Chemical characterization of synthetic cannabinoids by electrospray ionization FT-ICR mass spectrometry Jade B. Kill a , Izabela F. Oliveira a,b , Lilian V. Tose a , Helber B. Costa a , Ricardo M. Kuster a , Leandro F. Machado c , Radigya M. Correia a , Rayza R.T. Rodrigues a , Géssica A. Vasconcellos d , Boniek G. Vaz d, **, Wanderson Romão a,b, * a Laboratório de Petroleômica e Química Forense, Departamento de Química, Universidade Federal do Espírito Santo, 29075-910 Vitória, ES, Brazil b Instituto Federal do Espírito Santo, 29106-010 Vila Velha, ES, Brazil c Instituto Nacional de Criminalística, Polícia Federal, Ministério da Justiça, 74001-970, 70610-200 Brasília, DF, Brazil d Instituto de Química, Universidade Federal de Goiás, 74001-970 Goiânia, GO, Brazil A R T I C L E I N F O Article history: Received 26 March 2016 Received in revised form 3 July 2016 Accepted 8 July 2016 Available online 19 July 2016 Keywords: Marijuana Synthetic cannabinoids NPS Mass spectrometry ESI-FT-ICR MS A B S T R A C T The synthetic cannabinoids (SCs) represent the most recent advent of the new psychotropic substances (NPS) and has become popularly known to mitigate the effects of the D 9 -THC. The SCs are dissolved in organic solvents and sprayed in a dry herbal blend. However, little information is reported on active ingredients of SCs as well as the excipients or diluents added to the herbal blend. In this work, the direct infusion electrospray ionization Fourier transform ion cyclotron mass spectrometry technique (ESI-FT- ICR MS) was applied to explore the chemical composition of nine samples of herbal extract blends, where a total of 11 SCs (UR-144, JWH-073, XLR-11, JWH-250, JWH-122, AM-2201, AKB48, JWH-210, JWH-081, MAM-2201 and 5F-AKB48) were identified in the positive ionization mode, ESI(+), and other 44 chemical species (saturated and unsaturated fatty acids, sugars, flavonoids, etc.) were detected in the negative ionization mode, ESI(). Additionally, CID experiments were performed, and fragmentation pathways were proposed to identify the connectivity of SCs. Thus, the direct infusion ESI-FT-ICR MS technique is a powerful tool in forensic chemistry that enables the rapid and unequivocal way for the determination of molecular formula, the degree of unsaturation (DBE—double bond equivalent) and exact mass (<1 ppm) of a total of 55 chemical species without the prior separation step. ã 2016 Elsevier Ireland Ltd. All rights reserved. 1. Introduction The Cannabis sativa L. plant has great therapeutic and psychotropic potentials. It contains more than 421 chemical substances, from which more than 60 were reported as cannabi- noids, being the D 9 -tetrahydrocannabinol (D 9 -THC), the principal cannabinoid found with the highest psychoactive activity [1]. The term cannabinoid is attributed to the group of molecules composed of 21 carbon atoms present in the C. sativa L., and their products of transformation [2]. In the last decades, analogous compounds to D 9 -THC were synthesized in order to explore the endocannabinoid system as having potential psychotherapeutic effects. This fact established the class of synthetic cannabinoids (SCs). The SCs represent the most recent advent of the designer drugs, which are drugs created or structurally modified to difficult their detection from conven- tional analytical methods, and its prohibition by current legisla- tion, thus facilitating its illicit market [3–5]. The SCs have become popular in the trying of to mitigate the effects of D 9 -THC, which is one of the most consumed drugs in the world [6]. In Europe, at the beginning of the 21st century, the SCs were freely commercialized, being not prescribed drugs. They were mainly named Spice and K2 and sold as incense and leaves extracts, which having or not metallic packages (Fig. 1) [5]. Currently, the SCs are synthesized in clandestine laboratories mostly in China. Afterwards, they are dissolved in organic solvents (ethanol, acetone or methanol) and sprayed in a dry herbal blend, which can also have intrinsic psychotropic effects. Among the natural products that can be mixed to the SCs, stand out: Melissa, Mentha, Thymus, Damiana, Indian Warrior , Lion’s Tail, Baybean, Blue Lotus, Vanilla, and Honey [7,8]. * Corresponding author at: Laboratório de Petroleômica e Química Forense, Departamento de Química, Universidade Federal do Espírito Santo, 29075- 910 Vitória, ES, Brazil. ** Corresponding author. E-mail addresses: boniek@ufg.br (B.G. Vaz), wandersonromao@gmail.com (W. Romão). http://dx.doi.org/10.1016/j.forsciint.2016.07.007 0379-0738/ã 2016 Elsevier Ireland Ltd. All rights reserved. Forensic Science International 266 (2016) 474–487 Contents lists available at ScienceDirect Forensic Science International journal homepage: www.elsevier.com/locate/forsciint