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GC-MS和LC-MS/MS法测定毛发中的6种苯丙胺类药物

韦棋 苏福海

韦棋,苏福海. GC-MS和LC-MS/MS法测定毛发中的6种苯丙胺类药物[J]. 计量科学与技术,2022, 66(4): 48-54 doi: 10.12338/j.issn.2096-9015.2021.0611
引用本文: 韦棋,苏福海. GC-MS和LC-MS/MS法测定毛发中的6种苯丙胺类药物[J]. 计量科学与技术,2022, 66(4): 48-54 doi: 10.12338/j.issn.2096-9015.2021.0611
WEI Qi, SU Fuhai. The Determination of 6 Amphetamine Drugs in Hair Samples by GC-MS and LC-MS/MS[J]. Metrology Science and Technology, 2022, 66(4): 48-54. doi: 10.12338/j.issn.2096-9015.2021.0611
Citation: WEI Qi, SU Fuhai. The Determination of 6 Amphetamine Drugs in Hair Samples by GC-MS and LC-MS/MS[J]. Metrology Science and Technology, 2022, 66(4): 48-54. doi: 10.12338/j.issn.2096-9015.2021.0611

GC-MS和LC-MS/MS法测定毛发中的6种苯丙胺类药物

doi: 10.12338/j.issn.2096-9015.2021.0611
基金项目: 国家重点研发计划( 2018YFC0807301-4) 。
详细信息
    作者简介:

    韦棋( 1995-),中国计量科学研究院硕士研究生,研究方向:药物分析,邮箱:weiqi18811@163.com

    通讯作者:

    苏福海( 1976-) ,中国计量科学研究院副研究员,研究方向:有机分析,邮箱:sufh@nim.ac.cn

The Determination of 6 Amphetamine Drugs in Hair Samples by GC-MS and LC-MS/MS

  • 摘要: 建立毛发样本中6种苯丙胺类药物的GC-MS和LC-MS/MS分析检测方法。选择合适的人体毛发,浸泡在药物-二甲基亚砜溶液中制备含6种苯丙胺类药物的毛发样本,采用单因素变量法优化样品前处理过程,利用GC-MS和LC-MS/MS法对制备的毛发样本进行定量分析。以甲基苯丙胺-D5为内标,采用工作曲线法进行定量分析。实验结果显示,制备的毛发样本中6种苯丙胺类药物的最佳前处理方法为:提取溶剂0.01 mol·L−1 HCl,液料比100:1(mL·g−1),提取温度40 ℃,提取时间50 min。GC-MS中,6种苯丙胺类药物在0.5~5.0 ng·mg−1浓度范围内线性关系良好,r2>0.999,检测限为0.04~0.08 ng·mg−1,回收率≥85.46%,RSDs≤ 3.6%(n=9);LC-MS/MS中,6种苯丙胺类药物在0.06~0.50 ng·mg−1浓度范围内线性关系良好,r2>0.999,检测限低至0.05~5.0 pg·mg−1,回收率在86.50%~111.9%范围内,RSDs≤ 4.2%(n=9)。这两种方法应用于毛发中苯丙胺类药物的检测,灵敏度高、准确度好、专属性强,可作为毛发中苯丙胺类药物基体标准物质的定值方法,用于标准物质的研制,应用于法医滥用药物检测和实验室质量控制领域。
  • 图  1  不同提取溶剂对苯丙胺类药物浓度的影响

    Figure  1.  The effect of different extraction solvents on the concentration of amphetamines

    图  2  不同提取温度对药物浓度的影响

    Figure  2.  The effect of different extraction temperature on drug concentration

    图  3  不同提取时间对药物浓度的影响

    Figure  3.  The effect of different extraction time on drug concentration

    图  4  不同液料比对药物浓度的影响

    Figure  4.  The effect of different liquid-to-material ratios on drug concentration

    图  5  不同盐酸浓度对药物浓度的影响

    Figure  5.  The effect of different hydrochloric acid concentration on drug concentration

