液相色谱-串联质谱法测定尿液中7种有机磷酸酯代谢物

引用本文: 李佩, 曾祥英, 崔君涛, 赵灵娟, 于志强. 液相色谱-串联质谱法测定尿液中7种有机磷酸酯代谢物[J]. 分析化学, 2017, 45(11): 1648-1654. doi: 10.11895/j.issn.0253-3820.171027 shu

Citation: LI Pei, ZENG Xiang-Ying, CUI Jun-Tao, ZHAO Ling-Juan, YU Zhi-Qiang. Determination of Seven Urinary Metabolites of Organophosphate Esters Using Liquid Chromatography-Tandem Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2017, 45(11): 1648-1654. doi: 10.11895/j.issn.0253-3820.171027 shu

液相色谱-串联质谱法测定尿液中7种有机磷酸酯代谢物

1.
中国科学院广州地球化学研究所, 有机地球化学国家重点实验室, 广东省环境资源利用与保护重点实验室, 广州 510640;
2.
中国科学院大学, 北京 100049
基金项目:
本文系国家杰出青年科学基金（No.41225013）和中国科学院战略性先导科技专项（B类）（No.XDB14010202）资助

摘要: 利用液相色谱-三重四极杆质谱（LC-MS/MS）联用技术，建立了人尿液中7种有机磷酸酯代谢产物-有机磷酸二酯的检测方法。针对不同理化性质的有机磷酸二酯，采用固相萃取技术进行富集净化，筛选出高效的固相萃取柱，并对其洗脱条件进行优化；同时，对流动相和质谱参数进行优化，获取用于各代谢产物定性与定量分析的特征离子对。研究结果表明，前处理采用Oasis WAX固相萃取柱富集、2 mL含5%氨水的甲醇和2 mL甲醇洗脱目标物，除磷酸二乙酯（DEP，17.8%~36.2%）外，其余目标化合物回收率均在60.5%~104.0%之间。在优化的液相色谱条件下，7种化合物可达到完全基线分离。7种有机磷酸二酯的检测限和定量限分别在0.005~0.2μg/L和0.02~0.5μg/L之间，日内和日间精密度结果（RSD≤15.4%）表明，本方法具有较好的稳定性和重现性。本方法用于普通人群尿液中有机磷酸二酯的检测，7种化合物在尿液中均有检出，总浓度在0.5~6.7μg/L之间。

关键词:

English

Determination of Seven Urinary Metabolites of Organophosphate Esters Using Liquid Chromatography-Tandem Mass Spectrometry

1.
State Key Laboratory of Organic Geochemistry, Guangdong Key Laboratory of Environment and Resources, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China
Received Date: 21 June 2017
Revised Date: 19 July 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (No. 41225013).

Abstract: A simple method was developed for simultaneous determination of seven urinary metabolites of organophosphate esters by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Based on different physical and chemical properties of these OPs metabolites, the solid phase extraction cartridges and the washing and eluting solvents were optimized in details. Furthermore, the mobile phase and mass spectrometric parameters were also investigated. The results showed that Oasis WAX cartridge was the best SPE column in this study, and 2 mL of NH₃·H₂O (5%) in methanol and 2 mL of methanol were chosen as the eluting solvents. The recoveries of six analytes were ranged from 60.5% to 104.0%, whereas DEP ranged from 17.8% to 36.2%. Seven analytes could be baseline separated from each other under the optimized chromatographic conditions. The limits of detection and quantification of seven analytes ranged from 0.005 to 0.2 μg/L and 0.02 to 0.5 μg/L, respectively. The standard deviations of response repeatability for intra-day and inter-day period were lower than 15.4%. This method was finally applied to determination of metabolites of OPs from 10 urines from general population in Guangzhou city. The concentrations of total OPs metabolites in urine samples ranged from 0.5 to 6.7 μg/L.

Key words:

Liquid chromatography-tandem mass spectrometry
/ Organophosphate esters
/ Urine
/ Metabolites

1. [1]
  Stapleton H M, Klosterhaus S, Eagle S, Fuh J, Meeker J D, Blum A, Webster T F. Environ. Sci. Technol., 2009, 43(19):7490-7495
2. [2]
  Marklund A, Andersson B, Haglund P. Chemosphere., 2003, 53(9):1137-1146
3. [3]
  van der Veen I, de Boer J. Chemosphere, 2012, 88(10):1119-1153
4. [4]
  Liu C, Su G, Giesy J P, Letcher R J, Li G, Agrawal I, Li J, Yu L, Wang J, Gong Z. Sci. Rep., 2016, 6:19045
5. [5]
  Wei G L, Li D Q, Zhuo M N, Liao Y S, Xie Z Y, Guo T L, Li J J, Zhang S Y, Liang Z Q. Environ Pollut., 2015, 196:29-46
6. [6]
  Van den Eede N, Tomy G, Tao F, Halldorson T,Harrad S, Neels H, Covaci A. Chemosphere, 2016, 144:1299-1305
7. [7]
  Hou R, Xu Y P, Wang Z J. Chemosphere, 2016, 153:78-90
8. [8]
  Schindler B K, Foerster K, Angerer J. J. Chromatogr. B, 2009, 877(4):375-381
9. [9]
  Schindler B K, Foerster K, Angerer J. Anal Bioanal Chem., 2009, 395(4):1167-1171
10. [10]
  Su G, Letcher R J, Yu H. J. Chromatogr. A, 2015, 1426:154-160
11. [11]
  Cequier E, Marce R M, Becher G, Thomsen C. Anal. Chim. Acta, 2014, 845:98-104
12. [12]
  van den Eede N, Neels H, Jorens P G, Covaci A. J. Chromatogr. A, 2013, 1303:48-53
13. [13]
  Cooper E M, Covaci A, van Nuijs A L N, Webster T F, Stapleton H M. Anal. Bioanal. Chem., 2011, 401(7):2123-2132
14. [14]
  Luo P, Bao L J, Guo Y, Li S M, Zeng EY. J. Hazardous Mater., 2016, 301:504-511
15. [15]
  Zeng X Y, He L X, Cao S X, Ma S T, Yu Z Q, Gui H Y, Sheng G Y, Fu J M. Environ. Toxicol. Chem., 2014, 33:1720-1725
16. [16]
  BickerW, Lämmerhofer M, Lindner W. J. Chromatogr. B, 2005, 822(1-2):160-169
17. [17]
  Reemtsma T, Lingott J, Roegler S. Sci. Total Environ., 2011, 409(10):1990-1993
18. [18]
  Kosarac I, Kubwabo C, Foster W G. J. Chromatogr. B, 2016, 1014:24-30

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沈阳化工大学材料科学与工程学院沈阳 110142

液相色谱-串联质谱法测定尿液中7种有机磷酸酯代谢物

English

Determination of Seven Urinary Metabolites of Organophosphate Esters Using Liquid Chromatography-Tandem Mass Spectrometry

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

液相色谱-串联质谱法测定尿液中7种有机磷酸酯代谢物

English

Determination of Seven Urinary Metabolites of Organophosphate Esters Using Liquid Chromatography-Tandem Mass Spectrometry

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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