色谱

色谱 ›› 2012, Vol. 30 ›› Issue (07): 665-671.DOI: 10.3724/SP.J.1123.2012.02028

• 研究论文 • 上一篇    下一篇

分散固相萃取-超快速液相色谱-串联质谱法测定牛蛙全血中6种酚类环境雌激素

赵永纲, 陈晓红, 姚珊珊, 李小平, 金米聪   

  1. 宁波市疾病预防控制中心 宁波市毒物研究与控制重点实验室, 浙江 宁波 315010
  • 收稿日期:2012-02-13 修回日期:2012-03-19 出版日期:2012-07-28 发布日期:2012-07-19
  • 通讯作者: 金米聪,博士,研究员,主要从事食品质量安全及化学性毒物的理化检测研究.
  • 基金资助:

    宁波市农业与社会发展项目(2011C50058)、浙江省公益性技术应用研究计划项目（2012C37002）、浙江省自然科学基金项目(LY12H26003)、浙江省医药卫生平台研究计划骨干人才项目(2011RCB033)和宁波市农业与社会发展重大(重点)择优委托项目(2011C11021).

Analysis of six phenolic environmental estrogens in bullfrog blood by using dispersive solid-phase extraction and ultrafast liquid chromatography-tandem mass spectrometry

ZHAO Yonggang, CHEN Xiaohong, YAO Shanshan, LI Xiaoping, JIN Micong   

  1. Ningbo Key Laboratory of Poison Research and Control, Ningbo Municipal Center for Disease Control and Prevention, Ningbo 315010, China
  • Received:2012-02-13 Revised:2012-03-19 Online:2012-07-28 Published:2012-07-19

PDF

587

被引次数

25

摘要： 建立了一种快速、灵敏、准确的同时测定牛蛙全血中双酚A、己烯雌酚、己二烯雌酚、己烷雌酚、4-叔辛基酚和4-壬基酚等6种酚类环境雌激素的分散固相萃取-超快速液相色谱-串联质谱(dSPE-UFLC-MS/MS)分析方法。牛蛙全血样品经含0.1%(v/v)甲酸的甲醇溶液沉淀蛋白后,利用自制的氨基功能化Fe3O4磁性高分子复合微粒(EDA-MPs)作为dSPE吸附剂进行净化,着重考察了沉淀剂、吸附净化时间、吸附剂用量等因素对6种酚类环境雌激素回收率的影响。采用Shim-pack XR-ODSII(100 mm×2.0 mm, 2.2 μm)反相液相色谱柱进行分离,在电喷雾离子源(ESI)负离子多反应监测(MRM)模式下进行检测。结果表明: 6种酚类环境雌激素在0.5～100.0 μg/L范围内具有良好的线性关系(r2≥0.9996),方法的定量限(信噪比大于10)为0.075～0.40 μg/L,方法的精密度为0.6%～6.3%,空白样品中3个不同水平的添加回收率为95.0%～110.0%。本方法适用于牛蛙全血中6种酚类环境雌激素的同时测定。

关键词: 氨基功能化Fe3O4磁性高分子复合微粒, 超快速液相色谱-串联质谱法, 多反应监测, 分散固相萃取, 酚类环境雌激素, 全血

Abstract: A rapid, sensitive and accurate method for the simultaneous determination of six phenolic environmental estrogens, i.e., bisphenol A (BPA), diethylstilbestrol (DES), dienestrol (DE), hexestrol (HEX), 4-(tert-octyl)-phenol (4-tOP) and 4-nonylphenol (4-NP) in bullfrog blood by dispersive solid-phase extraction-ultrafast liquid chromatography-tandem mass spectrometry (dSPE-UFLC-MS/MS) was established. After protein precipitation, bullfrog blood samples were cleaned-up by dSPE method with ethylenediamine-functionalized Fe3O4 magnetic polymers (EDA-MPs) as adsorbent. The effects of precipitation solvents, adsorption time and the amount of EDA-MPs used on the recoveries of six phenolic environmental estrogens were investigated in detail. Chromatographic separation was performed on a Shim-pack XR-ODSIIanalytical column (100 mm×2.0 mm, 2.2 μm). The mass spectrometer was operated by using electrospray ion (ESI) source in the multiple reaction monitoring (MRM) mode. The results showed that the linearities were in the range of 0.5~100.0 μg/L with correlation coefficients (r2) not less than 0.9996 for all the six phenolic environmental estrogens. The limits of quantification (LOQs) (S/N＞10) in bullfrog blood samples were between 0.075 μg/L and 0.40 μg/L. The recoveries were between 95.0% and 110.0% at three spiked levels. The precision values expressed as relative standard deviations (RSDs) were in the range of 0.6%~6.3%. The developed method can be applied to the routine analysis of the six phenolic environmental estrogens in bullfrog blood samples.

Key words: blood, ethylenediamine-functionalized Fe3O4 magnetic polymers (EDA-MPs) , multiple reaction monitoring (MRM) , phenolic environmental estrogens, ultrafast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) , dispersive solid-phase extraction (dSPE)