涉案乌头生物碱与1-甲基海因的LC-MS/MS快速检测  

Rapid detection of aconitum alkaloids and 1-methylhydantoin by LC-MS/MS

作　　者：徐恩宇 蒋锐 朱琳[1] 王子威 张师儒 袁慧雅 高利娜[1] 刘俊亭[1] XU En-yu;JIANG Rui;ZHU Lin;WANG Zi-wei;ZHANG Shi-ru;YUAN Hui-ya;GAO Li-na;LIU Jun-ting(Department of Forensic Analytical Toxicology,China Medical University,Shenyang 110122)

机构地区：[1]中国医科大学法医毒物分析教研室,沈阳110122

出　　处：《分析试验室》2019年第2期125-130,共6页Chinese Journal of Analysis Laboratory

基　　金：国家自然科学基金面上项目(81671864);中国医科大学校内基金(XZR20160033);中国医科大学大学生创新训练项目(201710159000022;201710159000053和201710159000191)资助

摘　　要：建立生物检材中1-甲基海因和乌头生物碱的快速分析方法,并提示检材新鲜度与1-甲基海因含量的相对关系。取全血样品经乙腈提取,使用Agilent Poroshell 120 SB-C_(18)(2. 1 mm×100 mm,2. 7μm)色谱柱,以0. 1%甲酸溶液-乙腈(30:70,V/V)为流动相等度洗脱,在多反应监测模式下测定全血样品中1-甲基海因和乌头生物碱成分。用于定量分析的离子对分别为1-甲基海因:m/z 115. 1 [M+H]^+→42. 2,乌头碱:m/z 646. 4 [M+H]^+→586. 3,新乌头碱:m/z 632. 3 [M+H]^+→572. 4和次乌头碱:m/z 616. 3 [M+H]^+→556. 3。4种目标物在各自的浓度范围内线性关系良好(R2≥0. 99),3个添加浓度(5,50,250 ng/mL)下,回收率在85. 7%～95. 2%之间,检出限(S/N=3)在0. 05～0. 5 ng/mL范围内,定量限(S/N=10)在0. 2～1 ng/mL范围内。利用建立的检测方法,发现与检材新鲜度有关的1-甲基海因和乌头生物碱的检出量有密切关系,为法医学鉴定结论的科学性服务。The goal of this study was to jointly employ liquid chromatography-tandem mass spectrometry (LC-MS/MS) to detect 1-methylhydantoin and aconitine alkaloids in specimen, and to investigate the relative relationship between sample freshness and 1-methylhydantoin content.The aconitum alkaloids and 1 -methylhydantoin were extracted from the whole blood by using acetonitrile and then analyzed by using HPLC-MS in multiple reaction monitoring ( MRM ) mode with positive ionization.The analytical column was Agilent Poroshell 120 SB-C18(2.1 mm×100mm, 2.7μm) and the mobile phase were water containing 0.1% formic acid : acetonitrile (30- 70, V/V) in isocratic elution.The precursor product ion combinations of 1 -methylhydantoin : m/z 115.1 [ M + H ] + →42.2, aconitine: m/z 646.4 [ M + H] +→586.3 , mesaconitine : m/z 632.3 [ M + H] +→-572.4 and hypaconitine: m/z 616.3 [ M + H] +→556.3 were used for quantitative analysis, respectively.The calibration curves were linear in their concentration ranges with the correlation coefficients (r^2) more than 0.99.The average recoveries of the method were 85.7 % to 95.2 %.The limits of detection (LODs) were in the range of 0.05 - 0.5 ng/mL ( S/N = 3 ) , and the limits of quantification ( LOQ ) were in the range of 0.2 - 1 ng/mL ( S/N = 10).It was found that 1-methylhydantoin related to sample freshness was closely related to the detection amount of aconitum alkaloids.This method holds the potontials in serving as a scientific service for forensic expert conclusions.

关 键 词：法医毒物分析 生物检材 液相色谱-串联质谱法 1-甲基海因 乌头生物碱 

分 类 号：R89[医药卫生—法医学] O657.6[医药卫生—临床医学]