Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province, Department of Criminal Science and Technology, Zhejiang Police College, Hangzhou 310053, China.
Green Pharmaceutical Collaborative Innovation Center of Yangtze River Delta Region, College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310053, China.
Molecules. 2023 Sep 8;28(18):6510. doi: 10.3390/molecules28186510.
Ketamine analogues have been emerging in recent years and are causing severe health and social problems worldwide. Ketamine analogues use 2-phenyl-2-aminocyclohexanone as the basic structure and achieve physiological reactions similar to or even more robust than the prototype of ketamine by changing the substituents on the benzene ring (R and R) and amine group (R). Therefore, the mass spectrometry (MS) fragmentation pathways and fragments of ketamine analogues have certain regularity. Eight ketamine analogues are systematically investigated by GC-QTOF/MS and LC-Q-Orbitrap MS/MS with the positive mode of electrospray ionization. The MS fragmentation patterns of ketamine analogues are summarized according to high-resolution MS data. The α-cleavage of carbon bond C-C in the cyclohexanone moiety and further losses of CO, methyl radical, ethyl radical and propyl radical are the characteristic fragmentation pathways of ketamine analogues in EI-MS mode. The loss of HO or the sequential loss of RNH, CO and CH are the distinctive fragmentation pathways of ketamine analogues in ESI-MS/MS mode. Moreover, these MS fragmentation patterns are first introduced for the rapid screening of ketamine analogues in suspicious powder. Furthermore, the structure of the ketamine analogue in suspicious powder is 2-(Methylamino)-2-(o-tolyl)cyclohexan-1-one, which is further confirmed by NMR. This study contributes to the identification of the chemical structure of ketamine analogues, which can be used for the rapid screening of ketamine analogues in seized chemicals.
近年来，氯胺酮类似物不断涌现，在全球范围内造成了严重的健康和社会问题。氯胺酮类似物以 2-苯基-2-氨基环己酮为基本结构，通过改变苯环（R 和 R'）和氨基（R）上的取代基，达到与氯胺酮原型相似甚至更强的生理反应。因此，氯胺酮类似物的质谱（MS）裂解途径和碎片具有一定的规律性。本研究采用气相色谱-四极杆飞行时间质谱（GC-QTOF/MS）和液相色谱-轨道阱质谱联用（LC-Q-Orbitrap MS/MS），在正离子模式下对 8 种氯胺酮类似物进行了系统研究。根据高分辨 MS 数据总结了氯胺酮类似物的 MS 裂解模式。在 EI-MS 模式下，环己酮部分的碳-碳键 C-C 的α裂解以及进一步失去 CO、甲基自由基、乙基自由基和丙基自由基是氯胺酮类似物的特征裂解途径。在 ESI-MS/MS 模式下，失去 HO 或依次失去 RNH、CO 和 CH 是氯胺酮类似物的特征裂解途径。此外，这些 MS 裂解模式首次被引入用于可疑粉末中氯胺酮类似物的快速筛选。此外，可疑粉末中氯胺酮类似物的结构为 2-（甲基氨基）-2-（邻甲苯基）环己-1-酮，通过 NMR 进一步证实。本研究有助于鉴定氯胺酮类似物的化学结构，可用于快速筛选缴获化学品中的氯胺酮类似物。
