人尿中氟胺酮代谢物气相色谱-质谱分析及其质谱特征  

Analysis of 2-fluorodeschloroketamine metabolites in human urine based on gas chromatography-mass spectrometry and their mass spectrometry characteristics

作　　者：张芳 张迪 罗轩[1,3] 黄克建 刘晓锋[2] 杨宁[2] 罗秋莲[1] 李骏波[4] 容创华 ZHANG Fang;ZHANG Di;LUO Xuan;HUANG Kejian;LIU Xiaofeng;YANG Ning;LUO Qiulian;LI Junbo;RONG Chuanghua(School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China;Evidence Identification Center,Guangxi Zhuang Autonomous Region Public Security Department,Nanning 530012,China;Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development,Nanning 530004,China;Anti-Drug Detachment,Public Security Bureau of Nanning,Nanning 530221,China;Criminal Investigation Detachment,Public Security Bureau of Yulin,Yulin 537000,China)

机构地区：[1]广西大学化学化工学院,广西南宁530004 [2]广西壮族自治区公安厅物证鉴定中心,广西南宁530012 [3]广西高校应用化学技术与资源开发重点实验室,广西南宁530004 [4]南宁市公安局禁毒支队,广西南宁530221 [5]玉林市公安局刑侦支队,广西玉林537000

出　　处：《广西大学学报(自然科学版)》2025年第1期200-212,共13页Journal of Guangxi University(Natural Science Edition)

基　　金：广西科学计划项目(桂科AD19259004)。

摘　　要：利用顶空吸附结合固相微萃取技术对10例疑似吸食氟胺酮人员尿样中的氟胺酮(2-fluorodeschloroketamine,2-FDCK)及其代谢物进行富集,并采用气相色谱-质谱联用仪(GC-MS)对尿样中2-FDCK代谢物进行鉴定。从中鉴定出4类共6个2-FDCK代谢物,分别为去甲氟胺酮、去甲去氢氟胺酮、2个去甲加氢氟胺酮和2个加氢氟胺酮。在此基础上,对GC-MS分析时获取的2-FDCK及其代谢物在电子电离(EI)和化学电离(CI)2种离子源下的质谱数据进行全面解析,给出主要碎片离子的裂解途径。结果表明:在EI源下,2-FDCK及其代谢物的裂解均围绕环己酮基展开,先后发生脱CO和脱酰基自由基裂解。而在CI源下,2-FDCK及其代谢物结构中的氮和氧原子均可以获得质子,生成2种准分子离子,前者以脱氨(甲胺)开始其断裂过程,后者则以脱水引发后续的各种裂解。对2-FDCK及其代谢物在CI和EI源下质谱裂解的研究,有助于对未来可能出现的氯胺酮类NPS及其代谢物的筛查及结构推断,实现对已知氯胺酮类NPS及其代谢物的快速定性以及对氯胺酮类NPS的预测和预警。Headspace adsorption and solid-phase microextraction technology was used for enriching 2-fluorodeschloroketamine(2-FDCK)and its metabolites in ten urine samples of persons suspected of taking 2-FDCK,then the metabolites were identified by gas chromatography-mass spectrometry(GC-MS).Four categories of six 2-FDCK metabolites were identified from the urine samples:they were nor-2-fluorodeschlorohydroxylimine,dehydro-nor-2-fluorodeschlorohydroxylimine,two dihydro-2-fluorodeschloroketamines,and two dihydro-nor-2-fluorodeschlorohydroxylimines.On this basis,the mass spectrometry(MS)data of 2-FDCK and its metabolites obtained under the electron ionization(EI)and chemical ionization(CI)sources were fully elucidated and the cleavage patterns of major fragments were provided.The results show that the cleavage of 2-FDCK and its metabolites under the EI source is all around the 2-oxo cyclohexyl group,followed by losing CO and acyl radical in turn.Under the CI source,both nitrogen and oxygen atoms in the structures of 2-FDCK and its metabolites can obtain protons,there are two types of excimer ions.The excimer ion with the protonated nitrogen atom starts its fracture process with deamination(methylamine)and the excimer ion having the protonated oxygen atoms begin various subsequent cleavages with the dehydration process.The study on the cleavage of 2-FDCK and its metabolites by mass spectrometry under CI and EI sources is helpful for the screening and structure inference of ketamine NPS and their metabolites in the future and can realize the rapid characterization of known ketamine NPS and their metabolites,as well as the prediction and early warning of ketamine NPS.

关 键 词：氟胺酮 代谢物 固相微萃取 气相色谱-质谱 质谱裂解 

分 类 号：O657.6[理学—分析化学]