Determination of paraquat and diquat in human body fluids by high-performance liquid chromatography/tandem mass spectrometry
Determination of paraquat and diquat in human body fluids by high-performance liquid chromatography/tandem mass spectrometry
复制标题
DOI：
10.1002/jms.695
复制
发表时间：
2004-10-01
影响因子：
2.3
通讯作者：
Sato, K
中科院分区：
文献类型：
--
作者：
Lee, XP;Kumazawa, T;Sato, K
采用高效液相色谱/串联质谱法（HPLC/MS/MS）结合正离子电喷雾电离（ESI）对人全血和尿液中的百草枯（PQ）和敌草快（DQ）进行了分析。以乙基百草枯为内标，用Sep - Pak C - 18柱从全血和尿液样本中提取化合物。采用离子对色谱法，以20 mmol/L醋酸铵中的七氟丁酸和乙腈进行梯度洗脱，实现了PQ和DQ的分离，以便成功与质谱联用。通过HPLC/ESI - MS，两种化合物均因[M - H]⁺离子形成基峰，通过HPLC/MS/MS，每种[M - H]⁺离子产生产物离子。选择反应监测（SRM）对两种体液均显示出高得多的灵敏度。因此，建立了用HPLC/MS/MS通过SRM检测化合物的详细方法，并进行了仔细验证。PQ和DQ在全血中的回收率为80.8% - 95.4%，在尿液中的回收率为84.2% - 96.7%。PQ和DQ在全血和尿液中的校准曲线在25 - 400 ng/mL范围内呈现良好的线性。两种化合物在两种体液中的检测限分别为PQ 10 ng/mL和DQ 5 ng/mL。全血和尿液样本中两种化合物的日内和日间精密度均不大于13.0%。还给出了大鼠口服这些化合物后血液中PQ和DQ的测定数据。版权所有（C）2004约翰威立父子有限公司
Paraquat (PQ) and diquat (DQ) in human whole blood and urine were analyzed by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) with positive ion electrospray ionization (ESI). The compounds were extracted with Sep-Pak C-18 cartridges from whole blood and urine samples containing ethyl paraquat as an internal standard. The separation of PQ and DQ was carried out using ionpair chromatography with heptafluorobutyric acid in 20 mm ammonium acetate and acetonitrile gradient elution for successful coupling with MS. Both compounds formed base peaks due to [M - H](+) ions by HPLC/ESI-MS and the product ions produced from each [M - H](+) ion by HPLC/MS/MS. Selective reaction monitoring (SRM) showed much higher sensitivity for both body fluids. Therefore, a detailed procedure for the detection of compounds by SRM with HPLC/MS/MS was established and carefully validated. The recoveries of PQ and DQ were 80.8-95.4% for whole blood and 84.2-96.7% for urine. The calibration curves for PQ and DQ showed excellent linearity in the range of 25-400 ng ml(-1) of whole blood and urine. The detection limits were 10 ng ml(-1) for PQ and 5 ng ml(-1) for DQ in both body fluids. The intra- and inter-day precision for both compounds in whole blood and urine samples were not greater than 13.0%. The data obtained from the determination of PQ and DQ in rat blood after oral administration of the compounds are also presented. Copyright (C) 2004 John Wiley Sons, Ltd.