快速溶剂萃取-离子色谱-质谱法测定人体血液、尿液中的氟乙酸  

Determination of fluoroacetic acid in human blood and urine by accelerated solvent extraction-ion chromatography-mass spectrometry

作　　者：王禹衡 张婧文 郑洪国 卢思佳 于素华 杨瑞琴[1] 王勇[3] WANG Yuheng;ZHANG Jingwen;ZHENG Hongguo;LU Sijia;YU Suhua;YANG Ruiqin;WANG Yong(School of Investigation,People’s Public Security University of China,Beijing 100038,China;Thermo Fisher Scientific Inc.,Chengdu 610023,China;Institute of Forensic Science and Technology of Nanjing Public Security Bureau,Nanjing 210001,China)

机构地区：[1]中国人民公安大学侦查学院,北京100038 [2]赛默飞世尔科技(中国)有限公司,四川成都610023 [3]南京市公安局刑事科学技术研究所,江苏南京210001

出　　处：《色谱》2023年第6期497-503,共7页Chinese Journal of Chromatography

基　　金：公安部技术研究计划项目(2021JSYJC20);公安部应用创新计划(2020YYCXJSST021);公安部刘耀院士专项基金项目(2021-ZZ-01).

摘　　要：建立了快速溶剂萃取-离子色谱-质谱法测定人体血液、尿液中氟乙酸的方法。以去离子水为萃取溶剂,使用快速溶剂萃取仪处理血液和尿液样品,取上清液依次经超滤管和0.22μm水相针式滤膜净化,稀释50倍后进样检测。采用Ion Pac AS20离子色谱柱以15.0 mmol/L的KOH溶液为淋洗液进行等度淋洗,流出液通过抑制器后进入三重四极杆质谱,在负离子、多反应监测模式下检测,外标法定量。结果表明,氟乙酸在0.5~500.0μg/L范围内线性关系良好(r>0.999),检出限和定量限分别为0.14、0.47μg/L。氟乙酸在血液和尿液中的回收率分别为93.4%~95.8%、96.2%~98.4%,日内精密度分别为0.8%~1.6%、0.2%~1.0%,日间精密度分别为2.3%~3.8%、3.9%~6.9%。进一步考察发现该方法在血液、尿液中的基质效应较弱,分别为-7.4%、-3.0%。该法无需衍生化处理,简便高效,灵敏度高,重复性好,适用于人体血液、尿液中氟乙酸的快速检测。Fluoroacetic acid is a highly polar poison used for rodent control.When ingested by the human body,it seriously damages nerve cells and heart tissues and even causes death by cardiac arrest or respiratory failure.Common detection methods for fluoroacetic acid include gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry,both of which require complex pretreatment methods,such as derivatization.In this study,a method to determine fluoroacetic acid in human blood and urine based on accelerated solvent extraction-ion chromatography-mass spectrometry(ASE-IC-MS)was established.Two pretreatment methods,namely,acetonitrile precipitation and accelerated solvent extraction,were compared.Furthermore,the effects of different extraction conditions,such as the extraction time,extraction temperature,and number of cycles,were investigated.The most suitable chromatographic separation conditions,such as the chromatographic column,column temperature,and elution procedure,were determined,and the MS conditions,such as the collision energy(CE)and declustering potential(DP)of the ion pairs of the target compound,were investigated.Based on the experimental results,the optimal pretreatment methods and detection conditions were obtained,and reliable data were collected.Deionized water was used as the extraction solvent,and blood and urine samples were processed by accelerated solvent extractor.The supernatant was sequentially collected via centrifugal ultrafiltration and 0.22μm membrane filtration,diluted 50 times,and then injected into the chromatographic column for detection.An Ion Pac AS20 IC column was used for isocratic elution with 15.0 mmol/L KOH solution as the eluent.The effluent was passed through a suppressor and into a triple quadrupole mass spectrometer,which was used to perform MS/MS(ESI^(-))in multiple reaction monitoring(MRM)mode.The quantitative ion was m/z 77.0>57.0 when the CE and DP were-15.0 eV and-20.0 V,respectively.An external standard method was used for quantitative analysis.The result

关 键 词：快速溶剂萃取 离心超滤 离子色谱-串联质谱法 氟乙酸 血液 尿液 

分 类 号：O658[理学—分析化学]