Qualitative and Quantitative Analysis of Five Indoles or Indazole Amide Synthetic Cannabinoids in Suspected E-Cigarette Oil by GC-MS

doi:10.12116/j.issn.1004-5619.2022.320101

Abstract

Abstract:

Objective To establish the GC-MS qualitative and quantitative analysis methods for the synthetic cannabinoids, its main matrix and additives in suspicious electronic cigarette （e-cigarette） oil samples. Methods The e-cigarette oil samples were analyzed by GC-MS after diluted with methanol. Synthetic cannabinoids, its main matrix and additives in e-cigarette oil samples were qualitatively analyzed by the characteristic fragment ions and retention time. The synthetic cannabinoids were quantitatively analyzed by using the selective ion monitoring mode. Results The linear range of each compound in GC-MS quantitative method was 0.025-1 mg/mL, the matrix recovery rate was 94%-103%, the intra-day precision relative standard deviations （RSD） was less than 2.5%, and inter-day precision RSD was less than 4.0%. Five indoles or indazole amide synthetic cannabinoids were detected in 25 e-cigarette samples. The main matrixes of e-cigarette samples were propylene glycol and glycerol. Additives such as N,2,3-trimethyl-2-isopropyl butanamide （WS-23）, glycerol triacetate and nicotine were detected in some samples. The content range of synthetic cannabinoids in 25 e-cigarette samples was 0.05%-2.74%. Conclusion The GC-MS method for synthesizing cannabinoid, matrix and additive in e-cigarette oil samples has good selectivity, high resolution, low detection limit, and can be used for simultaneous qualitative and quantitative analysis of multiple components; The explored fragment ion fragmentation mechanism of the electron bombardment ion source of indole or indoxamide compounds helps to identify such substances or other compounds with similar structures in cases.

Key words: forensic toxicology, e-cigarette oil, synthetic cannabinoids, gas chromatography-mass spectrometry （GC-MS）, indole, indazole amide

CLC Number:

Cui-mei LIU, Wei JIA, Chun-hui SONG, Zhen-hua QIAN, Zhen-dong HUA, Yue-meng CHEN. Qualitative and Quantitative Analysis of Five Indoles or Indazole Amide Synthetic Cannabinoids in Suspected E-Cigarette Oil by GC-MS[J]. Journal of Forensic Medicine, 2023, 39(5): 457-464.

