Topic: forensic toxicology
WU Bo, QIE Yiqi, YANG Qiao, TIAN Bingbing, ZHAO Yuxin, SU Mengxiang, DI Bin
2-Fluoro-deschloroketamine (2-FDCK), a new substitute for ketamine undergone into changing halogenated element and a new psychoactive substance of phencyclidine class that is being widely abused, has been presently paid of its main research on the analysis of suspected seizures and biological samples. In terms of qualitative determination about 2-FDCK, there are publications relating to the data from IR, mass spectrometry (MS) and NMR (1H NMR, 13C NMR, 19F NMR). 2-FDCK’s quantitative detection primarily adopts gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry, yet leaving it prone to be influenced with the factors of difficulty in obtaining the reference substance and high price. In this paper, one seizure was to identify whether it harbors 2-FDCK via the measures of confirmation of evidential structure and determination of the content of the 2-FDCK hydrochloride, with the qualitative analysis being carried out by elemental analysis, ultraviolet absorption spectrometry (UV), infrared absorption spectrometry (IR), time of flight mass spectrometry (TOF/MS) and nuclear magnetic resonance spectrometry (1H NMR, 13C NMR, DEPT, 1H-1H COSY, 1H-13C HMBC, 1H-13C HSQC). Meanwhile, a 1H quantitative NMR (1H-qNMR) method was hence established and validated for determination of the seized 2-FDCK hydrochloride. For the method, the sample solution was prepared with fumaric acid as the internal standard and the mixture of 0.5 mL DMSO-d6 plus 0.1 mL D2O as the solvent. The NMR spectra were recorded through a standard pulse sequence at a pulse width of 30°. The determination temperature was set at 303 K. The relaxation delay time and the number of scans were optimized to 30 s and 16 times, respectively. The results showed that the accurate mass-to-charge (m/z) of the compound was 222.128 3 under positive electrospray ionization, with the element analysis revealing the percentage content of C, H and N elements as the respective 60.24%, 6.15% and 5.51%. The UV spectrums indicated the absorption peaks at 270 nm and 263 nm corresponded to the B band of the benzene ring, and the IR spectrums demonstrated the presence of functional groups including benzene ring and carbonyl group. All 1H and 13C signals of the compound were fully attributed by combining with one-dimensional (1H NMR, 13C NMR, DEPT) and two-dimensional (1H-1H COSY, 1H-13C HMBC, 1H-13C HSQC) spectra, along with the verification about the existence of the compound in the form of secondary amine salt. Based on the above results, this seizure was confirmed to be 2-(2-Fluorophenyl)-2-(methylamino)cyclohexan-1-one hydrochloride, that is, the 2-FDCK hydrochloride, indeed. More importantly, a 1H-qNMR method was successfully established and validated, showing good specificity and durability. Within the molar ratios of 0.453 0-2.151 2, there was a clear linear relationship between the molar ratio and the integral area ratio of quantitative peak, turning out the correlation coefficient (R2) of 1.000. The final content of the seized 2-FDCK hydrochloride was measured of 99.86%. Accordingly, the complete spectroscopy data of 2-FDCK hydrochloride were obtained through utilization of various analytical techniques, and a 1H-qNMR method was successfully established for determination of the absolute content of 2-FDCK hydrochloride in the seizure, eligible as a reference for quantifying arylcyclohexylamine derivatives. Evidently, when a reference standard is absent or difficult to obtain, NMR approach will be a powerful tool for an unidentified substance to carry out into qualitative and quantitative analysis.