    图  6  头发样本中6种苯丙胺类药物MRM色谱图

    Figure  6.  MRM chromatograms of 6 amphetamine drugs in hair samples

    图  7  头发样本中6种苯丙胺类药物的含量

    Figure  7.  The levels of 6 amphetamine drugs in hair samples

    表  1  实验仪器信息表

    Table  1.   Experimental instrument information sheet

    仪器名称型号生产厂家
    液质联用仪TQS Waters,美国
    气质联用仪7890A-7000Agilent,美国
    超声波清洗机Branson 8510Danbury,美国
    氮吹仪N-EVAP 112Organomation,美国
    超纯水机Milli-QMillipore,美国
    电热恒温鼓风干燥箱DGG-9123AD上海森信实验仪器有限公司
    多用途冷冻离心机CF16RXIIHITACHI公司
    电子天平XP205Mettler Toledo公司,瑞士
    下载: 导出CSV

    表  2  实验试剂信息表

    Table  2.   Laboratory reagent information sheet

    试剂名称纯度生产厂家
    甲醇色谱纯Merck KGaA,德国
    乙腈色谱纯Merck KGaA,德国
    盐酸分析纯北京化学试剂研究所有限责任公司,中国
    二甲基亚砜>99.5%Honeywell,美国
    甲酸色谱纯Honeywell,美国
    乙酸铵色谱纯Honeywell,美国
    下载: 导出CSV

    表  3  GC-MS中化合物的保留时间和特征离子

    Table  3.   Retention time and characteristic ions of amphetamine compounds in GC-MS

    药物名称SIM离子保留时间(min)RSD
    n=3, %)
    标准溶液头发样本
    AP44*,91,117,655.695.700.07
    MA58*,91,566.456.460.09
    MDEA72*,135,136,7711.6011.600.02
    MDMA58*,77,59,13511.1011.100.01
    MDA44*,136,77,5110.4010.400.06
    麻黄碱58*,77,1059.039.030.02
    甲基苯丙胺-D562*,66,92,1396.416.410.02
    注:*为定量离子
    下载: 导出CSV

    表  4  LC-MS/MS梯度洗脱程序表

    Table  4.   LC-MS/MS gradient elution program table

    时间(min)流动相A(%)流动相B(%)
    08515
    47228
    57228
    107030
    135545
    13.5595
    14.58515
    208515
    下载: 导出CSV

    表  5  LC-MS/MS中6种苯丙胺类化合物质谱参数表

    Table  5.   Mass spectrometry parameters of 6 amphetamine compounds in LC-MS/MS

    药物
    名称
    分子量母离子
    m/z
    子离子
    m/z
    锥孔电
    压(V)
    CE
    (V)
    内标
    AP135.00136.0091.00*5525甲基苯
    丙胺-D5
    119.005515
    MA149.23148.24133.24*6418
    117.266416
    MDEA207.00208.22105.23*2822
    132.852824
    MDMA194.00194.22163.27*3212
    105.233222
    MDA179.20180.00135.007026
    163.00*7013
    麻黄碱148.00148.16114.914216
    133.24*4216
    注:*为定量离子
    下载: 导出CSV

    表  6  6种苯丙胺类化合物的检测限和定量限

    Table  6.   LOD and LOQ of 6 amphetamine compounds

    药物名称LOD(ng·mg−1)LOQ(ng·mg−1)
    GC-MSLC-MSGC-MSLC-MS
    AP0.040.0050.080.02
    MA0.040.000050.080.0003
    MDEA0.040.000050.080.0003
    MDMA0.040.000050.080.0003
    MDA0.040.0050.080.01
    麻黄碱0.080.000050.10.0003
    下载: 导出CSV

    表  7  GC-MS中6种苯丙胺类化合物的线性与范围

    Table  7.   Linearity and range of 6 amphetamine compounds in GC-MS

    药物名称线性范围(ng·mg−1)回归方程r2
    AP0.5~5.0y=0.5272x−0.00090.9995
    MA0.5~5.0y=0.206x+0.03580.9992
    MDEA0.5~5.0y=0.6042x−0.02480.9993
    MDMA0.5~5.0y=0.5188x−0.0110.9997
    MDA0.5~5.0y=0.2284x−0.02750.9998
    麻黄碱0.5~5.0y=0.2303x−0.14610.9990
    下载: 导出CSV