Figures/Tables 9

References 15

1	KORFEI M. The underestimated danger of e-cigarettes - also in the absence of nicotine[J]. Respir Res，2018，19（1）：159. doi：10.1186/s12931-018-0870-4 .
2	金吉琼，陈超，胡佳倩，等. 国内电子烟市场产品特征分析[J].烟草科技，2021，54（2）：71-77. doi：10.16135/j.issn1002-0861.2020.0236 .
	JIN J Q， CHEN C， HU J Q， et al. Product features of electronic cigarettes in domestic markets[J]. Yancao Keji，2021，54（2）：71-77.
3	BUDZYŃSKA E， SIELEMANN S， PUTON J， et al. Analysis of e-liquids for electronic cigarettes using GC-IMS/MS with headspace sampling[J]. Talanta，2020，209：120594. doi：10.1016/j.talanta.2019.120594 .
4	GIROUD C， DE CESARE M， BERTHET A， et al. E-cigarettes： A review of new trends in cannabis use[J]. Int J Environ Res Public Health，2015，12（8）：9988-10008. doi：10.3390/ijerph120809988 .
5	KENNE D R， FISCHBEIN R L， TAN A S， et al. The use of substances other than nicotine in electronic cigarettes among college students[J]. Subst Abuse，2017，11：1178221817733736. doi：10.1177/ 1178221817733736 .
6	GRAFINGER K E， KRÖNERT S， BROILLET A， et al. Cannabidiol and tetrahydrocannabinol concentrations in commercially available CBD e-liquids in Switzerland[J]. Forensic Sci Int，2020，310：110261. doi：10.1016/j.forsciint.2020.110261 .
7	钱振华，郑珲，高利生. 新型毒品5F-AMB电子烟油的定性检验[J].刑事技术，2019，44（2）：109-112. doi：10.16467/j.1008-3650.2019.02.004 .
	QIAN Z H， ZHENG H， GAO L S. Identifying e-cigarette-liquid-contained 5F-AMB by UPLC-Q-TOF MS and GC-MS[J]. Xingshi Jishu，2019，44（2）：109-112.
8	李园园，丁希强，韩朋. 电子烟油中新型合成大麻素5F-ADBICA和5F-MDMB-PICA的GC-MS检验分析[J].广东化工，2020，47（23）：126-127，140. doi：10.3969/j.issn.1007-1865.2020.23.060 .
	LI Y Y， DING X Q， HAN P. Identifying synthetic cannabis 5F-ADBICA and 5F-MDMB-PICA in electronic cigarette oil with GC-MS[J]. Guangdong Huagong，2020，47（23）：126-127，140.
9	POKLIS J L， MULDER H A， PEACE M R. The unexpected identification of the cannabimimetic，5F-ADB， and dextromethorphan in commercially available cannabidiol E-liquids[J]. Forensic Sci Int，2019，294： e25-e27. doi：10.1016/j.forsciint.2018.10.019 .
10	PEACE M R， KRAKOWIAK R I， WOLF C E， et al. Identification of MDMB-FUBINACA in commercially available e-liquid formulations sold for use in electronic cigarettes[J]. Forensic Sci Int，2017，271：92-97. doi：10.1016/j.forsciint.2016.12.031 .
11	WU N， DANOUN S， BALAYSSAC S， et al. Synthetic cannabinoids in e-liquids： A proton and fluorine NMR analysis from a conventional spectrometer to a compact one[J]. Forensic Sci Int，2021，324：110813. doi：10.1016/j.forsciint.2021.110813 .
12	POTTS A J， CANO C， THOMAS S H L， et al. Synthetic cannabinoid receptor agonists： Classification and nomenclature[J]. Clin Toxicol （Phila），2020，58（2）：82-98. doi：10.1080/15563650.2019.1661425 .
13	王跨陡，袁晓亮，张玉荣，等. 合成大麻素类新精神活性物质4F-MDMB-BUTINACA和MDMB-4en-PINACA的检测[J].法医学杂志，2021，37（4）：505-510. doi：10.12116/j.issn.1004-5619.2020.300501 .
	WANG K D， YUAN X L， ZHANG Y R， et al. Identification of synthetic cannabinoid new psychoactive substances 4F-MDMB-BUTINACA and MDMB-4en-PINACA[J]. Fayixue Zazhi，2021，37（4）：505-510.
14	李家玉，张弛. 新型凉味剂N，2，3-三甲基-2-异丙基丁酰胺（WS-23）的合成[J].香料香精化妆品，2007（6）：17-18. doi：10.3969/j.issn.1000-4475.2007.06.005 .
	LI J Y， ZHANG C. The synthesis of new cooling agent N，2，3-trimethyl-2-isopropl butanamide（WS-23）[J]. Xiangliao Xiangjing Huazhuangpin，2007（6）：17-18.
15	许蔼飞，章平泉，范忠，等. 用气相色谱法同时测定薄荷型卷烟滤嘴中的薄荷醇、三乙酸甘油酯和烟碱含量[J].轻工学报，2018，33（5）：53-59. doi：10.3969/j.issn.2096-1553.2018.05.007 .
	XU A F， ZHANG P Q， FAN Z， et al. Simultaneous determination of the content of menthol， triacetin and nicotine in mint cigarette filter by gas chromatography[J]. Qinggong Xuebao，2018，33（5）：53-59.

物质	m/z	线性方程	线性范围/（mg·mL^-1）	相关系数	定量限/（mg·mL^-1）
MDMB-4en-PINACA	213	y=0.807 4x-0.007 1	0.025~1.000	0.999	0.025
4F-MDMB-BUTINACA	219	y=1.088 9x-0.005 7	0.025~1.000	0.999	0.025
ADB-BUTINACA	201	y=1.209 3x-0.023 9	0.025~1.000	0.998	0.025
4F-MDMB-BUTICA	218	y=1.431 2x-0.116 0	0.025~1.000	0.999	0.025
5F-MDMB-PICA	232	y=1.306 5x-0.014 8	0.025~1.000	0.999	0.025
JWH-250	214	-	-	-	-

物质	m/z	线性方程	线性范围/（mg·mL^-1）	相关系数	定量限/（mg·mL^-1）
MDMB-4en-PINACA	213	y=0.807 4x-0.007 1	0.025~1.000	0.999	0.025
4F-MDMB-BUTINACA	219	y=1.088 9x-0.005 7	0.025~1.000	0.999	0.025
ADB-BUTINACA	201	y=1.209 3x-0.023 9	0.025~1.000	0.998	0.025
4F-MDMB-BUTICA	218	y=1.431 2x-0.116 0	0.025~1.000	0.999	0.025
5F-MDMB-PICA	232	y=1.306 5x-0.014 8	0.025~1.000	0.999	0.025
JWH-250	214	-	-	-	-

