色谱

色谱 ›› 2018, Vol. 36 ›› Issue (9): 895-903.DOI: 10.3724/SP.J.1123.2018.04002

• 研究论文 • 上一篇    下一篇

超高效液相色谱-三重四极杆质谱法测定人尿中9种邻苯二甲酸酯代谢物

张续, 邱天, 付慧, 杨艳伟, 赵峰, 林少彬, 胡小键   

  1. 中国疾病预防控制中心环境与健康相关产品安全所, 北京 100021
  • 收稿日期:2018-04-01 出版日期:2018-09-08 发布日期:2014-08-05
  • 通讯作者: 胡小键,E-mail:huxj163@163.com
  • 基金资助:

    北京市自然科学基金（7182119）.

Determination of nine phthalate ester metabolites in human urine using ultra high performance liquid chromatography-tandem triple quadrupole mass spectrometry

ZHANG Xu, QIU Tian, FU Hui, YANG Yanwei, ZHAO Feng, LIN Shaobin, HU Xiaojian   

  1. National Institute of Environmental Health, Chinese Center for Disease Control and Prevention, Beijing 100021, China
  • Received:2018-04-01 Online:2018-09-08 Published:2014-08-05
  • Supported by:

    Natural Science Foundation of Beijing (No. 7182119).

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摘要：

建立了人尿中9种邻苯二甲酸酯（PAE）代谢物的超高效液相色谱-三重四极杆质谱（UPLC-MS/MS）测定方法。2 mL尿液样本酶解2 h后，经强阴离子固相萃取净化处理；选用Waters ACQUITY UPLC BEH Phenyl色谱柱（100 mm×2.1 mm，1.7 μ m），以0.1%（体积分数）乙酸乙腈和0.1%（体积分数）乙酸水溶液为流动相进行梯度洗脱；在负离子电喷雾多反应监测模式（MRM）下测定9种PAE代谢物含量。8种PAE代谢物在0.39~200 μ g/L范围内、1种PAE代谢物在1.17~600 μ g/L范围内线性关系良好，相关系数均大于0.995。方法检出限为0.06~0.85 μ g/L，定量限为0.20~2.80 μ g/L。3个加标水平的加标回收率为84.1%~122%，精密度为4.5%~14.3%；日内精密度不高于9.3%，日间精密度不高于10.1%；基质效应和稳定性符合分析要求。应用该方法测定50份人尿液样本，邻苯二甲酸单环已酯（MCHP）和邻苯二甲酸单苄酯（MBZP）的检出率分别为0和44.0%，其余7种PAE代谢物的检出率为100%。该方法操作简单、定量准确、稳定性好，适用于人尿中9种PAE代谢物的定量分析。

关键词: 超高效液相色谱-三重四极杆质谱, 固相萃取, 邻苯二甲酸酯代谢物, 尿液

Abstract:

A method was developed to determine trace concentrations of phthalate ester (PAE) metabolites in human urine by using ultra high performance liquid chromatography-triple quadrupole mass spectrometry. Aliquots (2 mL) of human urine samples were purified using strong anion-exchange solid-phase extraction after enzymatic deconjugation by glucuronidase for 2 h. The separation was performed on a Waters ACQUITY UPLC BEH Phenyl column (100 mm×2.1 mm, 1.7 μ m) with gradient elution by 0.1% (v/v) acetic acid in acetonitrile and 0.1% (v/v) acetic acid aqueous solution. The concentrations of nine PAE metabolites were determined under a multiple reaction monitoring mode by negative electrospray ionization. Eight of the determined metabolites showed good linearities in the range of 0.39-200 μ g/L, and the ninth metabolite showed linearity in the range of 1.17-600 μ g/L with correlation coefficients > 0.995. The limits of detection ranged from 0.06 to 0.85 μ g/L, and the limits of quantification ranged from 0.20 to 2.80 μ g/L. The recovery rates at all three spiked levels ranged from 84.1% to 122% with relative standard deviations between 4.5% and 14.3%. The intra-and inter-day precisions were not more than 10.1% and 9.3%, respectively. The matrix effect and stability were found to be favorable for analysis. This method was utilized for the determination of 50 human urine samples. The detection rates of monocyclohexyl phthalate (MCHP) and monobenzyl phthalate (MBZP) were 0 and 44.0%, and the detection rates of the other seven PAE metabolites was 100%. This method has the advantage of convenient operation and good accuracy and stability, and is suitable for the quantitative determination of the nine PAE metabolites in human urine.

Key words: phthalate ester (PAE) metabolites, solid phase extraction (SPE), ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), urine

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