新型多孔有机骨架材料在地表水中21种糖皮质激素高通量筛查中的应用

Application of Novel Porous Organic Frameworks in High- Throughput Screening of 21 Glucocorticoids in Surface Water

以1,2-二氯乙烷为溶剂,三氯化铁为催化剂,1,3,5-三苯基苯、甲苯为单体,二甲氧基甲烷为交联剂进行聚合反应,反应完成后,以甲醇为溶剂索氏提取粗产物,干燥、研磨后得到含有苯基官能团的新型多孔有机骨架材料(POFs)。用优化的填料量填装了一种新型POFs固相萃取柱,旨在发展一种新的地表水中21种糖皮质激素的前处理方法,并对新型POFs固相萃取柱的吸附性能进行了重复性试验。结果表明:使用填料量为20 mg的POFs固相萃取柱时,吸附性能和稳定性较好,且该POFs固相萃取柱至少可以重复使用5次,减少了一次性试验用品的消耗。用此POFs固相萃取柱对地表水进行前处理,采用高效液相色谱-四极杆/静电场轨道阱高分辨质谱对地表水中21种糖皮质激素进行高通量筛查检测,21种糖皮质激素标准曲线的线性范围为20~100μg·L^(-1),测定下限为20μg·L^(-1)。方法用于实际水库中水样分析,6个水库水样中均有糖皮质激素检出,检出总量为2.68~11.64μg·L^(-1),与使用Cleanert PEP-2固相萃取柱的测定结果相比,所得结果在同一个数量级水平,说明二者对水样中的糖皮质激素的富集浓缩具有相似的效果。

The polymerization was carried out with 1,2-dichloroethane as solvent, ferric chloride as catalyst, 1,3,5-triphenylbenzene and toluene as monomers and dimethoxymethane as crosslinking agent. When the reaction was completed, the crude product was extracted by Soxhlet with methanol as solvent. The novel porous organic frameworks(POFs) with phenyl functional group were obtained after drying and grinding. The novel POFs solid phase extraction(SPE) column was filled with optimized packing amounts. The aim was to develop a new pretreatment method for the analysis of 21 glucocorticoids in surface water. And the adsorption performance of the novel POFs SPE column was tested by repeatability test. It was shown that the adsorption performance and stability were good with 20 mg of the POFs SPE column. And the POFs SPE column could be reused at least 5 times, which reduced the consumption of disposable experimental supplies. Based on the pretreatment of the surface water with the POFs SPE column, high performance liquid chromatography-quadrupole/field orbitrap high resolution mass spectrometry(HPLC-Q/Orbitrap MS) was used for high-throughput screening of 21 glucocorticoids in surface water. The linear ranges of the standard curves for 21 glucocorticoids were 20-100 μg·L^(-1), with the same lower limits of determination of 20 μg·L^(-1). This method was applied to the analysis of water samples in actual reservoirs, and glucocorticoids were widely detected in the water samples of the six reservoirs with total detected amounts in the range of 2.68-11.64 μg·L^(-1). The results were on the same level of magnitude to those obtained using the Cleanert PEP-2 SPE column, which indicated that two SPE columns had similar effects on the enrichment and concentration of glucocorticoids in water samples.