色谱

色谱 ›› 2018, Vol. 36 ›› Issue (6): 523-530.DOI: 10.3724/SP.J.1123.2018.03002

• 生物基质农兽药残留检测专栏 • 上一篇    下一篇

高效液相色谱-串联质谱法测定兔尿中溴氰菊酯及其毒性生物标志物

曹文卿1,2, 吴振兴1, 梁成珠1, 静平1, 崔淑华1, 杨桂朋2, 林黎明1   

  1. 1. 山东出入境检验检疫局检验检疫技术中心, 山东 青岛 266002;
    2. 中国海洋大学化学化工学院, 山东 青岛 266100
  • 收稿日期:2018-03-26 出版日期:2018-06-08 发布日期:2014-04-24
  • 通讯作者: 林黎明,E-mail:sdciqllm@126.cn
  • 基金资助:

    国家质检总局科技支撑项目（2008IK263）；青岛市创业创新领军人才项目计划（13-CX-28）.

Determination of deltamethrin and its toxicity biomarkers in rabbit urine by high performance liquid chromatography-tandem mass spectrometry

CAO Wenqing1,2, WU Zhenxing1, LIANG Chengzhu1, JING Ping1, CUI Shuhua1, YANG Guipeng2, LIN Liming1   

  1. 1. Technical Center of Inspection and Quarantine, Shandong Entry-Exit Inspection and Quarantine Bureau, Qingdao 266002, China;
    2. College of Chemistry and Chemical Engineering of Ocean University of China, Qingdao 266100, China
  • Received:2018-03-26 Online:2018-06-08 Published:2014-04-24
  • Supported by:

    Science and Technology Project of General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China (No.2008IK263);Project Plan of Leading Talent for Entrepreneurship and Innovation in Qingdao (No.13-CX-28).

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摘要：

建立了一种应用高效液相色谱-串联质谱（HPLC-MS/MS）测定兔尿中与溴氰菊酯毒性相关的多种生物标志物的检测方法。分析物包括溴氰菊酯及其代谢产物1R，3R-二溴菊酸、3-苯氧基苯甲酸，以及5种生物标志物5-羟色胺、5-羟基吲哚乙酸、3-硝基丙酸、8-羟基脱氧鸟苷和6-甲氧基鸟嘌呤。样品经硅藻土基质固相分散萃取、三氯乙酸沉淀蛋白质和HLB固相萃取小柱净化，使用电喷雾离子源，在多反应监测模式下正负切换采集测定，其中溴氰菊酯、5-羟色胺、5-羟基吲哚乙酸、8-羟基脱氧鸟苷和6-甲氧基鸟嘌呤采用正离子模式，1R，3R-二溴菊酸、3-苯氧基苯甲酸和3-硝基丙酸采用负离子模式。基质校准曲线外标法定量。结果表明，7种生物标志物在各自的浓度范围内线性关系良好（R2不小于0.9914），5-羟基吲哚乙酸的检出限和定量限分别为20 μg/L和50 μg/L，其余化合物的检出限和定量限分别为0.2~5.0 μg/L和0.5~10 μg/L；在兔尿中3个不同添加水平的平均回收率为74.2%~98.7%，相对标准偏差（RSD）不大于12%，方法简单、快速、准确、灵敏，可作为溴氰菊酯暴露评估的检测方法。

关键词: 1R, 3R-二溴菊酸, 3-苯氧基苯甲酸, 高效液相色谱-串联质谱, 生物标志物, 溴氰菊酯

Abstract:

A method was developed for the determination of biomarkers related to toxicity of deltamethrin in rabbit urine by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The target analytes in this method are as follows:deltamethrin and its two metabolites (1R-cis)-3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane carboxylic acid (dibromochrysanthemic acid) and 3-phenoxybenzoic acid (3-PBA), and five toxic biomarkers, viz. serotonin hydrochloride (5-HT), 5-hydroxyindole-3-acetic acid (5-HIAA), 3-nitropropionic acid (3-NPA), 8-hydroxy-2'-deoxyguanosine (8-OHdG), and 6-methoxyguanine. Urine samples were cleaned by matrix solid-phase dispersion extraction (MSPD) with diatomite; and protein was precipitated with trichloroacetic acid; and then the sample solutions were purified with hydrophilic-lipophilic balance (HLB) solid-phase extraction cartridges. The biomarkers were analyzed with electrospray ionization (ESI) in a positive and negative switching scan mode, in which the positive scan mode was used for deltamethrin, 5-HT, 5-HIAA, 8-OHdG, and 6-methoxyguanine, and the negative scan mode was used for (1R-cis)-3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane, 3-PBA, and 3-NPA. The target compounds were quantified with the external standard using matrix calibration curves. The linear regression curves of the eight target compounds were linear with correlation coefficients no less than 0.9914. The LOD and LOQ of 5-HIAA were 20 μg/L and 50 μg/L, respectively, and the LODs and LOQs of the other analytes were 0.2-5.0 μg/L and 0.5-10 μg/L, respectively. The average recoveries of the analytes spiked in rabbit urine ranged from 74.2% to 98.7% at three levels, with relative standard deviations (RSDs) no more than 12%. The method was simple, fast, accurate, sensitive, and suitable for the detection for the exposure evaluation of deltamethrin.

Key words: (1R-cis)-3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane carboxylic acid (dibromochrysanthemic acid), 3-phenoxybenzoic acid, biomarkers, deltamethrin, high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

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