Parameters for ultra-performance liquid chromatographic/tandem mass spectrometric analysis of selected androgens versus estrogens in aqueous matrices.
Parameters for ultra-performance liquid chromatographic/tandem mass spectrometric analysis of selected androgens versus estrogens in aqueous matrices.
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DOI：
10.1021/ac900134m
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发表时间：
2009-07
影响因子：
7.4
通讯作者：
S. Rice;R. Hale
中科院分区：
文献类型：
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作者：
S. Rice;R. Hale
这项研究是对环境基质中雄激素与雌激素相关文献相对缺乏的回应。固相萃取（SPE）和超高效液相色谱/（电喷雾电离）串联质谱（UPLC/（ESI）MS（2））的方法平行开发检测四种天然雄激素和四种常用的研究雌激素，三种天然和一种合成，在水基质。仪器参数进行了优化和激素类之间的比较，与应用程序加标去离子水，池塘水，和废水。雄激素与雌激素相比，电子离域和极性较小，睾酮表现居中，这解释了激素类行为的差异。一般而言，雄激素需要更强的UPLC移动的相，流速更慢，ESI极性相反，添加改性剂（0.9 mM乙酸铵）。仪器检测限的雄酮，表雄酮，脱氢表雄酮是1-2个数量级大于睾酮和雌激素，但雄激素更难以分散在提取物储存。在池塘水样品中遇到了可管理的基质干扰。在处理后的废水中引入的是明显的共洗脱峰和偏斜的化合物回收率。观察到雌激素替代物的离子抑制和雄激素的增强。UPLC提供的分析速度证明在简单基质的分析中是有益的，但在复杂环境样品中应被认为是次要的。
This study is a response to the relative lack of literature concerning androgenic versus estrogenic hormones in environmental matrices. Methods of solid-phase extraction (SPE) and ultra-performance liquid chromatography/(electrospray ionization) tandem mass spectrometry (UPLC/(ESI)MS(2)) were developed in parallel for detection of four natural androgens and four commonly studied estrogens, three natural and one synthetic, in aqueous matrices. Instrumental parameters were optimized and compared between hormone classes, with application to spiked deionized water, pond water, and wastewater. Differences in behavior of the hormone classes were explained by the lesser electron delocalization and polarity of the androgens versus estrogens, with testosterone behaving intermediately. In general, androgens required a stronger UPLC mobile phase with a slower flow rate and ESI of the opposite polarity with modifier addition (0.9 mM ammonium acetate). Instrumental detection limits of androsterone, epiandrosterone, and dehydroepiandrosterone were 1-2 orders of magnitude greater than those of testosterone and the estrogens, but androgens were more recalcitrant to dispersal during extract storage. Manageable matrix interference was encountered in pond water samples. That introduced in treated wastewater was evident as coeluting peaks and skewed compound recoveries. Ion suppression of the estrogen surrogate and enhancement of the androgen were observed. The analytical rapidity afforded by UPLC proved beneficial in the analysis of simple matrices but should be considered secondary to enhanced resolution in complex environmental samples.