RESULTS: In this work, a honeycomb-like triazine-based conjugated microporous polymers (T-CMPs) were prepared by Yamamoto reaction and firstly used as SPME coating material for the ultrasensitive direct-immersion-SPME of PAHs prior to high performance liquid chromatography-fluorescence detector (HPLC-FLD). The synthesized T-CMPs was characterized using various spectroscopy and electron microscopy techniques. The unique porous network of T-CMPs might deliver abundant adsorption sites for PAHs. Orthogonal experimental design (OED) was used to investigate the influence of four experimental parameters on the enrichment ability. Under optimal situation, a wide linear range (which lasted from 0.003 to 1000 μg L-1) with the coefficients of determination (R2) varying 0.9981 to 0.9993 was obtained. The limits of detection (LODs) for the analytes varied from 0.001 to 1.650 μg L-1, and the limits of quantification (LOQs) were between 0.003 and 4.960 μg L-1. The proposed method was effectively employed to the simultaneous and ultrasensitive detection of fifteen PAHs in industrial wastewaters. The relative recoveries for PAHs analysis varied from 74.6 % to 105 % with the relative standard deviations (RSD) of 0.1 %-7.5 % in real water samples.
CONCLUSIONS: The prepared SPME coating material exhibited a simultaneous, high extraction and adsorption capacity for fifteen PAHs due to its honeycomb-like porous structure, ultra-large specific surface area, strong π-π stacking, and hydrophobic interactions. The present research developed a novel strategy for the construction of SPME fiber coating composites and demonstrated great application potential in the field of sample pretreatment and environmental analytical chemistry.
结果:在这项工作中,通过Yamamoto反应制备了蜂窝状的三嗪基共轭微孔聚合物(T-CMPs),并首先在高效液相色谱-荧光检测器(HPLC-FLD)之前将其用作SPME涂层材料,用于PAHs的超灵敏直接浸入SPME。使用各种光谱学和电子显微镜技术表征合成的T-CMP。T-CMP的独特多孔网络可能为PAHs提供丰富的吸附位点。采用正交试验设计(OED)研究了4个实验参数对富集能力的影响。在最优情况下,获得了一个宽的线性范围(从0.003到1000μgL-1),测定系数(R2)在0.9981到0.9993之间变化。分析物的检出限(LOD)在0.001至1.650μgL-1之间变化,定量限(LOQ)在0.003至4.960μgL-1之间。该方法有效地用于工业废水中15种多环芳烃的同时和超灵敏检测。在实际水样中,PAHs分析的相对回收率从74.6%到105%不等,相对标准偏差(RSD)为0.1%-7.5%。
结论:制备的SPME涂层材料表现出同时,由于其蜂窝状多孔结构,对15种多环芳烃具有很高的提取和吸附能力,超大比表面积,强π-π堆叠,和疏水相互作用。本研究开发了一种用于构建SPME纤维涂层复合材料的新策略,并在样品预处理和环境分析化学领域展示了巨大的应用潜力。