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.

Add to citation manager EndNote|Ris|BibTeX

URL: http://www.fyxzz.cn/EN/10.12116/j.issn.1004-5619.2022.320101

http://www.fyxzz.cn/EN/Y2023/V39/I5/457

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]	Hang CHEN. Letter to the Editor： On Critical Toxicological Information of Newly Discovered Toxic Substances and Illegal Drugs [J]. Journal of Forensic Medicine, 2026, 42(1): 64-65.
[2]	Jin-xuan YANG, Dong-an TIAN, Xin-yu TANG, Zhan-ying ZHAO, Xi-yue JING, Dong-mei WANG, Xiao-fei TIAN. The Role of Iron Dysregulation in White Matter Injury Induced by Carbon Mono- xide Poisoning [J]. Journal of Forensic Medicine, 2025, 41(6): 545-551.
[3]	Li-liang LI, Jian-hua ZHANG, Feng CHEN, Rui ZHAO, Ya-dong GUO, Zhen-yuan WANG, Yi-wu ZHOU, Da-wei GUAN, Bin CONG. Expert Consensus on Cause of Death Determinations in Antipsychotics-Related Deaths with Negative Autopsy Findings [J]. Journal of Forensic Medicine, 2025, 41(6): 537-544.
[4]	Xue-yan LIU, Wei JIA, Cui-mei LIU, Zhen-dong HUA, Zhen-chuan MA, Zhi-yu LI. Qualitative Analysis of Precursor Substances of Phenyl-2-Acetone and 3，4-Methylenedioxyphenyl-2-Acetone [J]. Journal of Forensic Medicine, 2025, 41(6): 566-573.
[5]	Hao-jie QIN, Chen MO, Hong-wei LI, Zhi-jiang LIU, Zhe ZHENG. Role of Ferroptosis in Paraquat-Induced Acute Lung Injury in Mice [J]. Journal of Forensic Medicine, 2025, 41(5): 494-501.
[6]	Min SHEN. Practice and Reflection on Forensic Toxicology from the Perspective of Evidence Reliability [J]. Journal of Forensic Medicine, 2025, 41(4): 297-306.
[7]	Xuan-long CHEN, Qiang YUAN, Yong SUN, Die ZHANG, Jian-bin FU, Li-liang LI. Forensic Research Progress on Bongkrekic Acid Poisoning [J]. Journal of Forensic Medicine, 2025, 41(2): 111-119.
[8]	Shuai ZHANG, Hong-fei XU, Zhi-xiang ZHANG, Ying WANG, Shao-hua ZHU. Research on Doxorubicin-Induced Cardiotoxicity Mechanism and Its Forensic Application [J]. Journal of Forensic Medicine, 2025, 41(2): 120-126.
[9]	Yu-meng ZUO, Wei HAN, Jian-bo ZHANG, Tao LI. Molecular Mechanisms and Toxic Effects of Ketamine [J]. Journal of Forensic Medicine, 2025, 41(2): 127-135.
[10]	Zhuo LI, Yi-ru ZENG, Zhi-long SHU, Xue-hong SUN, Kui ZHANG. Research Status of Caenorhabditis elegans Model in Toxicology and Its Applications in Forensic Science [J]. Journal of Forensic Medicine, 2025, 41(2): 136-143.
[11]	Rong-shuai WANG, Si-zhe HUANG, Yun-yun WANG, Yan-fei DENG, Zi-jiao DING, Jie ZHANG, Yong LIU, Liang REN, Liang LIU. The Mechanism of Calcium Handling Proteins and NF-κB in Calcium Dyshomeostasis of Cardiomyocytes Caused by Acute MDMA Exposure [J]. Journal of Forensic Medicine, 2025, 41(2): 144-151.
[12]	Hao-wei WANG, Xiao-xing ZHANG, Gen-meng YANG, Shang-wen WANG, Xiao-feng ZENG. The Role of Ferroptosis in Hepatocyte Injury Induced by α-Amanitin [J]. Journal of Forensic Medicine, 2025, 41(2): 152-159.
[13]	Ze-qi LI, Lei XING, Hui-ge ZHANG, Li-rou HE, Jia-yi ZHANG, Jia-qi WANG, Shi-hao LIU, Wei-hong YANG. Analysis of Methadone-Related Poisoning Cases [J]. Journal of Forensic Medicine, 2025, 41(2): 160-167.
[14]	Yu-hao YUAN, Zhong-hao YU, Jia-xin ZHANG, Long-da MA, Shu-quan ZHAO, Ning-guo LIU, Rong-qi WU, Biao ZHANG, Xin-biao LIAO, Xin CHEN, Guang-long HE, Yi-wu ZHOU. Recommendation for Forensic Identification Guidelines on Insulin Overdoes [J]. Journal of Forensic Medicine, 2025, 41(2): 168-175.
[15]	Jin-ting LIU, Li-ying ZHOU, Jia-hong XIANG, Zi-yi LI, Wan-ting XIE, Ke-ming YUN, Yan SHI. Research Progress on Detection of New Psychoactive Substance Piperazines in vivo [J]. Journal of Forensic Medicine, 2024, 40(3): 276-283.