Abstract：
BACKGROUND: Since the severe hazard to the ecosystem and widespread distribution through biological and man-made ways of polycyclic aromatic hydrocarbons (PAHs), it is very urgent to establish the ultrasensitive analytical method to quantitatively and directly monitor PAHs in real samples. However, because of the complicated environmental matrix and their trace concentration, the pre-concentration process is a necessary step to analyze of these compounds. In this study, solid phase microextraction (SPME) technique was proposed to separate and enrich fifteen trace PAHs from environmental samples.
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.
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.
摘要：
背景：由于多环芳烃（PAHs）对生态系统的严重危害以及通过生物和人为方式的广泛分布，建立超灵敏的分析方法对实际样品中的PAHs进行定量、直接的监测是非常迫切的。然而,由于复杂的环境基质和它们的痕量浓度，预浓缩过程是分析这些化合物的必要步骤。在这项研究中,提出了固相微萃取（SPME）技术从环境样品中分离和富集15种痕量PAHs。
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。
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。
