合成大麻素类新精神活性物质EI质谱特征研究  

Fragmentation patterns of synthetic cannabinoids based on electron impact ionization mass spectrometry

作　　者：范一雷 陈显鑫 吴昊 柯星 徐雨 FAN Yi-lei;CHEN Xian-xin;WU Hao;KE Xing;XU Yu(Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province,Zhejiang Police College,Hangzhou 310052,China;National Narcotic Laboratory Zhejiang Regional Center,Hangzhou 310052,China;Zhejiang Dian Regional Forenic Science Institute,Hangzhou 310007,China)

机构地区：[1]全省毒品防控技术研究重点实验室,浙江警察学院,杭州310052 [2]国家毒品实验室浙江分中心,杭州310052 [3]浙江迪安司法鉴定中心,杭州310007

出　　处：《药物分析杂志》2024年第9期1463-1474,共12页Chinese Journal of Pharmaceutical Analysis

基　　金：浙江省自然科学基金资助项目(LTGC23H230001、LTGC23B050003);毒品监测管控与禁毒关键技术公安部重点实验室开放基金资助项目(2022-KLDMC-06);全省毒品防控技术研究重点实验室,国家毒品实验室浙江分中心资助项目(NNLZRC-2024-001)。

摘　　要：目的:对合成大麻素类新精神活性物质在电子轰击模式下质谱(EI-MS)的裂解规律进行探讨。方法:采用气相色谱-质谱(GC-MS)对40种合成大麻素类进行系统研究,电子轰击电离源,电子能量70 eV;扫描范围m/z 50~600。结果:依据“头部基团”和“连接基团”结构的不同,将40种合成大麻素分为6类,分别为苯基异丙基-酰胺类、金刚烷-酰胺类、氨甲酰基/丁酸甲酯-酰胺类、萘甲酰类、苯甲/乙酰类和四甲基环丙烷-酰类。通过对合成大麻素EI-MS质谱图的解析,给出了不同种类合成大麻素的EI-MS裂解规律以及特征离子。合成大麻素主要的EI-MS裂解规律为“连接基团”中羰基的两侧极易发生α断裂,以及吲哚/吲唑母核上的N原子易发生γ-H重排,并失去一分子R1。此外,碎片离子m/z 116、130、144为吲唑母核的特征碎片,而碎片离子m/z 117、131、145为吲哚母核的特征碎片离子,可用于确定合成大麻素母核。结论:该类化合物有着较强的裂解规律,在缺少标准物质或商业化的质谱库难以获取时,所提出的合成大麻素EI-MS裂解规律可以帮助对未知的合成大麻素进行快速结构鉴定。Objective:To explore the fragmentation patterns of synthetic cannabinoids by electron impact(EI)ionization mass spectrometry.Methods:Forty synthetic cannabinoids were systematically investigated by gas chromatography coupled to mass spectrometry(GC-MS).Ionization mode was EI(70 eV)and the acquisition range was m/z 50-600.Results:According to the different structures of the“head group”and“linked group”,forty synthetic cannabinoids were divided into six categories,namely cumyl-carboxamide type,adamantyl-carboxamide type,carbamoyl/methyl butyrate-carboxamide type,naphthylformyl type,benzoyl/phenylacetyl type and tetramethylcyclopropane-acyl type.Through the analysis of the mass spectrum of synthetic cannabinoids,the fragmentation pathways and characteristic ions of different types of synthetic cannabinoids were given.The main EI-MS fragmentation patterns of synthetic cannabinoids were that both sides of the carbonyl group in the“linking group”undergoα-cleavage,and the N atom on the indole/indazole parent nucleus was prone toγ-H rearrangement,and loss of a R_1.In addition,fragment ions m/z 116,130,144 and fragment ions m/z 117,131,145 were the characteristic fragments of indazole and indole parent nucleus,which could be used to identify the parent nucleus of synthetic cannabinoids.Conclusion:These kind of compounds have strong fragmentation regularity.When standard substances are lacking or commercial mass spectral libraries are difficult to obtain,the proposed synthetic cannabinoids EI-MS fragmentation pathways can help to rapidly identify the structures of unknown synthetic cannabinoids.

关 键 词：合成大麻素类 气相色谱-质谱 电子轰击模式 结构分类 裂解规律 特征碎片离子 

分 类 号：R917[医药卫生—药物分析学]