超高效液相色谱-三重四极杆/线性离子阱串联质谱法同时快速筛查和检测食物中毒样品中的12种抗凝血杀鼠剂
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摘要
目的建立食物中毒样品中12种抗凝血杀鼠剂的超高效液相色谱-三重四极杆/线性离子阱串联质谱(QTrap LC-MS/MS)的检测方法。方法样品经快速分散固相萃取法(QuEChERS)提取和净化,ACQUITY UPLC BEH-C18柱(1.7μm,2.1mm×50mm)分离,5mmol/L乙酸铵和乙腈为流动相梯度洗脱,按照多级反应监测(MRM)→信息相关采集(IDA)→增强子离子扫描(EPI)→谱库检索的模式进行分析。结果 12种抗凝血杀鼠剂线性相关系数均大于0.99,平均回收率为78.2%~108.2%,相对标准偏差为1.8%~12.3%,方法的检出限为0.006~0.03μg/kg,定量限为0.02~0.10μg/kg。结论该法简便快速,灵敏度高、重现性较好,适用于食物中毒样品中12种抗凝血杀鼠剂同时快速测定。
Objective To establish a rapid analytical method for the simultaneous screening and detection of 12 anticoagulant rodenticides in food poisoning samples using an ultra-performance liquid chromatography-triple quadrupole/linear ion trap tandem mass spectrometry( UPLC-QTrap-MS/MS). Methods Food poisoning samples were extracted and purified with modified QuEChERS method. The 12 anticoagulant rodenticides and the internal standard( warfarin-D5) were separated using an ACQUITY UPLC BEH-C18 column( 1. 7μm,2. 1 mm × 50 mm) and gradient eluent was conducted with a mobile phase consisting of 5 mmol/L ammonium acetate formate buffer and acetonitrile. A multiple reaction monitoring( MRM) scan and an enhanced product ion( EPI) scan were performed in an information dependent acquisition( IDA) experiment. Results The calibration curves were linear( r > 0. 99) for all the compounds. The mean recoveries for the 12 analytes at three spiked levels were in the range of 78. 2% ~ 108. 2% with RSDs of 1. 8% ~ 12. 3%. The limits of detection( LODs) for the 12 rodenticides ranged from 0. 006 to 0. 03μg/kg. The limits of quantification( LOQs) for the 12 rodenticides were between 0. 02 and 0. 10 μg/kg. Conclusion The developed method is simple,rapid,sensitive and can be used for screening 12 kinds of anticoagulant rodenticide residues in food poisoning samples.
Objective To establish a rapid analytical method for the simultaneous screening and detection of 12 anticoagulant rodenticides in food poisoning samples using an ultra-performance liquid chromatography-triple quadrupole/linear ion trap tandem mass spectrometry( UPLC-QTrap-MS/MS). Methods Food poisoning samples were extracted and purified with modified QuEChERS method. The 12 anticoagulant rodenticides and the internal standard( warfarin-D5) were separated using an ACQUITY UPLC BEH-C18 column( 1. 7μm,2. 1 mm × 50 mm) and gradient eluent was conducted with a mobile phase consisting of 5 mmol/L ammonium acetate formate buffer and acetonitrile. A multiple reaction monitoring( MRM) scan and an enhanced product ion( EPI) scan were performed in an information dependent acquisition( IDA) experiment. Results The calibration curves were linear( r > 0. 99) for all the compounds. The mean recoveries for the 12 analytes at three spiked levels were in the range of 78. 2% ~ 108. 2% with RSDs of 1. 8% ~ 12. 3%. The limits of detection( LODs) for the 12 rodenticides ranged from 0. 006 to 0. 03μg/kg. The limits of quantification( LOQs) for the 12 rodenticides were between 0. 02 and 0. 10 μg/kg. Conclusion The developed method is simple,rapid,sensitive and can be used for screening 12 kinds of anticoagulant rodenticide residues in food poisoning samples.
引文
[1]朱姝,周亚娟,王娅芳.2004-2013年贵州省鼠药中毒情况分析[J].微量元素与健康研究,2015,32(4):37-39.
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[9]陈闻,耿梅梅,张丽萍,等.高效液相色谱法测定土壤中香豆素类灭鼠药残留[J].色谱,2016,34(9):912-917.
[10]何岸檐,周倩如,王正虹,等.尿液中鼠药代谢产物亚苄基丙酮测定方法研究[J].中国卫生检验杂志,2016,26(13):1841-1846.
