基于GC-Q TOF MS和LC-Q Orbitrap MS的依托咪酯及其类似物质谱裂解规律研究  

Fragmentation patterns of etomidate analogues based on GC-Q TOF MS and LC-Q Orbitrap MS

作　　者：范一雷 赵森[1] 杨奕轩 柯星 徐雨 陈显鑫 FAN Yi-lei;ZHAO Sen;YANG Yi-xuan;KE Xing;XU Yu;CHEN Xian-xin(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 Narcotics Laboratory Zhejiang Regional Center,Hangzhou 310053,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

出　　处：《药物分析杂志》2025年第1期116-124,共9页Chinese Journal of Pharmaceutical Analysis

基　　金：国家重点研发计划项目(2023YFC3303903-3);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-2024-005);上海市现场物证重点实验室开放课题基金资助项目(2024XCWZK11)。

摘　　要：目的:探讨依托咪酯及其类似物在质谱下的裂解规律,为该类物质的鉴定及结构分析提供参考。方法:基于气相色谱-四极杆飞行时间质谱(GC-Q TOF MS)联用技术和液相色谱-静电场轨道阱质谱(LC-Q Orbitrap MS)技术在EI和ESI正电离模式下对依托咪酯、美托咪酯、丙帕酯和异丙帕酯进行质谱分析,推测该类物质的EI-MS以及ESI-MS/MS裂解规律。结果:依托咪酯及其类似物具有相似的裂解途径,在EI-MS模式下断裂过程主要集中在碳氮键的断裂,形成特定的离子碎片(m/z 105和m/z 77)。在ESI-MS/MS正离子模式下断裂过程主要集中在碳氮键的断裂,形成以苯乙烯为中性丢失的特征碎片离子,接着依次丢失中性碎片R_(1)及H_(2)O,形成特定的离子碎片(m/z 113和m/z 95)。此外,在ESI-MS/MS正离子模式中丢失的中性碎片R_(1)可以较直观地反映母核上的取代基,从而进一步确定依托咪酯及其类似物结构。结论:依托咪酯及其类似物质谱裂解规律有助于对该类物质的结构进行解析与推断,为法庭科学实验室该类物质的鉴定及结构分析提供参考。Objective:To explore the fragmentation patterns of etomidate analogues by mass spectrometry to provide reference for the identification and structural analysis of these substances.Methods:Etomidate,metomidate,propaxate and isopropaxate were analyzed by gas chromatography-quadrupole time-of-flight mass spectrometry(GC-Q TOF MS)and liquid chromatography high-resolution mass spectrometry(LC-Q Orbitrap MS)under EI and ESI positive ionization modes.And the EI-MS and ESI-MS/MS fragmentation patterns of etomidate analogues were deduced.Results:Etomidate and its analogues had similar fragmentation pathways.In EI-MS mode,the fragmentation pathway was mainly focused on the breaking of carbon-nitrogen bonds,and the specific fragment ions(m/z 105 and m/z 77)were formed.In ESI-MS/MS positive ion mode,the fragmentation pathway was mainly focused on the fracture of carbon-nitrogen bond,resulting in the formation of the characteristic fragment ion with styrene as neutral loss,Subsequently,the neutral fragments R_(1)and H_(2)O were lost in turn,and the specific fragment ions(m/z 113 and m/z 95)was formed.Moreover,the neutral loss of R_(1)in ESI-MS/MS positive ion mode could more intuitively indicate the substituents on the parent nucleus and further determine the structure of etomidate and its analogues.Conclusion:The fragmentation patterns of etomidate and its analogues are helpful to analyze and infer the structure of these substances,and provide reference for the identification and structural analysis of these substances in forensic laboratory.

关 键 词：依托咪酯及其类似物 质谱裂解规律 快速筛查 电子轰击质谱 电喷雾质谱 毒品替代物 新精神活性物质 

分 类 号：R917[医药卫生—药物分析学]