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標題: Magnetic Molecularly Imprinted Polymers for Dispersive micro Solid - Phase Extraction of Estrogens in Environmental Aqueous Samples by Liquid Chromatography-Tandem Mass Spectrometry
作者: Cheng-Chieh Huang
關鍵字: 雌激素;磁性奈米粒子;分子印模聚合物;環境水樣;液相層析串聯質譜;estrogen;magnetic nanoparticles;molecularly imprinted polymers;environmental aqueous samples;LC-MS/MS
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Endocrine disrupting chemicals (EDCs) in aquatic environment have gained global attention because they may interfere with central regulatory functions by antagonizing or mimicking the effects of endogenous hormones even at extremely low concentrations. In human life, the use of estrogens, the group of steroidal hormones of EDCs, in animal feeds, contraceptives, and hormone replacement therapy drugs is increasing dramatically. Estrogens enter the human living environment may cause many diseases such as breast and prostate cancers. Hence, to develop an efficiency analytical method for determination of estrogens in aquatic samples is important. This study developed magnetic molecularly imprinted polymers (mMIPs) for dispersive micro solid-phase extraction (DμSPE) combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) for characterization of trace estrogens in aquatic samples. The experimental conditions including the synthesis of mMIPs and extraction parameters were optimized. In this study, 10 mg mMIPs were placed in a 1.5 mL microtube, subsequently added 1 mL water sample pH adjusted to 8. The mixed solution was vortexed for 3 min and separated using an external magnet followed by washing with pH 8 buffer. Then added 200 μL 5% NH4OH in acetonitrile and vortexed for 1 min. After separated, the supernatant was injected into the LC-MS/MS. The linearity of the proposed method ranged from 0.1 – 50 ng/mL for estradiol (E2), 17α-Ethinylestradiol (EE2), and 0.05 – 50 ng/mL for estrone (E1), diethylstilbestrol (DES) with the coefficients of determination above 0.9968. The limit of detection (LODs) ranged from 0.4 – 1.4 pg/mL. The feasibility of applying the proposed method to determine the trace estrogens in environmental water samples of Taichung area was also examined. The trace amount of DES, E1, E2, and EE2 in environmental water were detected by proposed method at 0.92, 1.16, 0.48, and 1 ng/mL, respectively. The results showed the developed method can be successfully utilized for analyzing the trace of estrogens.

環境水樣中所含的內分泌干擾物近年來逐漸受到世界各國的重視,主要原因為其會干擾或著模仿有機體內分泌賀爾蒙,即使在極低的濃度之下 (ng/L) 也會影響到人體健康。在生活中,雌激素常被應用在添加於養殖飼料、賀爾蒙治療藥物與避孕藥中,經由環境而長期接觸雌激素化合物有可能造成癌症病發。因此,開發一有效率檢測環境水樣中雌激素的分析方法是一個值得重視的課題。本研究開發磁性分子印模聚合物 (magnetic molecularly imprinted polymers, mMIPs) 利用分散式固相微萃取法結合液相層析串聯質譜術,於環境水樣中的微量雌激素進行分析。在研究中磁性分子印模聚合物合成及前處理方法均進行最佳化測試。實驗結果顯示前處理最佳化步驟為取 10 mg 的磁性分子印模聚合物加入 1.5 mL 微量離心管中,添加經 pH 值調整為 8 之 1 mL樣品,以渦流震盪萃取 3 分鐘後,利用外加磁場使磁性分子印模聚合物與水溶液快速分離,以 pH 8 緩衝溶液清洗,再加入 200 μL 5% 之 25% 氨水之乙腈溶液進行脫附,分離後取上清液並以液相層析串聯質譜儀系統進行分析。從實驗結果可得雌二醇和 17α-乙炔基雌脂二醇之線性範圍介於 0.1至 50 ng/mL 之間,雌酮和二乙基己烯雌酚之線性範圍介於 0.05 至 50 ng/mL 之間。線性相關係數皆在 0.9968 以上,方法偵測極限介於 0.41 至 1.4 pg/mL 之間。將此方法用於台中市環境水樣中進行偵測,可測得微量雌激素,二乙基己烯雌酚為 0.92 ng/mL、雌酮為 1.16 ng/mL、雌二醇為為 0.48 ng/mL 以及 17α-乙炔基雌脂二醇為為 1 ng/mL。故此方法可作為環境水樣中微量雌激素檢測方法之參考。
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