In this work, hollow-fiber microporous membrane liquid–liquid extraction (HF-MMLLE) was associated with a 96-well plate system for the determination of estrone, 17-β-estradiol, estriol and 17-α-ethinylestradiol in urine samples. This method exhibited some advantages, such as low cost, easy application, high-throughput and environmentally-friendly aspects. The type of organic solvent to fill the membrane, ionic strength effect, sample dilution, extraction and desorption time, and desorption solvent were examined. After the optimizations, the conditions were comprised of 45 min of extraction, 1-octanol as organic solvent and 15% (w/v) of NaCl; methanol was used as desorption solvent, and the desorption time was fixed at 10 min. The dilution of the sample increased the sensitivity due to the reduction of matrix effects; thus, urine samples were diluted 40-fold. The limits of detection ranged from 0.03 μg L⁻¹ for 17-β-estradiol to 15 μg L⁻¹ for estrone, and the limits of quantification ranged from 0.1 μg L⁻¹ for 17-β-estradiol to 10 μg L⁻¹ for estrone. The intra-day precision varied from 1.0% for estriol to 13.3% for 17-α-ethinylestradiol, and inter-day precision varied from 7.3% for estrone to 18.1% for estriol. The relative recoveries varied from 82 to 118%.

在这项工作中，中空纤维微孔膜液-液萃取 (HF-MMLLE) 与 96 孔板系统相关联，用于测定尿液样品中的雌酮、17-β-雌二醇、雌三醇和 17-α-炔雌醇。该方法具有成本低、应用方便、通量高、环境友好等优点。对填充膜的有机溶剂类型、离子强度效应、样品稀释度、提取和解吸时间以及解吸溶剂进行了检查。优化后的条件为萃取45 min，1-辛醇为有机溶剂，15% (w/v) NaCl；脱附溶剂为甲醇，脱附时间固定为 10 min。由于基质效应的减少，样品的稀释提高了灵敏度；因此，尿液样本被稀释 40 倍。检测限为 0.03 μg L17-β-雌二醇的 -1 至雌酮的 15 μg L ^{-1 ，}定量限从17-β-雌二醇的0.1 μg L ^{-1到雌酮的 10 μg L -1}不等。日内精度从雌三醇的 1.0% 到 17-α-炔雌醇的 13.3% 不等，日间精度从雌酮的 7.3% 到雌三醇的 18.1% 不等。相对回收率从 82% 到 118% 不等。