色谱

色谱 ›› 2015, Vol. 33 ›› Issue (7): 691-698.DOI: 10.3724/SP.J.1123.2015.03010

• 研究论文 • 上一篇    下一篇

在线固相萃取/液相色谱-线性离子阱质谱法同时定性定量检测全血和尿液中7种抗凝血杀鼠药

黄克建1, 卢敏萍2, 周哲3, 林翠梧2, 杨宁1, 刘晓锋1, 朱定姬4, 梁平1, 乔文涛1, 李宏森1, 李璐1, 黄晓青1   

  1. 1. 广西壮族自治区公安厅物证鉴定中心, 广西 南宁 530012;
    2. 广西大学化学化工学院, 广西 南宁 530004;
    3. 赛默飞世尔科技(中国)有限公司, 上海 201206;
    4. 广西壮族自治区职业病防治研究院, 广西 南宁 530021
  • 收稿日期:2015-03-16 出版日期:2015-07-08 发布日期:2015-07-27
  • 通讯作者: 黄克建

Simultaneous qualitative and quantitative determination of seven anticoagulant rodenticides in whole blood and urine samples using on-line solid phase extraction with liquid chromatography-linear ion trap mass spectrometry

HUANG Kejian1, LU Minping2, ZHOU Zhe3, LIN Cuiwu2, YANG Ning1, LIU Xiaofeng1, ZHU Dingji4, LIANG Ping1, QIAO Wentao1, LI Hongsen1, LI Lu1, HUANG Xiaoqing1   

  1. 1. Institute of Forensic Science, Public Security Department of Guangxi Zhuang Autonomous Region, Nanning 530012, China;
    2. School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China;
    3. Thermo Fisher Scientific (China) Co., Ltd., Shanghai 201206, China;
    4. Guangxi Zhuang Autonomous Region Institute for the Prevention and Treatment of Occupational Diseases, Nanning 530021, China
  • Received:2015-03-16 Online:2015-07-08 Published:2015-07-27

PDF

166

被引次数

9

摘要：

建立了同时测定全血和尿液样品中7种抗凝血杀鼠药的在线固相萃取/液相色谱-线性离子阱质谱(on-line SPE/LC-LIT/MS)分析方法。用乙腈沉淀样品中的蛋白质,于稀释、离心、过滤后直接进样。经在线固相萃取柱富集纯化;以C18柱为分析柱,甲醇-乙酸铵水溶液(0.02 mol/L)为流动相进行梯度洗脱;在电喷雾电离(ESI)负离子模式下,记录目标母离子在锁定保留时间窗口内的二级全扫描信号,通过自建数据库进行定性确证,挑选高灵敏度与专属性的二级子离子进行定量,从而实现7种杀鼠药的同时定性和定量分析。7种杀鼠药在各自质量浓度范围内线性关系良好,相关系数为0.9946~0.9997,检出限和定量限分别为0.02~1.00 ng/mL和0.10~4.00 ng/mL, 3个添加水平的回收率为81.0%~113.9%,相对标准偏差为0.1%~6.2% (n=6)。该方法简单方便,灵敏度高,能够满足全血和尿液样品中7种抗凝血杀鼠药的快速筛查和准确定量。

关键词: 抗凝血杀鼠药, 尿液, 全血, 液相色谱-线性离子阱质谱法, 在线固相萃取

Abstract:

A new and sensitive analytical method has been developed for the simultaneous determination of seven anticoagulant rodenticides in whole blood and urine samples by liquid chromatography-linear ion trap mass spectrometry (LC-LIT/MS) with on-line solid phase extraction (on-line SPE). The samples were treated with acetonitrile, followed by dilution, centrifugation, and filtration. The resulting solution was injected into the LC system directly and processed by on-line SPE column for enrichment and purification. Separation was performed on a C18 column with mixed mobile phases of methanol and 0.02 mol/L ammonium acetate aqueous solution for gradient elution. The analytes were detected by the mass spectrometer with electrospray ionization (ESI) in negative mode. MS2 full scan signals of the target parent ions within the locked retention time window were recorded. Self-built database searching was performed for qualitative confirmation, and MS2 fragment ions with high sensitivity and specificity were selected for quantification. Simultaneous qualitative and quantitative analyses of the seven rodenticides were achieved in this way. Good linearities were obtained within the investigated mass concentration ranges of the seven rodenticides, with r2≥0.9958 in blood and r2≥0.9946 in urine. The LODs varied from 0.02 ng/mL to 1.00 ng/mL, and the LOQs varied from 0.10 ng/mL to 4.00 ng/mL. The recoveries at three spiked levels in blood and urine samples ranged from 81.0% to 113.9%, with RSDs of 0.1%-6.2% (n=6). The developed method is simple, sensitive, and can be used for the rapid detection and accurate quantification of the seven anticoagulant rodenticides in whole blood and urine samples.

Key words: anticoagulant rodenticides, liquid chromatography-linear ion trap mass spectrometry (LC-LIT/MS), on-line solid phase extraction (on-line SPE), urine, whole blood

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