[11]Vindenes V,Karinen R,Hasvold I,et al.Bromadiolone poisoning:LC-MS method and pharmacokinetic data[J].Journal of Forensic Sciences,2008,53(4):993-996.
[12]Grobosch T,Angelow B,Sch?nberg L,et al.Acute bromadiolone intoxication[J].Journal of Analytical Toxicology,2006,30(4):281-286.
[13]贾玉珠,蔡伟鹏,陈丽惠,等.三重四级杆液质联用法快速测定全血样中9种抗凝血类灭鼠剂[J].中国卫生检验杂志,2016,26(22):3196-3200.
[14]Imran M,Shafi H,Wattoo SA,et al.Analytical methods for determination of anticoagulant rodenticides in biological samples[J].Forensic Science International,2015,253:94-102.
[15]黄克建,卢敏萍,周哲,等.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[J].色谱,2015,33(7):691-698.
[16]Dong XF,Liang SX,Sun HW.Determination of seven anticoagulant rodenticides in human serum by ultra-performance liquid chromatography-mass spectrometry[J].Analytical Methods,2015,7(5):1884-1889.
[17]Chen ML,Zhu GF,Zhou LX,et al.Analysis of trace bromadiolone and brodifacoum in environmental water samples by ionic liquid ultrasound-assisted dispersive liquid–liquid microextraction and LC-MS/MS[J].Analytical Methods,2014,6(15):5879-5885.
[2]姜婷,王魏魏,李春雨,等.一家六口人抗凝血灭鼠药中毒临床特点分析[J].中华卫生应急电子杂志,2016,2(2):129-130.
[3]李蕙,贺钰磊,李丹,等.以凝血障碍为主要表现的儿童鼠药中毒15例临床分析[J].四川医学,2016,38(8):907-909.
[4]青胜兰,周婕,王艳.获得性凝血功能障碍29例临床分析[J].现代预防医学,2011,38(14):2887-2888.
[5]施向东.南宁市3年内儿童食物中毒现况调查[J].现代预防医学,2007,34(11):2115-2120.
[6]秦桂林,白桦林,陈洁.小儿急性中毒的临床特点及预防探讨[J].现代预防医学,2012,39(11):2728-2729.
[7]王洪宗,冯辉,胡开发,等.GC/ECD法测定生物检材中溴敌隆和大隆[J].中国法医学杂志,2008,23(6):405-406.
[8]Armentano A,Iammarino M,Lo Magro S,et al.Validation and application of multi-residue analysis of eight anticoagulant rodenticides by high-performance liquid chromatography with fluorimetric detection[J].Journal of veterinary diagnostic investigation:official publication of the American Association of Veterinary Laboratory Diagnosticians,Inc,2012,24(2):307-311.
[9]陈闻,耿梅梅,张丽萍,等.高效液相色谱法测定土壤中香豆素类灭鼠药残留[J].色谱,2016,34(9):912-917.
[10]何岸檐,周倩如,王正虹,等.尿液中鼠药代谢产物亚苄基丙酮测定方法研究[J].中国卫生检验杂志,2016,26(13):1841-1846.
[11]Vindenes V,Karinen R,Hasvold I,et al.Bromadiolone poisoning:LC-MS method and pharmacokinetic data[J].Journal of Forensic Sciences,2008,53(4):993-996.
[12]Grobosch T,Angelow B,Sch?nberg L,et al.Acute bromadiolone intoxication[J].Journal of Analytical Toxicology,2006,30(4):281-286.
[13]贾玉珠,蔡伟鹏,陈丽惠,等.三重四级杆液质联用法快速测定全血样中9种抗凝血类灭鼠剂[J].中国卫生检验杂志,2016,26(22):3196-3200.
[14]Imran M,Shafi H,Wattoo SA,et al.Analytical methods for determination of anticoagulant rodenticides in biological samples[J].Forensic Science International,2015,253:94-102.
[15]黄克建,卢敏萍,周哲,等.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[J].色谱,2015,33(7):691-698.
[16]Dong XF,Liang SX,Sun HW.Determination of seven anticoagulant rodenticides in human serum by ultra-performance liquid chromatography-mass spectrometry[J].Analytical Methods,2015,7(5):1884-1889.
[17]Chen ML,Zhu GF,Zhou LX,et al.Analysis of trace bromadiolone and brodifacoum in environmental water samples by ionic liquid ultrasound-assisted dispersive liquid–liquid microextraction and LC-MS/MS[J].Analytical Methods,2014,6(15):5879-5885.