Fattahi Nazir, Shamsipur Mojtaba, Nematifar Ziba, Babajani Nasrin, Moradi Masoud, Soltani Shahin, Akbari Shahram
Research Center for Environmental Determinants of Health (RCEDH), Health Institute, Kermanshah University of Medical Sciences Kermanshah Iran
Department of Analytical Chemistry, Faculty of Chemistry, Razi University Kermanshah Iran.
RSC Adv. 2022 May 13;12(23):14467-14476. doi: 10.1039/d2ra01754g. eCollection 2022 May 12.
Steroid hormones, such as estrone (E1), 17β-estradiol (E2), 17β-ethinylestradiol (EE2) and estriol (E3) are a group of lipophilic active substances, synthesized biologically from cholesterol or chemically. A pH-switchable hydrophobic deep eutectic solvent-based liquid phase microextraction (DES-LPME) technique was established and combined with gas chromatography-mass spectroscopy for the determination of estrogenic compounds in environmental water and wastewater samples. A DES was synthesized using -menthol as HBA and (1)-(+)-camphor-10-sulfonic acid (CSA) as HBD, and used as a green extraction solvent. By adjusting the pH of the solution, the unique behavior of the DES in the phase transition and extraction of the desired analytes was investigated. The homogenization process of the mixture is done only by manual shaking in less than 30 seconds and the phase separation is done only by changing the pH and without centrifugation. Some effective parameters on the extraction and derivatization, such as molar ratio of DES components, DES volume, KOH concentration, HCl volume, salt addition, extraction and derivatization time and derivatization prior or after extraction were studied and optimized. Under the optimum conditions, relative standard deviation (RSD) values for intra-day and inter-day of the method based on 7 replicate measurements of 20 ng L of estrogenic compounds and 10 ng L for internal standard in different samples were in the range of 2.2-4.6% and 3.9-5.7%, respectively. The calibration graphs were linear in the range of 0.5-100 ng L and the limits of detection (LODs) were in the range of 0.2-1.0 ng L. The relative recoveries of environmental water and wastewater samples which have been spiked with different levels of target compounds were 91.0-108.8%.
类固醇激素，如雌酮（E1）、17β-雌二醇（E2）、17β-乙炔雌二醇（EE2）和雌三醇（E3），是一类亲脂性活性物质，可由胆固醇生物合成或化学合成。建立了一种基于pH可切换的疏水性低共熔溶剂的液相微萃取（DES-LPME）技术，并将其与气相色谱-质谱联用，用于测定环境水和废水样品中的雌激素化合物。使用薄荷醇作为氢键受体（HBA）和（1）-（+）-樟脑-10-磺酸（CSA）作为氢键供体（HBD）合成了一种DES，并将其用作绿色萃取溶剂。通过调节溶液的pH值，研究了DES在所需分析物的相变和萃取中的独特行为。混合物的均质化过程仅通过手动摇晃在不到30秒内完成，相分离仅通过改变pH值完成，无需离心。研究并优化了一些对萃取和衍生化有影响的有效参数，如DES组分的摩尔比、DES体积、KOH浓度、HCl体积、加盐量、萃取和衍生化时间以及萃取前或萃取后的衍生化。在最佳条件下，基于对不同样品中20 ng/L雌激素化合物和10 ng/L内标物进行7次重复测量，该方法的日内和日间相对标准偏差（RSD）值分别在2.2-4.6%和3.9-5.7%范围内。校准曲线在0.5-100 ng/L范围内呈线性，检测限（LOD）在0.2-1.0 ng/L范围内。添加了不同水平目标化合物的环境水和废水样品的相对回收率为91.0-108.8%。
