摘要
建立了超高效液相色谱-四极杆-飞行时间质谱法(UPLC-Q-TOF/MS)同时分析血液中110种农药的方法。在2mL离心管中,加入200μL血液样品和1 000μL甲醇,混合均匀,涡旋振荡2min,离心10min,取上清液在优化的仪器工作条件下进行测定。采用Kinetex Biphenyl色谱柱为固定相,以5mmol·L^-1甲酸铵溶液(A)和含5mmol·L^-1甲酸铵的甲醇溶液(B)的混合溶液为流动相进行梯度洗脱。在电喷雾离子源正离子(ESI+)模式和信息依赖采集(IDA)模式下,依次采集一级和二级质谱信息。采用Master View软件通过质量误差、保留时间误差、差异同位素比、谱库相似程度等4个因子获得的综合得分来进行定性筛查;采用Multi Quant软件通过提取离子流(XIC)色谱图中的前体离子的峰面积进行定量分析。结果表明:110种目标农药化合物的综合得分为81.8~97.0分,所得结果均大于定性筛查的最低限(80分)。110种目标农药化合物的质量浓度在5~200μg·L^-1内与其对应的色谱峰面积呈线性关系,相关系数在0.99以上,检出限(3S/N)为2μg·L^-1。以空白血为基质进行3个浓度水平的加标回收试验,目标农药的回收率为80.3%~120%,测定值的相对标准偏差(n=6)为1.9%~20%。以混合标准溶液和用空白基质配制的同浓度的混合标准溶液中各农药的峰面积的比值评估基质效应,110种农药的基质效应为80.65%~119.86%。采用此方法分析了2起农药中毒案件中的血液样品,分别检出了敌敌畏、毒死蜱、氯氰菊酯(案件1)和阿特拉津、氯氟氰菊酯、克百威(案件2),其定性筛查中4个因子的综合得分均大于80分,质量浓度分别为183.98,156.79,104.67μg·L^-1和144.57,165.32,138.91μg·L^-1。
A method of ultra-high performance liquid chromatography-quadrupole-time of flight mass spectrometry(UPLC-Q-TOF/MS)for simultaneous analysis of 110 pesticides in blood was established.200μL blood sample and 1000μL methanol were mixed in a 2 mL centrifuge tube,and the mixture was vortexed for 2 min to have the target extracted.After centrifuging for 10 min,the supernatant was analyzed under the optimized instrumental conditions.A Kinetex Biphenyl chromatographic column was used as the stationary phase,and a mixed solution containing of 5 mmol·L-1 ammonium formate solution(A)and methanol solution containing 5 mmol·L-1 ammonium formate(B)was used as the mobile phase for gradient elution.Under the mode of ESI+and IDA,primary and secondary mass spectrometry information were collected in sequence.Qualitative screening was performed using Master View software through a combined score obtained from 4 factors including mass error,retention time error,isotope ratio difference and library similarity;Multi Quant software was used for quantitative analysis by the peak area of the precursor ion in XIC chromatogram.The results showed that the combined scores of110 target pesticides were ranged from 81.8 to 97.0 points,all above the minimum score of qualitative screening(80 point).The mass concentrations of 110 target pesticides were linearly related to the corresponding chromatographic peak areas in the range of 5-200μg·L-1,and the correlation coefficients were all above 0.99.The limits of detection(3 S/N)found were same of 2μg·L-1.The spiked recovery test was made by using the blank blood as matrix at 3 concentration levels,giving the recoveries of the target pesticides in the range of 80.3%-120%,and RSDs(n=6)of the determined values were ranged from 1.9%to 20%.The matrix effects were evaluated by the ratio of the peak area of the same compound with the same mass concentration between the standard solution and the blank matrix matching solution,and matrix effects of 110 pesticides were found in the range of 80.65%-119.
作者
杜秋瑶
张云峰
王继芬
王璐
常靖
董林沛
吴小军
刘冰洁
DU Qiuyao;ZHANG Yunfeng;WANG Jifen;WANG Lu;CHANG Jing;DONG Linpei;WU Xiaojun;LIU Bingjie(College of Investigation,People′s Public Security University of China,Beijing 100038,China;Institute of Forensic Science,Ministry of Public Security,Beijing 100038,China;Agro-Environmental Protection Institute,Ministry of Agriculture and Rural Affairs,Tianjin 300191,China;SCIEX Asia Pacific Application Support Center,Beijing 100015,China)
出处
《理化检验（化学分册）》
CAS
CSCD
北大核心
2020年第8期851-864,共14页
Physical Testing and Chemical Analysis(Part B:Chemical Analysis)
基金
国家重点研发计划项目(2017YFC0803504)。
关键词
超高效液相色谱-四极杆-飞行时间质谱法
农药
血液
定性筛查
定量分析
ultra-high performance liquid chromatography-quadrupole-time of flight mass spectrometry
pesticide
blood
qualitative screening
quantitative analysis
