Ministry of Education Key Laboratory of Environmental Medicine and Engineering, School of Public Health, Southeast University, Nanjing, 210009, China.
Analyst. 2011 Dec 7;136(23):5030-7. doi: 10.1039/c1an15494j. Epub 2011 Oct 12.
A simple, rapid and sensitive method for the determination of diethylstilbestrol (DES), dienestrol (DE) and hexestrol (HEX) was developed by using the Nylon 6 nanofibers mat-based solid-phase extraction (SPE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS). These estrogens were separated within 8 min by LC using an ODS column and methanol/water (80/20, v/v) at a flow rate of 1.0 mL min(-1). Electrospray ionization conditions in the negative ion mode were optimized for MS detection of the estrogens. Under the optimum SPE conditions, all target analytes in 50 mL environmental water samples can be completely extracted by 1.5 mg Nylon 6 nanofibers mat at flow rate of 3.0 mL min(-1) and easily eluted by passage of 500 μL mobile phase. By using the novel SPE-LC/MS method, good linearity of the calibration curve (r(2) ≥ 0.9992) was obtained in the concentration range from 0.10 ng L(-1) to 1.0 mg L(-1) (except for DE which was 0.20 ng L(-1) to 1.0 mg L(-1)) for all analytes examined. The limits of detection (S/N = 3) of the three estrogens ranged from 0.05 ng L(-1) to 0.10 ng L(-1). This method was applied successfully to the analysis of environmental water samples without any other pretreatment and interference peaks. Several water samples were collected from Jinchuan River and Xuanwu Lake, and in Jinchuan River water DES was detected at 0.13 ng L(-1). The recoveries of estrogens spiked into tap water were above 98.2%, and the relative standard deviations were below 4.78%.
建立了尼龙 6 纳米纤维垫固相萃取（SPE）结合液相色谱-串联质谱（LC-MS）测定己烯雌酚（DES）、双烯雌酚（DE）和己烷雌酚（HEX）的方法。采用 ODS 柱和甲醇/水（80/20，v/v）作为流动相，流速为 1.0 mL/min，LC 在 8 min 内将这些雌激素分离。在负离子模式下进行电喷雾电离条件优化，用于雌激素的 MS 检测。在最佳 SPE 条件下，50 mL 环境水样中的所有目标分析物都可以在 3.0 mL/min 的流速下完全被 1.5 mg 尼龙 6 纳米纤维垫提取，然后用 500 μL 流动相轻松洗脱。采用新型 SPE-LC/MS 方法，在所研究的所有分析物中，校准曲线在 0.10 ng/L（除 DE 为 0.20 ng/L）至 1.0 mg/L（除 DE 为 0.20 ng/L）浓度范围内均具有良好的线性关系（r²≥0.9992）。三种雌激素的检出限（S/N=3）范围为 0.05 ng/L 至 0.10 ng/L。该方法无需任何其他预处理和干扰峰即可成功应用于环境水样的分析。从金川河和玄武湖采集了几个水样，在金川河水样中检测到 DES 为 0.13 ng/L。雌激素加入自来水的回收率在 98.2%以上，相对标准偏差低于 4.78%。