    表  8  LC-MS/MS种6种苯丙胺类化合物的线性与范围

    Table  8.   Linearity and range of 6 amphetamine compounds in LC-MS/MS

    药物名称线性范围(ng·mg−1)回归方程r2
    AP0.06~0.50y=0.1779x+0.01630.9991
    MA0.06~0.50y=4.5592x+0.10730.9992
    MDEA0.06~0.50y=10.369x+0.20260.9992
    MDMA0.06~0.50y=15.063x+0.44450.9990
    MDA0.06~0.50y=0.0566x+0.00620.9992
    麻黄碱0.06~0.50y=5.4438x+0.11920.9998
    下载: 导出CSV

    表  9  6种苯丙胺类化合物重复性实验结果(n=6)

    Table  9.   Results of reproducible experiments of amphetamine compounds(n=6)

    药物名称RSD (%)
    GC-MSLC-MS/MS
    AP0.682.5
    MA1.11.0
    MDEA1.91.2
    MDMA0.320.75
    MDA1.92.7
    麻黄碱20.41
    下载: 导出CSV

    表  10  苯丙胺类化合物的空白加标回收率(GC-MS)

    Table  10.   Results of blank spike recovery of amphetamine compounds(GC-MS)

    药物名称添加浓度/ng·mg−1测得浓度/ng·mg−1回收率/%RSD/%
    AP0.87760.9240105.31.5
    1.5641.796114.81.0
    3.0483.090101.42.6
    MA0.99000.858386.692.0
    1.7641.69195.861.6
    3.4383.760109.41.6
    MDEA0.98530.842185.460.66
    1.7561.58690.310.72
    3.4223.16392.442.4
    MDMA0.98140.885790.253.6
    1.7491.798102.80.21
    3.4083.40399.853.6
    MDA1.0040.874287.100.78
    1.7892.124118.71.5
    3.4864.122118.31.7
    麻黄碱0.90220.9246102.51.2
    1.6081.706106.12.0
    3.1332.87291.660.48
    下载: 导出CSV

    表  11  苯丙胺类化合物的空白加标回收率(LC-MS/MS)

    Table  11.   Results of blank spike recovery of amphetamine compounds(LC-MS/MS)

