Key Laboratory for Applied Technology of Sophisticated Analytical Instruments, Shandong Analysis and Test Centre, Qilu University of Technology (Shandong Academy of Sciences), Jinan, Shandong, 250014, PR China.
Department of Chemistry, The Chinese University of Hong Kong, HKSAR, PR China.
J Chromatogr A. 2019 Sep 13;1601:27-34. doi: 10.1016/j.chroma.2019.05.004. Epub 2019 May 3.
Multifunctional polymeric microspheres were prepared using hyper-cross-linking chemistry combined with surface-initiated atom transfer radical polymerization. The synthesized microspheres exhibited good water dispersibility, a high surface area, and pH/thermo dual-responsiveness. Fluoroquinolones (FQs), which contains a hydrophilic piperazine ring and hydrophobic fluorine atoms, were used as target analytes to assess the performance of the microspheres as a sorbent for dispersive solid-phase extraction (d-SPE). The d-SPE experimental parameters, including extraction time, amount of microspheres, extraction temperature, and sample solution pH, as well as the desorption conditions, were systematically studied. Coupled with LCMS/MS, an analytical method for analysis of trace-level FQs in water samples was developed and validated. Under optimal conditions, linearity with correlation coefficients (r) of >0.99 was achieved in the concentration range of 0.02-10 μg L. The limits of detection and quantification for the selected FQs were 5.0-6.7 and 12-20 ng L, respectively. High recovery values (93.1%-97.2%), a high enrichment factor (˜180), and good precision (RSD < 8%, n = 6) were obtained for FQ determination in spiked purified water samples. It was proposed that hydrophilic-hydrophobic transition induced by stretching and shrinking of polymer chains under different pH and temperature conditions offered good control of the surface wettability and altered the extraction behavior. The developed method was validated and was successfully applied to the analysis of FQs in environmental water samples, meat and milk samples. These results demonstrated that the water-dispersible polymeric microspheres have good potential for use in separation and extraction techniques.
采用超交联化学结合表面引发原子转移自由基聚合制备了多功能聚合物微球。所合成的微球具有良好的水分散性、高比表面积和 pH/热双重响应性。氟喹诺酮类（FQs）含有亲水性哌嗪环和疏水性氟原子，被用作目标分析物，以评估微球作为分散固相萃取（d-SPE）吸附剂的性能。系统研究了 d-SPE 的实验参数，包括萃取时间、微球用量、萃取温度和样品溶液 pH 以及解吸条件。与 LCMS/MS 相结合，建立并验证了用于水样中痕量 FQs 分析的分析方法。在最佳条件下，在所研究的浓度范围内（0.02-10μg L），线性相关系数（r）>0.99。所选 FQs 的检出限和定量限分别为 5.0-6.7 和 12-20 ng L。在加标净化水中测定 FQ 时，回收率值高（93.1%-97.2%），富集因子高（˜180），精密度好（RSD<8%，n=6）。在不同 pH 和温度条件下，聚合物链的拉伸和收缩引起的亲水性-疏水性转变提供了对表面润湿性的良好控制，并改变了萃取行为。该方法得到了验证，并成功应用于环境水样、肉类和奶制品中 FQs 的分析。这些结果表明，水分散性聚合物微球在分离和提取技术中具有良好的应用潜力。
