目的: 建立采用低场核磁共振波谱(LF-qNMR)和高场核磁共振波谱(HF-qNMR)测定缴获甲基苯丙胺晶体及片剂中甲基苯丙胺及掺杂物含量的方法。方法: 采用1H定量核磁共振波谱法(1H quantitative nuclear magnetic resonance,1H qNMR),使用Magritek SpinsolveTM 80ULTRA型低场核磁波谱仪和Bruker Avance III 400 MHz型高场核磁波谱仪,以氘代甲醇(methanol-d4)和重水(D2O)为溶剂,马来酸为内标,测定73份晶体及34份片剂样品中甲基苯丙胺和掺杂物的含量。结果: 2种核磁定量法测量结果的线性相关系数(r)大于0.99,Bland-Altman图显示对于93%的样品,2种测量方法的定量结果差值位于95%一致限内,表明2种方法具有较高一致性。结论: 本研究建立的LF-qNMR和HF-qNMR甲基苯丙胺晶体及片剂定量法前处理简单,检测时间短,无需待测物标准物质,可用于缴获甲基苯丙胺晶体及片剂样品中甲基苯丙胺和掺杂物含量的快速定量。
Objective: To establish a method for the quantitative analysis of methamphetamine and adulterants in seized methamphetamine crystals and tablets by low field LF-qNMR and high field HF-qNMR. Methods: 1H quantitative nuclear magnetic resonance (1H qNMR) was used to determine the content of methamphetamine and adulterants in seized methamphetamine crystal samples and methamphetamine tablets by Magritek SpinsolveTM 80ULTRA benchtop NMR spectrometer and Bruker Avance Ⅲ 400 MHz NMR spectrometer. Methanol-d4 and D2O were used as solvent. Maleic acid was used as internal standard. Results: The coefficients of determination (r) were all greater than 0.99. Bland-Altman plots showed that the differences between two measurement methods are within the 95% limits of agreement for 93% samples. The contents of methamphetamine and adulterants obtained by LF-qNMR spectrometer and HF-qNMR spectrometer can statistically be considered equal. Conclusion: The LF-qNMR and HF-qNMR quantitative method developed in this work applied to methamphetamine quantification is validated with good results. The sample preparation is simple and test time is short. This method is suitable for fast quantitative analysis of methamphetamine and adulterants.
[1] UNODC.World Drug Report 2020, Booklet 4, Cross-Cutting Issues:Evolving Trends and New Challenges[R].United Nations Publication, 2020:47
[2] 刘翠梅, 韩煜, 贾薇, 等. 近红外光谱用于甲基苯丙胺快速定量分析方法研究[J].光谱学与光谱分析, 2020, 40(9):2732
LIU CM, HAN Y, JIA W, et al. Rapid quantitative analysis of methamphetamine by near infrared spectroscopy[J].Spectrosc Spectral Anal, 2020, 40(9):2732
[3] GB/T 29636-2013疑似毒品中甲基苯丙胺的气相色谱、高效液相色谱和气相色谱-质谱检验方法[S].2013
GB/T 29636-2013 GC. HPLC and GC-MS Examination Methods for Methylamphetamine in Suspected Drug[S].2013
[4] JUAN FA, MICHAEL AB, TERRY C, et al. NMR Spectroscopy in the Undergraduate Curriculum, Volume 4:In-Person and Distance Learning Approaches[M].Washington: American Chemical Society, 2021:111
[5] HOLLIS DP. Quantitative analysis of aspirin, phenacetin, and caffeine mixtures by nuclear magnetic resonance spectrometry[J].Anal Chem, 1963, 35(11):1682
[6] SAMUELS ER, WANG T. Quantitative 1H-NMR analysis of a difficult drug substance and its exo-isomer as hydrochloride salts using alkaline deuterated methanol[J].J Pharm Biomed Anal, 2020, 187:113338
[7] SIMMLER C, NAPOLITANO JG, MCALPINE JB, et al. Universal quantitative NMR analysis of complex natural samples[J].Curr Opin Biotechnol, 2014, 25(1):51
[8] TSIRIVAKOU A, MELLIOU E, MAGIATIS P. A method for the rapid measurement of alkylresorcinols in flour, bread and related products based on 1H qNMR[J].Foods, 2020, 9(8):1025
[9] CROOK AA, POWERS R. Quantitative NMR-based biomedical metabolomics:current status and applications[J].Molecules, 2020, 25(21):5128
[10] DRAPER SL, MCCARNEY ER. Benchtop nuclear magnetic resonance spectroscopy in forensic chemistry[J/OL].Magn Reson Chem, 2021:1[2021-07-14]. https://doi.org/10.1002/mrc.5197
[11] JONATHAN D, AARON U, MATTHIAS N, et al. Differentiation of fentanyl analogues by low-field NMR spectroscopy[J].Anal Chim Acta, 2018, 1049(10):161
[12] GILBERT N, MEWIS RE, SUTCLIFFE OB.Fast & fluorinated-Development and validation of a rapid benchtop NMR approach and other routine screening methods for the detection and quantification of synthesized fluorofentanyl derivatives[J].Forensic Chem, 2021, 23:100321
[13] ARANEDA JF, CHU T, LECLERC MC, et al. Quantitative analysis of cannabinoids using benchtop NMR instruments[J].Anal Methods, 2020, 12(40):4853
[14] HULME MC, HAYATBAKHSH A, BRIGNALL RM, et al. Detection, discrimination and quantification of amphetamine, cathinone and nor-ephedrine regioisomers using benchtop 1H and 19F NMR spectroscopy[J/OL]. Magn Reson Chem, 2021:1[2021-03-23]. https://doi.org/10.1002/mrc.5156
[15] ANTONIDES LH, BRIGNALL RM, COSTELLO A, et al. Rapid identification of novel psychoactive and other controlled substances using low-field 1H-NMR spectroscopy[J].Am Chem Soc, 2019, 4(4):7103
[16] CASTAING-CORDIER T, LADROUE V, BESACIER F, et al. High-field and benchtop NMR spectroscopy for the characterization of new psychoactive substances[J].Forensic Sci Int, 2021, 321:110718
[17] HUSSAIN JH, GILBERT N, COSTELLO A, et al. Quantification of MDMA in seized tablets using benchtop 1H-NMR spectroscopy in the absence of internal standards[J].Forensic Chem, 2020, 20:100263
[18] GIAVARINA D. Understanding bland altman analysis[J].Biochem Med, 2015, 25(2):141
[19] HOLZGRABE U. Quantitative NMR spectroscopy in pharmaceutical applications[J].Prog Nucl Magn Reson Spectrosc, 2010, 57(2):229
[20] TAN DC, QUEK A, KASSIM K, et al. Rapid quantification and validation of biomarker scopoletin in paederia foetida by qNMR and UV-Vis for herbal preparation[J].Molecules, 2020, 25(21):1
[21] BERNSTEIN MA, SYKORA S, PENG C, et al. Optimization and automation of quantitative NMR data extraction[J].Anal Chem, 2013, 85(12):5778
[22] KHAKIMOV B, MOBARAKI N, TRIMIGNO A, et al. Signature Mapping(SigMa):an efficient approach for processing complex human urine 1H-NMR metabolomics data[J].Anal Chim Acta, 2020, 1108:142