    药物名称添加浓度/ng·mg−1测得浓度/ng·mg−1回收率/%RSD/%
    AP0.073700.07916107.44.2
    0.17500.151486.502.0
    0.34870.320791.962.6
    MA0.065200.0564986.641.1
    0.17920.1840102.71.0
    0.35690.3604101.01.7
    MDEA0.064210.0598993.271.8
    0.17640.1899107.60.37
    0.35150.3662104.21.0
    MDMA0.063970.0556587.002.5
    0.17580.1967111.91.4
    0.35020.3545101.21.5
    MDA0.062830.06698106.60.53
    0.17260.152588.321.2
    0.34390.322893.871.6
    麻黄碱0.062510.0548087.671.6
    0.17180.1747101.71.4
    0.34210.3492102.10.69
    下载: 导出CSV
  • [1] SHI Q, SHI Y, PAN Y, et al. Colorimetric and bare eye determination of urinary methylamphetamine based on the use of aptamers and the salt-induced aggregation of unmodified gold nanoparticles[J]. Microchimica Acta, 2014, 182(3-4): 505-511.
    [2] PHD J, RUTKOWSKI B. The prevalence of methamphetamine and amphetamine abuse in North America: a review of the indicators, 1992 ~ 2007[J]. Drug and Alcohol Review, 2008, 27(3): 229-235. doi: 10.1080/09595230801919460
    [3] NATH R, KUMAR D, LI T, et al. Metallothioneins, oxidative stress and the cardiovascular system[J]. Toxicology, 2000, 155(1): 17-26.
    [4] 卢建珍, 谢明仁, 管海彦. 甲基苯丙胺的毒性作用与检测方法[J]. 中国公共安全(学术版), 2020(1): 128-132.
    [5] Coning E D, Stolsvik G. United Nations Office on Drugs and Crime: “Methamphetamine Continues to Dominate Synthetic Drug Markets”[J]. Global Smart Update, 2018, 20: 1-16.
    [6] KWON NH, LEE YR, KIM HS, et al. Hybrid Solid-Phase Extraction for Selective Determination of Methamphetamine and Amphetamine in Dyed Hair by Using Gas Chromatography-Mass Spectrometry[J]. Molecules, 2019, 24(13): 2501. doi: 10.3390/molecules24132501
    [7] ANDO E, HAYASHIDA M, NIHIRA M, et al. GC-MS analysis of methamphetamine and amphetamine in hair of Thai drug addicts[J]. Nihon Arukoru Yakubutsu Igakkai zasshi = Japanese journal of alcohol studies & drug dependence, 2004, 39(3): 168-179.
    [8] 沈敏, 姜宴, 向平, 等. 毛发中违禁苯丙胺类的代谢研究[J]. 质谱学报, 2000(1): 7-13. doi: 10.3969/j.issn.1004-2997.2000.01.002
    [9] PASCAL K. , MARION V, VINCENT C. Hair analysis for drug detection[J]. Therapeutic drug monitoring, 2006, 28(3): 442-446. doi: 10.1097/01.ftd.0000211811.27558.b5
    [10] KHAJURIA H, NAYAK BP, BADIYE A. Toxicological hair analysis: Pre-analytical, analytical and interpretive aspects[J]. Med Sci Law, 2018, 58(3): 137-146. doi: 10.1177/0025802418768305
    [11] KAPP RW. Clarke’s Analysis of Drugs and Poisons, 3rd edition Edited by Anthony C. Moffat, M. David Osselton, and Brian Widdop Publisher: Pharmaceutical Press: London[J]. International Journal of Toxicology, 2016, 25(1): 81-82.
    [12] CHEONG J, SUH S, KO BJ, et al. Screening method for the detection of methamphetamine in hair using fluorescence polarization immunoassay[J]. J Anal Toxicol, 2013, 37(4): 217-221. doi: 10.1093/jat/bkt011
    [13] SEO MJ, SONG SH, KIM S, et al. Characteristics of Korean patients with methamphetamine use disorder based on the quantitative analysis of methamphetamine and amphetamine in hair[J]. Arch Pharm Res, 2020, 43(8): 798-807. doi: 10.1007/s12272-020-01259-6
    [14] CHEN S, MA J, WANG X, et al. UPLC–MS/MS simultaneous determination of methamphetamine, amphetamine, morphine, monoacetylmorphine, ketamine, norketamine, MDMA, and MDA in hair[J]. Acta Chromatographica, 2020, 32(2): 145-148. doi: 10.1556/1326.2019.00615
    [15] BRCIC KARACONJI I, BRAJENOVIC N. Evaluation of amphetamine-type stimulant abuse through hair analysis: Results from 12 years of work[J]. Arh Hig Rada Toksikol, 2014, 65(2): 225-230. doi: 10.2478/10004-1254-65-2014-2514
    [16] 苏福海. 《液相色谱-飞行时间质谱联用仪性能测定方法》国家标准解读[J]. 计量科学与技术, 2020(10): 3-5.
    [17] KINTZ P. Hair Analysis in Forensic Toxicology: An Updated Review with a Special Focus on Pitfalls[J]. Current Pharmaceutical Design, 2017, 23(36): 5480-5486.
    [18] 杨洪国, 李重阳, 丁斌. 毒品与毛发的结合及其影响因素[J]. 中国司法鉴定, 2013(1): 46-49. doi: 10.3969/j.issn.1671-2072.2013.01.008
    [19] KINTZ P, CIRIMELE V, LUDES B. Pharmacological criteria that can affect the detection of doping agents in hair[J]. Forensic Science International, 2000, 107(1-3): 325-334. doi: 10.1016/S0379-0738(99)00176-0
    [20] TESTORF MF, KRONSTRAND R, SVENSSON S, et al. Characterization of [3H] Flunitrazepam Binding to Melanin[J]. Analytical Biochemistry, 2001, 298(2): 259-264. doi: 10.1006/abio.2001.5364
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  • 录用日期:  2022-03-31
  • 网络出版日期:  2022-04-12
  • 刊出日期:  2022-06-02

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