在线固相萃取/液质联用法检测血液和尿液中10种巴比妥类药物
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摘要
文中建立了在线固相萃取/液相色谱—三重串联四极杆质谱(on-line SPE/LC-MS/MS)方法同时测定血液和尿液中10种巴比妥类药物。样品用乙腈沉淀蛋白,经在线固相萃取柱(HLB)富集纯化,以Poroshell 120EC-C18柱(2. 1 mm×50 mm,1. 9μm)为分析柱,乙腈—水为流动相进行梯度洗脱。电离模式为电喷雾电离负模式(ESI-),扫描方式为多反应监控模式(MRM),定量方法采用外标法。结果表明,10种化合物在各自质量浓度范围内线性关系良好(权重因子1/x),相关系数为0. 998 8～0. 999 5,方法检出限(MDL)和定量限(LOQ)分别为10. 0～20. 0 ng/m L和20. 0～50. 0 ng/m L,回收率为95. 8%～109. 5%,相对标准偏差(RSD)为0. 5%～3. 8%(n=6)。检测方法操作简单,耗时短,检测灵敏度高且结果准确,能够满足血液和尿液样品中10种化合物同时快速筛查和准确定量。
A method of liquid chromatography-tandem mass spectrometry(LC-MS/MS) with on-line solid phase extraction(on-line SPE) for the simultaneous determination of 10 barbiturates in blood and urine was developed and validated. The samples were treated with acetonitrile,and then purified by a column with polymer of hydrophilic-lipophilic balance(HLB). The samples were eluted on aPoroshell 120 EC-C18 column by acetonitrile and water. The analysis was detected in multiplereaction monitoring(MRM) mode under negative electrospray ionization mode(ESI-) and quantified by external standard method. The results show that the correlation coefficients are 0.9988～ 0.9995 within the investigated mass concentration ranges of the 10 barbiturates. The LODs vary from 10. 0 ng/m L to 20. 0 ng/m L,and the LOQs vary from 20. 0 ng/m L to 50. 0 ng/m L. The recoveries at different spiked levels in blood and urine range from 95. 8% to 109. 5%,and RSDs range from 0. 5% to 3. 8%(n = 6). The method is simple,reliable and highly sensitive for the rapid detection and accurate quantification of the 10 barbiturates in blood and urine.
A method of liquid chromatography-tandem mass spectrometry(LC-MS/MS) with on-line solid phase extraction(on-line SPE) for the simultaneous determination of 10 barbiturates in blood and urine was developed and validated. The samples were treated with acetonitrile,and then purified by a column with polymer of hydrophilic-lipophilic balance(HLB). The samples were eluted on aPoroshell 120 EC-C18 column by acetonitrile and water. The analysis was detected in multiplereaction monitoring(MRM) mode under negative electrospray ionization mode(ESI-) and quantified by external standard method. The results show that the correlation coefficients are 0.9988～ 0.9995 within the investigated mass concentration ranges of the 10 barbiturates. The LODs vary from 10. 0 ng/m L to 20. 0 ng/m L,and the LOQs vary from 20. 0 ng/m L to 50. 0 ng/m L. The recoveries at different spiked levels in blood and urine range from 95. 8% to 109. 5%,and RSDs range from 0. 5% to 3. 8%(n = 6). The method is simple,reliable and highly sensitive for the rapid detection and accurate quantification of the 10 barbiturates in blood and urine.
引文
[1]曾苏. GC/MSD分析生物样品中的巴比妥类药物[J].法医学杂志,1994,10(4):158-159.
[2] IWAI M,HATTON H,ARINOBU T,et al. Simultaneous determination of barbiturates in human biological fluids by direct immersion solid-phase microextraction and gas chromatography-mass spectrometry[J]. Journal of Chromatography B,2004,806:65-73.
[3] ALMEIDA R M D,LIMA D S D,SEULIN S C,et al. Hollow-fiber liquid-phase microextraction and gas chromatographymass spectrometry of barbiturates in whole blood samples[J]. Journal of Separation Science,2012,35:3361-3368.
[4] ZHAO H X,WANG L P,QIU Y M,et al. Multiwalled carbon nanotubes as a solid-phase extraction adsorbent for the determination of three barbiturates in pork by ion trap gas chromatography-tandem mass spectrometry(GC/MS/MS)following microwave assisted derivatization[J]. Analytica Chimica Acta,2001,586:399-406.
[5]赵海香,杨素萍,刘海萍,等.微波辅助衍生化/气相色谱串联质谱同时测定猪肝与猪肾中4种巴比妥药物残留[J].分析测试学报,2012,31(12):1525-1530.