样品编号	性状	MDMB-4en-PINACA	4F-MDMB- BUTINACA	ADB-BUTINACA	4F-MDMB-BUTICA	5F-MDMB-PICA	丙二醇	丙三醇	WS-23	三乙酸甘油酯	尼古丁
S-01	深黄色液体	-	-	-	0.12	0.05	+	+	+	+	+
S-02	浅黄色液体	-	-	-	-	0.14	+	+	+	+	+
S-03	浅黄色液体	-	-	-	-	0.13	+	+	+	-	+
S-04	浅黄色液体	-	-	-	-	0.13	+	+	+	-	+
S-05	浅黄色液体	-	-	-	-	0.13	+	+	+	-	+
S-06	浅黄色液体	-	-	-	-	0.07	+	+	+	-	+
S-07	浅红色液体	-	-	-	0.21	-	+	+	+	+	+
S-08	浅黄色液体	-	-	-	-	0.17	+	+	+	+	+
S-09	深黄色液体	0.57	-	-	-	-	+	+	+	-	+
S-10	浅黄色液体	0.08	-	-	-	-	+	+	+	-	+
S-11	浅黄色液体	0.13	-	-	-	-	+	+	+	+	+
S-12	深黄色液体	0.25	-	-	-	-	+	+	+	-	-
S-13	浅红色液体	-	-	-	0.12	-	+	+	+	-	-
S-14	浅黄色液体	-	-	-	-	0.32	+	+	+	+	+
S-15	浅黄色液体	-	-	-	-	0.34	+	+	+	+	+
S-16	深黄色液体	-	-	-	-	0.08	+	+	+	-	+
S-17	浅黄色液体	-	-	-	-	0.19	+	+	+	-	+
S-18	浅绿色液体	-	0.73	-	-	-	-	+	-	-	-
S-19	浅绿色液体	-	0.71	-	-	-	-	+	-	-	-
S-20	浅黄色液体	-	-	-	0.28	0.53	+	-	-	-	-
S-21	浅黄色液体	0.58	-	0.80	-	-	+	-	+	-	-
S-22	浅黄色液体	-	-	0.70	-	-	+	+	+	-	-
S-23	浅黄色液体	-	-	0.89	-	-	+	+	-	-	-
S-24	浅黄色液体	-	-	2.74	-	-	+	-	-	-	-
S-25	浅黄色液体	-	-	1.85	-	-	+	-	-	-	-

样品编号	性状	MDMB-4en-PINACA	4F-MDMB- BUTINACA	ADB-BUTINACA	4F-MDMB-BUTICA	5F-MDMB-PICA	丙二醇	丙三醇	WS-23	三乙酸甘油酯	尼古丁
S-01	深黄色液体	-	-	-	0.12	0.05	+	+	+	+	+
S-02	浅黄色液体	-	-	-	-	0.14	+	+	+	+	+
S-03	浅黄色液体	-	-	-	-	0.13	+	+	+	-	+
S-04	浅黄色液体	-	-	-	-	0.13	+	+	+	-	+
S-05	浅黄色液体	-	-	-	-	0.13	+	+	+	-	+
S-06	浅黄色液体	-	-	-	-	0.07	+	+	+	-	+
S-07	浅红色液体	-	-	-	0.21	-	+	+	+	+	+
S-08	浅黄色液体	-	-	-	-	0.17	+	+	+	+	+
S-09	深黄色液体	0.57	-	-	-	-	+	+	+	-	+
S-10	浅黄色液体	0.08	-	-	-	-	+	+	+	-	+
S-11	浅黄色液体	0.13	-	-	-	-	+	+	+	+	+
S-12	深黄色液体	0.25	-	-	-	-	+	+	+	-	-
S-13	浅红色液体	-	-	-	0.12	-	+	+	+	-	-
S-14	浅黄色液体	-	-	-	-	0.32	+	+	+	+	+
S-15	浅黄色液体	-	-	-	-	0.34	+	+	+	+	+
S-16	深黄色液体	-	-	-	-	0.08	+	+	+	-	+
S-17	浅黄色液体	-	-	-	-	0.19	+	+	+	-	+
S-18	浅绿色液体	-	0.73	-	-	-	-	+	-	-	-
S-19	浅绿色液体	-	0.71	-	-	-	-	+	-	-	-
S-20	浅黄色液体	-	-	-	0.28	0.53	+	-	-	-	-
S-21	浅黄色液体	0.58	-	0.80	-	-	+	-	+	-	-
S-22	浅黄色液体	-	-	0.70	-	-	+	+	+	-	-
S-23	浅黄色液体	-	-	0.89	-	-	+	+	-	-	-
S-24	浅黄色液体	-	-	2.74	-	-	+	-	-	-	-
S-25	浅黄色液体	-	-	1.85	-	-	+	-	-	-	-

