Structural confirmation of synthetic cannabinoids in seized electronic cigarette oil: A combined mass spectrometric and computational study

Abstract

Rationale Synthetic cannabinoids are some of the most used and abused new psychoactive substances, because they can produce a stronger intense pleasure than natural cannabis. Most of the new synthetic cannabinoids are structurally similar to existing synthetic cannabinoids and can be obtained by modifying partial structures of the latter without changing their effects. Therefore, the derivatization rules and common fragmentation patterns of synthetic cannabinoids could be used for rapid screening and structural identification of them. Methods The derivatization rules of synthetic cannabinoids are summarized, and the common fragmentation pattern of synthetic cannabinoids including three typical cleavage pathways was explored and extended in this work based on combined mass spectrometry (MS) and density functional theory studies. Five synthetic cannabinoids in electronic cigarette oil from a drug case were separated and characterized using gas chromatography with MS and liquid chromatography coupled to high‐resolution quadrupole Orbitrap MS. Results The structures of five synthetic cannabinoids in seized electronic cigarette oil were deduced from electron impact ion source (EI) MS and high‐resolution electrospray ionization (ESI) MSn data, along with the derivatization rules and common fragmentation pattern of synthetic cannabinoids. The proposed structures of these synthetic cannabinoids were further verified via reference substances. Computational study showed that selective cleavage of these compounds was mainly controlled by spin population in EI‐MS, but a tunneling effect arose from proton transfer in ESI‐MSn detection, which has been rarely reported in previous works. Conclusions Our results showed that EI‐MS was suitable for identifying synthetic cannabinoids with aromatic ketone structure, which could also be extended to adamantane linked group. Nevertheless, synthetic cannabinoids with carbamoyl linked group were better characterized by high‐resolution ESI‐MSn compared to EI‐MS. This study demonstrated a method with promising potential for rapid and reliable screening of synthetic cannabinoids in mixtures with enhanced detection throughput and operation simplicity.

Exploring α-electron-deficiency-induced [1,2]-fluorine migration

“…20 It has been proved by several reviews and research studies that this theoretical level is suitable for evaluating organic system. [21][22][23] Frequency calculations are performed at the same theoretical level as that of optimization in order to ensure no imaginary frequency for stationary points and only one for transition states. Thermal corrections for enthalpy, entropy and Gibbs free energy at 298.15 K are directly generated from this.…”