Dirtu Alin C, Roosens Laurence, Geens Tinne, Gheorghe Adriana, Neels Hugo, Covaci Adrian
Toxicological Centre, Department of Pharmaceutical Sciences, University of Antwerp, Universiteitsplein 1, 2610, Wilrijk, Belgium.
Anal Bioanal Chem. 2008 Jun;391(4):1175-81. doi: 10.1007/s00216-007-1807-9. Epub 2008 Jan 11.
This study aimed at optimizing and validating a sensitive method for simultaneous determination of bisphenol A (BPA), triclosan (TCS), and tetrabromobisphenol A (TBBPA) in human serum using solid-phase extraction (SPE) and gas chromatography coupled to electron-capture negative-ionization mass spectrometry (GC-ECNI/MS). Sample preparation involved denaturation of serum proteins with formic acid followed by SPE on an Oasis HLB cartridge. Fractionation was performed on Florisil from which the phenolic compounds were eluted with methanol-dichloromethane (DCM) (5:1, v/v). The phenolic fraction was further derivatized with pentafluoropropionic acid anhydride (30 min at 70 degrees C). Further liquid-liquid partitioning using hexane-DCM (4:1, v/v) and K(2)CO(3) 3% aqueous solution was used to eliminate excess reagent and acidic by-products formed during derivatization. The cleaned extract was injected into a GC-ECNI/MS system operated in selected ion monitoring mode. For thorough method validation, each step of the procedure was rigorously optimized. The method limits of quantitation for BPA, TCS, and TBBPA were 0.28 ng mL(-1), 0.09 ng mL(-1) and 0.05 ng mL(-1), respectively. Furthermore, the method was applied to 21 Belgian human serum samples. The median concentrations obtained for BPA (0.71 ng mL(-1)) and TCS (0.52 ng mL(-1)) in Belgian human serum samples were similar to previously reported data for human fluids. Slightly higher levels of TBBPA (0.08 ng mL(-1)) were found in Belgium samples compared to Norwegian serum.
本研究旨在优化并验证一种灵敏的方法,该方法采用固相萃取(SPE)和气相色谱-电子捕获负离子化质谱联用(GC-ECNI/MS)技术,同时测定人血清中的双酚A(BPA)、三氯生(TCS)和四溴双酚A(TBBPA)。样品制备过程包括先用甲酸使血清蛋白变性,然后在Oasis HLB柱上进行固相萃取。在弗罗里硅土上进行分馏,用甲醇-二氯甲烷(DCM)(5:1,v/v)从其中洗脱酚类化合物。酚类馏分再用五氟丙酸酐在70℃下衍生化30分钟。进一步用正己烷-DCM(4:1,v/v)和3%碳酸钾水溶液进行液-液分配,以去除衍生化过程中形成的过量试剂和酸性副产物。将净化后的提取物注入以选择离子监测模式运行的GC-ECNI/MS系统。为了进行全面的方法验证,对该程序的每个步骤都进行了严格优化。BPA、TCS和TBBPA的方法定量限分别为0.28 ng mL-1、0.09 ng mL-1和0.05 ng mL-1。此外,该方法应用于21份比利时人血清样本。比利时人血清样本中BPA(0.71 ng mL-1)和TCS(0.52 ng mL-1)的中位数浓度与先前报道的人体体液数据相似。与挪威血清相比,在比利时样本中发现TBBPA的水平略高(0.08 ng mL-1)。