超高效液相色谱-质谱联用法同时测定中毒样品中12种鼠药
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摘要
目的建立超高效液相色谱-质谱联用法同时测定疑似鼠药中毒患者残留食物、呕吐物、洗胃液、血清及尿液中毒鼠强、杀鼠灵和杀鼠迷等12种鼠药的方法。方法采集疑似鼠药中毒患者残留食物、呕吐物、洗胃液、血清及尿液;其中食物、呕吐物、洗胃液和尿液样品中先加入浓度为2 mol/L的乙酸铵,随后加入乙酸乙酯重复提取2次,血清样品加入乙腈进行提取。样品经氮气吹干后,以甲醇∶乙酸铵溶液(60∶40,V/V)溶解,离心取上清液经C18柱分离,标准曲线法定量,采用超高效液相色谱-质谱联用仪检测。结果 12种鼠药在疑似鼠药中毒患者残留食物、呕吐物、洗胃液、血清及尿液的定量范围内线性关系良好,相关系数为0.992 3～0.999 9。方法检出限在食物、呕吐物或洗胃液为0.03～0.14μg/kg,在血清、尿液分别为0.10～0.30和0.02～0.04μg/L。加标回收率为84.4%～114.0%,批内、批间相对标准偏差分别为2.7%～6.2%和2.4%～9.5%。结论本方法操作简单、高效、准确,适用于因误食鼠药或投毒引起的中毒事件的应急处理。
Objective To establish an ultra-high performance liquid chromatography-tandem mass spectrometry(HPLC-MS) method for simultaneous detection of 12 kinds of rodenticides such as tetramine, warfarin and rodenticide in suspected poisoning patients' residual food, vomit, gastric lavage, serum and urine. Methods The residual food, vomit, gastric lavage, serum and urine of patients with suspected rodenticide poisoning were collected. The food, vomit, gastric lavage and urine samples were added with ammonium acetate at a concentration of 2 mol/L, and than were repeatedly extracted twice by ethyl acetate. The serum sample was extracted by adding acetonitrile. After the sample was dried by nitrogen, it was dissolved in methanol ∶ammonium acetate(60 ∶40, V/V), and the supernatant was centrifuged and separated by a C18 column, and quantified by a standard curve method. Samples were detected by HPLC-MS. Results The linearity of the 12 kinds of rodenticides in the quantitative range of residual food, vomit, gastric lavage, serum and urine in patients with suspected rodenticide poisoning was good, and the correlation coefficient was 0.992 3-0.999 9. The detection limit of food, vomit or gastric lavage was 0.03-0.14 μg/kg, and that in serum and urine were 0.10-0.30 and 0.02-0.04 μg/L, respectively. The standard recovery rate was 84.4%-114.0%, and the within-run and between-run relative standard deviations were 2.7%-6.2% and 2.4%-9.5%, respectively.Conclusion The method has advantages of simple operation, high efficiency and good accuracy. This method is suitable for emergency treatment of poisoning events caused by rodent drugs or poisoning.
Objective To establish an ultra-high performance liquid chromatography-tandem mass spectrometry(HPLC-MS) method for simultaneous detection of 12 kinds of rodenticides such as tetramine, warfarin and rodenticide in suspected poisoning patients' residual food, vomit, gastric lavage, serum and urine. Methods The residual food, vomit, gastric lavage, serum and urine of patients with suspected rodenticide poisoning were collected. The food, vomit, gastric lavage and urine samples were added with ammonium acetate at a concentration of 2 mol/L, and than were repeatedly extracted twice by ethyl acetate. The serum sample was extracted by adding acetonitrile. After the sample was dried by nitrogen, it was dissolved in methanol ∶ammonium acetate(60 ∶40, V/V), and the supernatant was centrifuged and separated by a C18 column, and quantified by a standard curve method. Samples were detected by HPLC-MS. Results The linearity of the 12 kinds of rodenticides in the quantitative range of residual food, vomit, gastric lavage, serum and urine in patients with suspected rodenticide poisoning was good, and the correlation coefficient was 0.992 3-0.999 9. The detection limit of food, vomit or gastric lavage was 0.03-0.14 μg/kg, and that in serum and urine were 0.10-0.30 and 0.02-0.04 μg/L, respectively. The standard recovery rate was 84.4%-114.0%, and the within-run and between-run relative standard deviations were 2.7%-6.2% and 2.4%-9.5%, respectively.Conclusion The method has advantages of simple operation, high efficiency and good accuracy. This method is suitable for emergency treatment of poisoning events caused by rodent drugs or poisoning.
引文
[1] 刘波.常见鼠药分类及其检测方法研究进展[J].职业与健康,2015,31(2):276-279.
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[3] 张继红,徐文泱,周兴旺,等.鼠药残留分析方法研究进展[J].分析试验室,2017,36(9):1111-1116.
[4] RICE N C, RAUSCHER N A, LANGSTON J L, et al. Behavioral intoxication following voluntary oral ingestion of tetramethylenedisul-fotetramine: Dose-dependent onset, severity, survival, and recovery[J]. Neurotoxicology,2017,63:21-32.
[5] BARNYCH B, VASYLIEVA N, JOSEPH T, et al. Development of tetramethylenedisulfotetramine (TETS) hapten library: synthesis, electrophysiological studies, and immune response in rabbits[J]. Chemistry,2017,23(35):8466-8472.
[6] 王云昊,孙桂芳.气相色谱-质谱联用法检测动物源性食品中的敌鼠[J].食品安全质量检测学报,2018,9(10):2451-2456.
[7] DOUBKOVá V, MARá LEK P, VEEREK V. The rapid determination of bromadiolone in liver and blood plasma by in-injector pyrolysis gas chromatography-Ion trap tandem mass spectrometry[J]. J Chromatogr B Analyt Technol Biomed Life Sci,2017,1070:117-120.
