供体 - 电子受体相互作用以及分析物与材料有机连接体之间的氢键吸附在NH-MIL-53（Al）上。基于NH-MIL-53（Al）的直接浸入（DI）SPME - 气相色谱 - 质谱法成功应用于自来水和河水样品的分析。SMs的回收率为80.3 - 115%，OCPs的回收率为77.4 - 117%。这些结果表明，NH-MIL-53（Al）涂层可能是用于富集SMs和OCPs的SPME涂层的一种有前景的替代品。
