Zhejiang Provincial Key Laboratory of Watershed Science and Health, Southern Zhejiang Water Research Institute, College of Public Health and Management, Wenzhou Medical University, Wenzhou 325035, China.
School of Sports Science, Fujian Normal University, Fuzhou 350117, China.
Ecotoxicol Environ Saf. 2021 Aug;219:112319. doi: 10.1016/j.ecoenv.2021.112319. Epub 2021 May 13.
Herein, we synthesized a kind of magnetic covalent organic framework nanohybrids (NiFeO@COF), and integrated it with polydimethyl siloxane and silicone rubber curing agent for solid phase microextraction (SPME) fiber coating. The fiber coating demonstrated a porous and uniform surface with the BET specific surface of 169.7 m g. As for seven environmental analytes, the NiFeO@COF-based SPME fiber coating gave the higher extraction recoveries for triclosan (TCS) and methyltriclosn (MTCS) than those of fenpropathrin, bifenthrin, permethrin, fenvalerate and deltamethrin. Several operational parameters were rigorously optimized, such as extraction temperature, extraction time, thermal desorption time, solution pH and salt effect. Combined with the GC-ECD detection, the newly developed microextraction method supplied the wide linear range of 0.1-1000 µg L with the correlation coefficients of > 0.9995. The limits of detection (LODs) and limits of quantitation (LOQs) reached as low as 1-7 ng L and 3.3-23 ng L, respectively. The intra-day and inter-day precisions in six replicates (n = 6 ) were < 3.55% and < 5.06%, respectively, and the fiber-to-fiber reproducibility (n = 3) was < 7.64%. To evaluate its feasibility in real samples, the fortified recoveries for TCS and MTCS, at low (0.2 µg L), middle (2.0 µg L) and high (20.0 µg L) levels, varied between 81.9% and 119.1% in tap, river and barreled waters as well as male, female and children urine samples. Especially, it is worth mentioning that the NiFeO@COF-based SPME coating fiber can be recycled for at least 150 times with nearly unchanged extraction efficiency. Moreover, the extraction recoveries by the as-fabricated fiber coating were much higher than those by three commercial fibers (PDMS, PDMS/DVB and PDMS/DVB/CAR). Overall, the NiFeO@COF-based SPME is a convenient, sensitive, efficient and "green" pretreatment method, thereby possessing important application prospects in trace monitoring of TCS-like pollutants in complex liquid matrices.
本文合成了一种磁性共价有机框架纳米杂化材料（NiFeO@COF），并将其与聚二甲基硅氧烷和硅橡胶固化剂集成用于固相微萃取（SPME）纤维涂层。该纤维涂层具有多孔且均匀的表面，BET 比表面积为 169.7 m g。对于七种环境分析物，基于 NiFeO@COF 的 SPME 纤维涂层对三氯生（TCS）和甲基三氯生（MTCS）的萃取回收率高于氯菊酯、联苯菊酯、氯氰菊酯、溴氰菊酯和氯氟氰菊酯。严格优化了几个操作参数，例如萃取温度、萃取时间、热解吸时间、溶液 pH 值和盐效应。结合 GC-ECD 检测，新开发的微萃取方法提供了 0.1-1000 µg L 的宽线性范围，相关系数大于 0.9995。检测限（LOD）和定量限（LOQ）低至 1-7 ng L 和 3.3-23 ng L。在六个重复（n = 6）中，日内和日间精密度均<3.55%和<5.06%，纤维间重现性（n = 3）<7.64%。为了评估其在实际样品中的可行性，TCS 和 MTCS 的加标回收率在低（0.2 µg L）、中（2.0 µg L）和高（20.0 µg L）水平下在自来水中、河水中和桶装水中以及男性、女性和儿童尿液样品中在 81.9%到 119.1%之间变化。特别是值得一提的是，基于 NiFeO@COF 的 SPME 涂层纤维可以至少回收 150 次，且萃取效率几乎不变。此外，通过所制备的纤维涂层进行的萃取回收率远高于三种商业纤维（PDMS、PDMS/DVB 和 PDMS/DVB/CAR）。总体而言，基于 NiFeO@COF 的 SPME 是一种方便、灵敏、高效且“绿色”的预处理方法，因此在复杂液体基质中痕量监测 TCS 类污染物方面具有重要的应用前景。