[8] 王璞,周丽屏,郭嘉明,等.高效液相色谱法测定全血中5种抗凝血类灭鼠剂[J].中国职业医学,2016,43(2):210-213.
[9] YAN Z, LI H, LI H, et al. Simultaneous determination of nine anticoagulant rodenticides by ultra-performance liquid chromatography-tandem mass spectrometry with ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction[J]. J Chromatogr B Analyt Technol Biomed Life Sci,2018,1092:453-458.
[10] SAITO-SHIDA S, NEMOTO S, TESHIMA R, et al. Determination of rodenticide tetramethylenedisulfotetramine (tetramine) in processed foods by gas chromatography-tandem mass spectrometry[J]. Shokuhin Eiseigaku Zasshi,2016,57(3):72-75.
[11] 郑三燕,吴俊,林少美.气相色谱-质谱、气相色谱-火焰光度、气相色谱-氮磷3种检测器测定毒鼠强的方法探讨[J].中国卫生检验杂志,2015,25(11):1719-1721.
[12] 李勇竞,郑妹凤,张丽珺.超高效液相色谱-二极管阵列-荧光检测器串联测定全血中的4种杀鼠剂[J].现代预防医学,2017,44(4):706-708,742.
[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] 欧阳燕玲,谢维平,苏碧玲.固相萃取-超高效液相色谱法同时测定血浆中8种抗凝血类杀鼠剂[J].中国卫生检验杂志,2015,25(3):323-325,329.
[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] 黄克建,莫静,刘晓锋,等.在线固相萃取/液相色谱-串联质谱法快速检测全血及尿液中15种杀鼠药[J].分析测试学报,2018,37(1):1-9.
[17] 麦沛明,余胜兵,吴西梅,等.分散液-液微萃取-气相色谱-质谱法同时测定中毒样品中有毒生物碱和鼠药[J].分析化学,2015,43(2):282-287.
[18] QIAO Z, XIANG P, SHEN B, et al. Simultaneous determination of 13 anticoagulant rodenticidesin human blood by liquid chromatography-tandem mass spectrometry and its application in three poisoning cases[J]. J Forensic Sci,2018,63(3):784-792.
[2] 严慧,沈敏.抗凝血杀鼠药的分析研究进展[J].复旦学报(医学版),2011,38(4):361-366.
[3] 张继红,徐文泱,周兴旺,等.鼠药残留分析方法研究进展[J].分析试验室,2017,36(9):1111-1116.
[4] RICE N C, RAUSCHER N A, LANGSTON J L, et al. Behavioral intoxication following voluntary oral ingestion of tetramethylenedisul-fotetramine: Dose-dependent onset, severity, survival, and recovery[J]. Neurotoxicology,2017,63:21-32.
[5] BARNYCH B, VASYLIEVA N, JOSEPH T, et al. Development of tetramethylenedisulfotetramine (TETS) hapten library: synthesis, electrophysiological studies, and immune response in rabbits[J]. Chemistry,2017,23(35):8466-8472.
[6] 王云昊,孙桂芳.气相色谱-质谱联用法检测动物源性食品中的敌鼠[J].食品安全质量检测学报,2018,9(10):2451-2456.
[7] DOUBKOVá V, MARá LEK P, VEEREK V. The rapid determination of bromadiolone in liver and blood plasma by in-injector pyrolysis gas chromatography-Ion trap tandem mass spectrometry[J]. J Chromatogr B Analyt Technol Biomed Life Sci,2017,1070:117-120.
[8] 王璞,周丽屏,郭嘉明,等.高效液相色谱法测定全血中5种抗凝血类灭鼠剂[J].中国职业医学,2016,43(2):210-213.
[9] YAN Z, LI H, LI H, et al. Simultaneous determination of nine anticoagulant rodenticides by ultra-performance liquid chromatography-tandem mass spectrometry with ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction[J]. J Chromatogr B Analyt Technol Biomed Life Sci,2018,1092:453-458.
[10] SAITO-SHIDA S, NEMOTO S, TESHIMA R, et al. Determination of rodenticide tetramethylenedisulfotetramine (tetramine) in processed foods by gas chromatography-tandem mass spectrometry[J]. Shokuhin Eiseigaku Zasshi,2016,57(3):72-75.
[11] 郑三燕,吴俊,林少美.气相色谱-质谱、气相色谱-火焰光度、气相色谱-氮磷3种检测器测定毒鼠强的方法探讨[J].中国卫生检验杂志,2015,25(11):1719-1721.
[12] 李勇竞,郑妹凤,张丽珺.超高效液相色谱-二极管阵列-荧光检测器串联测定全血中的4种杀鼠剂[J].现代预防医学,2017,44(4):706-708,742.
[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] 欧阳燕玲,谢维平,苏碧玲.固相萃取-超高效液相色谱法同时测定血浆中8种抗凝血类杀鼠剂[J].中国卫生检验杂志,2015,25(3):323-325,329.
[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] 黄克建,莫静,刘晓锋,等.在线固相萃取/液相色谱-串联质谱法快速检测全血及尿液中15种杀鼠药[J].分析测试学报,2018,37(1):1-9.
[17] 麦沛明,余胜兵,吴西梅,等.分散液-液微萃取-气相色谱-质谱法同时测定中毒样品中有毒生物碱和鼠药[J].分析化学,2015,43(2):282-287.
[18] QIAO Z, XIANG P, SHEN B, et al. Simultaneous determination of 13 anticoagulant rodenticidesin human blood by liquid chromatography-tandem mass spectrometry and its application in three poisoning cases[J]. J Forensic Sci,2018,63(3):784-792.