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采用超高效液相色谱串联质谱法同时测定尿液中多种异构羟基化多环芳烃

Simultaneous determination of multiple isomeric hydroxylated polycyclic aromatic hydrocarbons in urine by using ultra-high performance liquid chromatography tandem mass spectrometry.

作者信息

Hua Liting, Guo Sai, Wang Yu, Sun Hongwen, Zhao Hongzhi

机构信息

Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China.

Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China.

出版信息

J Chromatogr B Analyt Technol Biomed Life Sci. 2021 Nov 1;1184:122983. doi: 10.1016/j.jchromb.2021.122983. Epub 2021 Oct 7.

DOI:10.1016/j.jchromb.2021.122983
PMID:34655894
Abstract

Monitoring the level of hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in urine is the key to exploring human metabolic changes and comprehensive potential toxicity of PAHs. The OH-PAHs with isomeric structure have different biological functions, indicating that their quantification is indispensable. However, the quantitation method is still dissatisfactory due to the poor separation of these isomeric OH-PAHs. The current study established a ultra-high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS) method to complete the simultaneous determination of 17 OH-PAHs, including two naphthalene metabolites (1-hydroxynaphthalene, 2-hydroxynaphthalene), two fluorene metabolites (2-hydroxyfluorene, 3-hydroxyfluorene), five phenanthrene metabolites (1-hydroxyphenanthrene, 2-hydroxyphenanthrene, 3-hydroxyphenanthrene, 4-hydroxyphenanthrene, 9-hydroxyphenanthrene), a pyrene metabolite (1-hydroxypyrene), five chrysene metabolites (1-hydroxychrysene, 2-hydroxychrysene, 3-hydroxychrysene, 4-hydroxychrysene, 6-hydroxychrysene) and two benzo[a]pyrene metabolites (3-hydroxybenzo[a]pyrene, 9-hydroxybenzo[a]pyrene). The method validation results showed good selectivity, linearity (r > 0.999), inter-day and intra-day precision (relative standard deviation (RSD) < 5.5% and RSD < 6.3%), stability (RSD < 19.3%), matrix effect (-8.3%-11.5%) and recovery (65.9%-116.2%). This method is convenient, sensitive and efficient, saving expensive materials and complicated derivatization procedures. The practical applicability of developed approach was also tested in urine samples to identify potential biomarkers of PAHs exposure in humans, and a great compromise was obtained between recoveries and extract convenience. The developed approach may be widely utilized for specific determination of OH-PAHs with isomer structure in urine samples. It is expected that the application of this method may provide powerful references for PAHs exposure assessment.

摘要

监测尿液中羟基化多环芳烃(OH-PAHs)的水平是探索人类代谢变化和PAHs综合潜在毒性的关键。具有异构体结构的OH-PAHs具有不同的生物学功能,这表明对它们进行定量分析是必不可少的。然而,由于这些异构体OH-PAHs的分离效果不佳,其定量方法仍不尽人意。当前研究建立了一种超高效液相色谱(UHPLC)串联质谱(MS)方法,以完成对17种OH-PAHs的同时测定,包括两种萘代谢物(1-羟基萘、2-羟基萘)、两种芴代谢物(2-羟基芴、3-羟基芴)、五种菲代谢物(1-羟基菲、2-羟基菲、3-羟基菲、4-羟基菲、9-羟基菲)、一种芘代谢物(1-羟基芘)、五种 Chrysene 代谢物(1-羟基 Chrysene、2-羟基 Chrysene、3-羟基 Chrysene、4-羟基 Chrysene、6-羟基 Chrysene)和两种苯并[a]芘代谢物(3-羟基苯并[a]芘、9-羟基苯并[a]芘)。方法验证结果表明该方法具有良好的选择性、线性(r > 0.999)、日间和日内精密度(相对标准偏差(RSD)< 5.5% 和 RSD < 6.3%)、稳定性(RSD < 19.3%)、基质效应(-8.3%-11.5%)和回收率(65.9%-116.2%)。该方法简便、灵敏、高效,节省了昂贵的材料和复杂的衍生化程序。还在尿液样本中测试了所开发方法的实际适用性,以确定人类PAHs暴露的潜在生物标志物,并且在回收率和提取便利性之间取得了很大的平衡。所开发的方法可广泛用于尿液样本中具有异构体结构的OH-PAHs的特异性测定。预计该方法的应用可为PAHs暴露评估提供有力参考。

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