Yang Lihua, Lan Chongyu, Liu Hongtao, Dong Jun, Luan Tiangang
State Key Laboratory of Biocontrol, School of Life Sciences, Sun Yat-Sen (Zhongshan) University, Guangzhou 510275, People's Republic of China.
Anal Bioanal Chem. 2006 Sep;386(2):391-7. doi: 10.1007/s00216-006-0631-y. Epub 2006 Jul 25.
A fully automated method using direct immersion solid-phase microextraction (DI-SPME) and headspace on-fiber silylation for simultaneous determinations of exogenous endocrine-disrupting chemicals (EDCs) and endogenous steroid hormones in environmental aqueous and biological samples by gas chromatography-mass spectrometry (GC-MS) was developed and compared to a previously reported manual method. Three EDCs and five endocrine steroid hormones were selected to evaluate this method. The extraction and derivatization time, ion strength, pH, incubation temperature, sample volume, and extraction solvent were optimized. Satisfactory results in pure water were obtained in terms of linearity of calibration curve (R2=0.9932-1.0000), dynamic range (3 orders of magnitude), precision (4-9% RSD), as well as LOD (0.001-0.124 microg L(-1)) and LOQ (0.004-0.413 microg L(-1)), respectively. These results were similar to those obtained using a manual method, and moreover, the precision was improved. This new automated method has been applied to the determinations of target compounds in real samples used in our previous study on a manual SPME method. Exogenous octylphenol (OP), technical grade nonylphenol (t-NP), and diethylstilbestrol (DES) were at 0.13, 5.03, and 0.02 microg L(-1) in river water and 3.76, 13.25, and 0.10 microg L(-1) in fish serum, respectively. Natural steroid hormones estrone (E1), 17beta-estradiol (E2), and testosterone (T) were at 0.19, 0.11, and 6.22 microg L(-1) in river water; and in female fish serum E1, E2, and pregnenolone (PREG) were at 1.37, 1.95, and 6.25 microg L(-1), respectively. These results were confirmed by the manual method. The developed fully automated SPME and on-fiber silylation procedures showed satisfactory applications in environmental analysis and the performances show improved precision and a reduced analysis time compared to the manual method.
建立了一种全自动方法，该方法采用直接浸入式固相微萃取（DI-SPME）和顶空纤维上硅烷化技术，通过气相色谱-质谱联用（GC-MS）同时测定环境水样和生物样品中的外源内分泌干扰化学物（EDC）和内源甾体激素，并与之前报道的手动方法进行了比较。选择了三种EDC和五种内分泌甾体激素来评估该方法。对萃取和衍生化时间、离子强度、pH值、孵育温度、样品体积和萃取溶剂进行了优化。在纯水中获得了令人满意的结果，校准曲线的线性（R2 = 0.9932 - 1.0000）、动态范围（3个数量级）、精密度（相对标准偏差为4 - 9%）以及检测限（0.001 - 0.124 μg L-1）和定量限（0.004 - 0.413 μg L-1）均表现良好。这些结果与手动方法获得的结果相似，而且精密度有所提高。这种新的自动化方法已应用于我们之前关于手动固相微萃取方法的研究中实际样品中目标化合物的测定。外源辛基酚（OP）、工业级壬基酚（t-NP）和己烯雌酚（DES）在河水中的含量分别为0.13、5.03和0.02 μg L-1，在鱼血清中的含量分别为3.76、13.25和0.10 μg L-1。天然甾体激素雌酮（E1）、17β-雌二醇（E2）和睾酮（T）在河水中的含量分别为0.19、0.11和6.22 μg L-1；在雌鱼血清中，E1、E2和孕烯醇酮（PREG）的含量分别为1.37、1.95和6.25 μg L-1。这些结果通过手动方法得到了证实。所开发的全自动固相微萃取和纤维上硅烷化程序在环境分析中显示出令人满意的应用效果，与手动方法相比，其性能表现出更高的精密度和更短的分析时间。
