酚类内分泌干扰化学物质(EDCs)是干扰内分泌系统并在进入生物体后破坏正常细胞功能的外源性物质。导致生殖和发育毒性。因此,开发一种快速有效的分析方法来检测环境水域中的酚类EDCs至关重要。由于环境水中酚类EDC的浓度较低,在仪器分析之前,需要适当的样品预处理方法来消除样品基质引起的干扰并富集目标分析物。分散固相萃取(DSPE)作为一种用于环境样品分析的简单,快速的样品预处理方法,已引起人们的广泛关注。在这种方法中,将吸附材料均匀地分散在样品溶液中,并且通过诸如涡旋的过程提取目标分析物。与传统的固相萃取(SPE)相比,DSPE增加了吸附剂和样品溶液之间的接触面积,减少所需的吸附剂和有机溶剂的量,提高了提取效率。吸附剂材料在DSPE中起着至关重要的作用,因为它决定了该方法的提取效率。金属有机骨架(MOFs)是由金属簇和多功能有机配体组成的多孔骨架材料。它们具有许多优异的性能,如可调孔径,大表面积,良好的热稳定性和化学稳定性,使它们成为样品预处理的理想吸附材料。通过高温碳化获得的MOF衍生的多孔碳材料不仅增加了MOF材料的密度以更好地分离,而且还保留了大表面积的优点,高度有序的多孔结构,和高孔隙率。在这项研究中,源自MOF的多孔碳材料,名为奥斯陆大学-66-碳(UiO-66-C),采用溶剂热法合成,并作为吸附剂富集四种酚类EDC(双酚A,4-叔辛基苯酚,4-壬基酚,和壬基酚)在水中。建立了一种将DSPE与超高效液相色谱-串联质谱(UPLC-MS/MS)联用的方法来分析水中酚类EDC。UiO-66-C剂量,水样的pH值,吸附时间,洗脱剂类型和体积,洗脱时间,并对离子强度进行了优化。使用甲醇-水作为流动相进行梯度洗脱。在ACQUITYUPLCBEHC18色谱柱上分离目标分析物(100mm×2.1mm,1.7μm),在负电喷雾电离模式下进行多反应监测(MRM)。该方法在0.5-100μg/L范围内表现出线性相关性。4种酚类EDC的检出限(LODs)和定量限(LOQs)分别为0.01-0.13μg/L和0.03-0.42μg/L,分别。通过日内和日间相对标准偏差(RSD)评估该方法的精密度,数值范围从1.5%到10.6%,从6.1%到13.2%,分别。当应用于检测自来水和地表水中的酚类EDC时,4种酚类EDCs的加标回收率为77.1%-116.6%。在地表水中检测到痕量的4-壬基酚和壬基酚,含量为1.38和0.26μg/L,分别。所提出的方法具有良好的准确性和精密度;因此,它提供了一种新的快速,高效,环境水体中酚类EDCs的检测方法。
Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 μg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 μg/L and 0.03-0.42 μg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 μg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.