新型靛红腙类合成大麻素质谱裂解规律研究  

Investigation of mass spectrometry-based fragmentation patterns of new “OXIZID” synthetic cannabinoids

作　　者：范一雷 陈显鑫 薛锦锋 吴昊 柯星 徐雨 FAN Yilei;CHEN Xianxin;XUE Jinfeng;WU Hao;KE Xing;XU Yu(Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province,Zhejiang Police College,Hangzhou 310053,China;Key Laboratory of Drug Monitoring and Control of Zhejiang Province,National anti-Drug Laboratory Zhejiang Regional Center,Hangzhou 310053,China;Jiaxing Public Security Bureau,Jiaxing 314015,China;Zhejiang Dian Regional Forenic Science Institute,Hangzhou 310007,China)

机构地区：[1]浙江省毒品防控技术研究重点实验室,浙江警察学院,杭州310053 [2]浙江省禁毒和毒情监测关键技术研究重点实验室,国家毒品实验室浙江分中心,杭州310053 [3]嘉兴市公安局,嘉兴314015 [4]浙江迪安司法鉴定中心,杭州310007

出　　处：《分析试验室》2024年第1期57-63,共7页Chinese Journal of Analysis Laboratory

基　　金：浙江省自然科学基金(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(2022-KLDMC-06);浙江省禁毒和毒情检测关键技术研究重点实验室开放基金(2022KLD⁃MC005)资助。

摘　　要：研究了新型靛红腙类合成大麻素在电子轰击(EI)和电喷雾(ESI)电离模式下的质谱裂解规律,并建立了可疑物中该类合成大麻素的鉴定方法。采用气相色谱-质谱联用(GC-MS)和液相色谱-高分辨质谱联用(LC-Q-Orbitrap/MS)技术,对5种新型靛红腙类合成大麻素(MDA-19 (BZO-HEXOXIZID),5C-MDA-19 (Pentyl MDA-19,BZO-POXIZID),CHM-MDA-19 (BZO-CHMOXIZID),4en-pentyl MDA-19(BZO-4en-POXIZID),5F-MDA-19 (5F-BZO-POXIZID))的主要碎片离子和碎裂过程进行分析,并对获得的质谱图进行解析,推测该类合成大麻素的EI-MS及ESI-MS^(n)碎裂规律。EI-MS可获得比ESI-MS^(n)更多的碎片离子用于该类合成大麻素的结构推断。碎片离子6,7和8对应的质荷比(m/z)118 (C_(8)H_(8)N^(+)),132(C_(8)H_(6)NO^(+))和146 (C_(8)H_(6)N_(2)O^(·+))为2-氧代吲哚母核的特征碎片离子。经酰胺键断裂(碎裂途径i)生成碎片离子1(m/z 105,C_(7)H_(5)O^(+)),以及通过腙键及N1与侧链之间发生断裂(碎裂途径iv)生成碎片离子8(m/z 146,C_(8)H_(6)N_(2)O^(·+)),可用于确定该类合成大麻素N8’位上取代基和N1末端取代侧链。本研究阐述了5种新型靛红腙类合成大麻素的质谱裂解规律,并根据获得的质谱裂解规律建立了可疑物中该类合成大麻素的鉴定方法,为其快速结构鉴定提供依据。The mass spectrometry-based fragmentation patterns of new “OXIZIDs”(N-alkylisatin-acylhydrazones) synthetic cannabinoids under electron ionization(EI) and electrospray ionization(ESI) modes were investigated,and the identification method for this kind of synthetic cannabinoids in the suspicious material was developed.Gas chromatography-mass spectrometry(GC-MS) and liquid chromatography high-resolution mass spectrometry(LC-Q-Orbitrap/MS) were used to analyze five new “OXIZID”synthetic cannabinoids,including MDA-19(BZO-HEXOXIZID),5C-MDA-19(Pentyl MDA-19,BZO-POXIZID),CHM-MDA-19(BZOCHMOXIZID),4en-pentyl MDA-19(BZO-4en-POXIZID) and 5F-MDA-19(5F-BZO-POXIZID.The obtained mass spectra of EI-MS and ESI-MSn were analyzed and the fragmentation patterns of “OXIZID” synthetic cannabinoids were speculated.The results showed that the EI-MS could obtain more fragment ions than that of the ESI-MSn for structural identification of “OXIZID”synthetic cannabinoids.The fragment ions 6,7 and 8 correspond to mass-tocharge ratios of 118(C_(8)H_(8)N^(+)),132(C_(8)H_(6)NO^(+)) and 146(C_(8)H_(6)N_(2)O^(·+)),respectively,which are characteristic fragment ions of the 2-oxoindole parent nucleus.Fragment ions 1(m/z 105,C_(7)H_(5)O^(+)) and 8(m/z 146,C_(8)H_(6)N_(2)O^(·+)),generated through the cleavage of amide bond(fragmentation pathway i),hydrazone bonds and the bond between N1 and side chains(fragmentation pathway iv),respectively,can be applied to infer the N8'position substituent and the N1 terminal substitution side chain of “OXIZID” synthetic cannabinoids.The results elucidated the mass spectrometry fragmentation patterns of new “OXIZID” synthetic cannabinoids.And the identification method for this kind of synthetic cannabinoids in the suspicious material was developed based on the obtained EI-MS and ESI-MSn fragmentation patterns of “OXIZID”synthetic cannabinoids,which could provide a basis for their rapid structural identification their.

关 键 词：靛红腙类合成大麻素 质谱裂解规律 快速筛查 电子轰击质谱 电喷雾质谱 

分 类 号：O657.31[理学—分析化学] X832[理学—化学]