[1]	Wen-ya ZHAI, Li-na WU, Shuo YANG, Bao-hua SHEN, Yan SHI. Detection and Analysis of Blood Dexmedetomidine in Drug-Facilitated Cases [J]. Journal of Forensic Medicine, 2023, 39(5): 452-456.
[2]	Wu LONG, Peng-fei QU, Lin MA, Rui WANG, Yan-mei XI, Yu-hua LI, Sheng-jie NIE, Ting DUAN, Jin-liang DU, Xue TANG, Jing-feng ZHAO, Pu-ping LEI, Yue-bing WANG. Cytotoxicity of 4 Wild Mushrooms in a Case of Yunnan Sudden Unexplained Death [J]. Journal of Forensic Medicine, 2023, 39(2): 121-128.
[3]	Tai-feng JIAO, Ya-qing LI, Gang KANG, Shen-shu CHEN, Liang-hong CHENG. Detection of Synthetic Cannabinoid CUMYL-PEGACLONE in E-Cigarette Oil and Hair [J]. Journal of Forensic Medicine, 2022, 38(5): 595-600.
[4]	Ping XIANG, Ning-guo LIU, Bao-hua SHEN, Huo-sheng QIANG, Min SHEN. Strategies for Collection and Analysis of Samples in Simple Asphyxiant Gas Acute Poisoning Death Cases [J]. Journal of Forensic Medicine, 2022, 38(4): 507-514.
[5]	Liu YANG, Ping XIANG, Hong-xiao DENG, Huo-sheng QIANG, Yong-hui DANG, Yan SHI, Bao-hua SHEN. Forensic Analysis of 9 Poisoning Death Cases Caused by Oral Administration of Diphenidol [J]. Journal of Forensic Medicine, 2022, 38(4): 495-499.
[6]	Xiu-ying YAN, Ping XIANG, Zhi-guo YU, Hui YAN. Application of Metabonomics in Substance Abuse Toxicology Research [J]. Journal of Forensic Medicine, 2022, 38(3): 400-407.
[7]	Shuang-ying HU, Xian-guo FU, Ming ZHANG, Lian-jun CAO, Reheman AIKEBAIER. Detection of Phosphatidylethanol in Whole Blood by UPLC-MS/MS [J]. Journal of Forensic Medicine, 2022, 38(3): 367-373.
[8]	Hui YAN, Meng DU, Zheng QIAO, Ping XIANG, Bao-hua SHEN, Min SHEN, Wei LIU. Analysis of the Distribution of Total Phosphine and the Characteristics of Phosphine Poisoning in 29 Victims [J]. Journal of Forensic Medicine, 2022, 38(2): 254-257.
[9]	Shi-jun HONG, Bao-yu SHEN, Rong-ji SUN, Gen-meng YANG, Chun-mei DUAN, Qian-yun NIE, Cong-bin ZHANG, Wen-juan DONG, Hao YU, Shang WANG, Peng-liang LIU, Pin-yuan WEN, Li-hua LI. Current Situation of Methamphetamine Abuse and Related Research Progress [J]. Journal of Forensic Medicine, 2021, 37(6): 763-775.
[10]	Cui ZHANG, Xu ZHAO, Hui-jun WANG, Xia YUE. Research Progress on the Omics of Methamphetamine Toxic Damage and Addiction [J]. Journal of Forensic Medicine, 2021, 37(6): 776-787.
[11]	Shi-qiu MENG, Jie SHI. Abuse of Pharmaceutical Drugs and Its Prevention [J]. Journal of Forensic Medicine, 2021, 37(6): 788-795.
[12]	Wu-hua ZHANG, Ming-long ZHANG, Wei-wei JING, Bing XIE, Hai-tao BI, Feng YU, Bin CONG, Chun-ling MA, Di WEN. Inhibitory Effect of CCK-8 on Methamphetamine-Induced Apoptosis [J]. Journal of Forensic Medicine, 2021, 37(6): 796-805.
[13]	Tao WANG, Sai-qun WU, Xiao-hui TAN, Chuan-xiang CHEN, Xia YUE, Hui-jun WANG, Si-hao DU, Dong-fang QIAO. Transcriptomic Changes of Astrocytes in the Brain of Rats with Subacute METH Exposure [J]. Journal of Forensic Medicine, 2021, 37(6): 806-812.
[14]	Yi-fan LI, Yi-bin CHENG, Zhi-ling TIAN, Ning-guo LIU. Research Progress of Zebrafish Model in Toxicology and Its Application Prospects in Forensic Science [J]. Journal of Forensic Medicine, 2021, 37(6): 867-872.
[15]	Rui BAI, Bing XIE, Bin CONG, Chun-ling MA, Di WEN. Epidemiological Characteristics of Sedative-Hypnotics and Opioid Painkillers at High-Frequency Exposure [J]. Journal of Forensic Medicine, 2021, 37(5): 694-698.