[6] BIRKLER R I D,TELVING R,INGEMANN-HANSEN O,et al. Screening analysis for medicinal drugs and drugs of abuse in whole blood using ultra-performance liquid chromatography time-of-flight mass spectrometry(UPLC-TOF-MS)—Toxicological findings in cases of alleged sexual assault[J]. Forensic Science International,2012,222:154-161.
[7] LIU Y,UBOH C E,LI X P,et al. Validated LC-MS-MS method for simultaneous analysis of 17 barbiturates in horse plasma for doping control[J]. Journal of Analytical Toxicology,2017,41:431-440.
[8] MONTESANO C,JOHANSEN S S,NIELSEN M K K. Validation of a method for the targeted analysis of 96 drugs in hair by UPLC-MS/MS[J]. Journal of Pharmaceutical and Biomedical Analysis,2014,88:295-306.
[9]卓先义,向平. LC-MS/MS同时分析血液中五种巴比妥类药物[J].中国司法鉴定:鉴定科学,2007(2):17-19.
[10]卢敏萍,黄克建,周哲,等.在线固相萃取/液相色谱—线性离子阱质谱法同时检测生物样品中18种氨基甲酸酯类农药[J].分析测试学报,2016,35(7):777-784.
[11]黄克建,莫静,刘晓峰,等.在线固相萃取/液相色谱—串联质谱法快速检测全血和尿液中15种杀鼠药[J].分析测试学报,2018,37(1):1-9.
[12]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.
[13]刘晓峰,黄克建,林翠梧,等.在线固相萃取—液相色谱—质谱法测定血液中9种局部麻醉药[J].理化检验—化学分册,2015,51(2):245-247.
[2] IWAI M,HATTON H,ARINOBU T,et al. Simultaneous determination of barbiturates in human biological fluids by direct immersion solid-phase microextraction and gas chromatography-mass spectrometry[J]. Journal of Chromatography B,2004,806:65-73.
[3] ALMEIDA R M D,LIMA D S D,SEULIN S C,et al. Hollow-fiber liquid-phase microextraction and gas chromatographymass spectrometry of barbiturates in whole blood samples[J]. Journal of Separation Science,2012,35:3361-3368.
[4] ZHAO H X,WANG L P,QIU Y M,et al. Multiwalled carbon nanotubes as a solid-phase extraction adsorbent for the determination of three barbiturates in pork by ion trap gas chromatography-tandem mass spectrometry(GC/MS/MS)following microwave assisted derivatization[J]. Analytica Chimica Acta,2001,586:399-406.
[5]赵海香,杨素萍,刘海萍,等.微波辅助衍生化/气相色谱串联质谱同时测定猪肝与猪肾中4种巴比妥药物残留[J].分析测试学报,2012,31(12):1525-1530.
[6] BIRKLER R I D,TELVING R,INGEMANN-HANSEN O,et al. Screening analysis for medicinal drugs and drugs of abuse in whole blood using ultra-performance liquid chromatography time-of-flight mass spectrometry(UPLC-TOF-MS)—Toxicological findings in cases of alleged sexual assault[J]. Forensic Science International,2012,222:154-161.
[7] LIU Y,UBOH C E,LI X P,et al. Validated LC-MS-MS method for simultaneous analysis of 17 barbiturates in horse plasma for doping control[J]. Journal of Analytical Toxicology,2017,41:431-440.
[8] MONTESANO C,JOHANSEN S S,NIELSEN M K K. Validation of a method for the targeted analysis of 96 drugs in hair by UPLC-MS/MS[J]. Journal of Pharmaceutical and Biomedical Analysis,2014,88:295-306.
[9]卓先义,向平. LC-MS/MS同时分析血液中五种巴比妥类药物[J].中国司法鉴定:鉴定科学,2007(2):17-19.
[10]卢敏萍,黄克建,周哲,等.在线固相萃取/液相色谱—线性离子阱质谱法同时检测生物样品中18种氨基甲酸酯类农药[J].分析测试学报,2016,35(7):777-784.
[11]黄克建,莫静,刘晓峰,等.在线固相萃取/液相色谱—串联质谱法快速检测全血和尿液中15种杀鼠药[J].分析测试学报,2018,37(1):1-9.
[12]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.
[13]刘晓峰,黄克建,林翠梧,等.在线固相萃取—液相色谱—质谱法测定血液中9种局部麻醉药[J].理化检验—化学分册,2015,51(2):245-247.