人血清中有机磷酸三酯和二酯的生物监测方法的建立

引用本文: 顾俊婕, 胡曼, 张益宁, 屈卫东, 周颖. 人血清中有机磷酸三酯和二酯的生物监测方法的建立[J]. 分析化学, 2021, 49(8): 1384-1392. doi: 10.19756/j.issn.0253-3820.201541 shu

Citation: GU Jun-Jie, HU Man, ZHANG Yi-Ning, QU Wei-Dong, ZHOU Ying. Ultra-High Performance Liquid Chromatography Coupled with Triple Quadrupole Mass Spectrometry for Simultaneous Determination of Organophosphate Triesters and Diesters in Serum for Human Biomonitoring Study[J]. Chinese Journal of Analytical Chemistry, 2021, 49(8): 1384-1392. doi: 10.19756/j.issn.0253-3820.201541 shu

人血清中有机磷酸三酯和二酯的生物监测方法的建立

1.
复旦大学公共卫生安全教育部重点实验室, 公共卫生学院饮水与健康研究中心, 上海 200032;
2.
复旦大学公共卫生学院营养与食品卫生学暨卫生化学教研室, 上海 200032;
3.
复旦大学公共卫生学院环境卫生学教研室, 上海 200032;
4.
复旦大学浦东预防医学研究院, 上海 200136

通讯作者: 周颖,E-mail:yingchou@fudan.edu.cn

基金项目:
国家重点研发计划项目（No.2017YFC1600500）和国家自然科学基金项目（No.81373089）资助。

摘要: 建立了超高效液相色谱/三重四极杆质谱联用技术测定血清中4种有机磷酸三酯（磷酸三苯酯（TPHP）、磷酸三乙酯（TEP）、磷酸三丁酯（TnBP）和磷酸三（2-氯乙基）酯（TCEP））和2种有机磷酸二酯（磷酸二苯酯（DPHP）和磷酸二乙酯（DEP））的生物监测分析方法。400 μL样品经乙酸乙酯（1.2 mL）-甲酸（FA，60 μL）萃取，采用冷冻真空离心进行浓缩，在Phenomenex Kinetex 2.6 μm F5 LC色谱柱上分离，采用H₂O（含0.1% FA）-甲醇溶液梯度洗脱，ESI正负离子切换模式下多反应监测（MRM）扫描，同位素内标法进行定量分析。结果表明，6种目标物在较宽浓度范围内线性关系良好（R²>0.99），检出限（LODs）为0.002~0.01 ng/mL，定量限（LOQs）为0.01~0.05 ng/mL，回收率为56.1%~112.2%，日内和日间精密度良好（RSD<15%）。采用本方法检测了30份上海居民血清样本，6种目标物的检出率为100%。本方法适用于大样本量人群血液中痕量有机磷酸三酯和二酯的生物监测研究，对于评价新型环境污染物有机磷酸酯（OPEs）的人群暴露与潜在的健康风险具有重要意义。

关键词:

English

Ultra-High Performance Liquid Chromatography Coupled with Triple Quadrupole Mass Spectrometry for Simultaneous Determination of Organophosphate Triesters and Diesters in Serum for Human Biomonitoring Study

1.
Centers for Water and Health, Key Laboratory of Public Health Safety, Ministry of Education, Fudan University, Shanghai 200032, China;
2.
Department of Chemistry in Public Health Science, School of Public Health, Fudan University, Shanghai 200032, China;
3.
Department of Environmental Health, School of Public Health, Fudan University, Shanghai 200032, China;
4.
Pudong New Area for Disease Control and Prevention, Fudan University Pudong Institute of Preventive Medicine, Shanghai 200136, China

Corresponding author: ZHOU Ying, yingchou@fudan.edu.cn

Received Date: 07 September 2020
Revised Date: 19 May 2021
Fund Project:
Supported by the National Key Research and Development Program of China (No.2017YFC1600500) and the National Natural Science Foundation of China (No.81373089).

Abstract: A method for rapid and simultaneous determination of organophosphate triesters (triphenyl phosphate (TPHP), triethyl phosphate (TEP), tri-n-butylphosphate (TnBP), tri(2-chloroethyl) phosphate (TCEP)) and diesters (diethyl phosphate (DEP) and diphenyl phosphate (DPHP)) in human serum by ultra-high performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC-MS/MS) was developed. Serum sample (400 μL) was extracted using 1.2 mL of ethyl acetate with 60 μL of formic acid, followed by concentrating the extracts with freeze vacuum centrifugation technology. The sample was separated on a Phenomenex Kinetex 2.6 μm F5 LC column with formic acid aqueous solution and methanol as the mobile phase, and then detected in turn under electrospray ionization (ESI) positive and negative ion multiple reactive monitoring (MRM) mode. Stable isotope-labeled internal standards were used to improve the assay performance of UPLC-MS/MS. The analytical parameters involving sample pretreatment, chromatographic separation and mass determination were optimized. Under the optimal conditions, low limits of detection (0.002-0.01 ng/mL), wide linearity (0.05-50 ng/mL) and good recovery (56.1%-112.2%) were achieved. The intra-day and inter-day precisions were expressed as variation coefficients within 15%. The proposed method was successfully applied to the determination of six target compounds in 30 serum specimens collected from residents living in Shanghai city. This method provided a reliable alternative for large-scale monitoring trace level of organophosphate triesters and diesters in human exposure measurement and risk assessment.

Key words:

Organophosphate triesters
/ Organophosphate diesters
/ Biomonitoring
/ Ultra-high performance liquid chromatography coupled with triple quadrupole mass spectrometry
/ Serum

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

人血清中有机磷酸三酯和二酯的生物监测方法的建立

通讯作者: 周颖,E-mail:yingchou@fudan.edu.cn

English

Ultra-High Performance Liquid Chromatography Coupled with Triple Quadrupole Mass Spectrometry for Simultaneous Determination of Organophosphate Triesters and Diesters in Serum for Human Biomonitoring Study

Corresponding author: ZHOU Ying, yingchou@fudan.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

人血清中有机磷酸三酯和二酯的生物监测方法的建立

通讯作者: 周颖,E-mail:yingchou@fudan.edu.cn

English

Ultra-High Performance Liquid Chromatography Coupled with Triple Quadrupole Mass Spectrometry for Simultaneous Determination of Organophosphate Triesters and Diesters in Serum for Human Biomonitoring Study

Corresponding author: ZHOU Ying, yingchou@fudan.edu.cn

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

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

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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