Application of ambient ionization high resolution mass spectrometry to determination of the botanical provenance of the constituents of psychoactive drug mixtures

Lesiak, Ashton D.; Musah, Rabi A.

doi:10.1016/j.forsciint.2016.06.009

Cited by 29 publications

(25 citation statements)

References 33 publications

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“…The chemical composition and the proportion of the identified compounds are variable in the different analyzed samples. It is difficult to compare the results obtained for the samples of B. caapi , M. hostilis , P. harmala and for the commercial mixture, since most chromatographic studies focus on the detection of psychoactive compounds, such as DMT, or β-carboline alkaloids [ 3 , 45 , 46 , 47 , 48 , 49 , 50 ]. Therefore, future research on these plant samples should be focused on the phytochemical characterization and potential bioactive effects associated with these compounds.…”

Section: Resultsmentioning

confidence: 99%

Ayahuasca Beverages: Phytochemical Analysis and Biological Properties

et al. 2020

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Ayahuasca is a psychoactive beverage, originally consumed by indigenous Amazon tribes, of which consumption has been increasing worldwide. The aim of this study was to evaluate the phytochemical profile, as well as the antioxidant, anti-inflammatory and antimicrobial properties of decoctions of four individual plants, a commercial mixture and four mixtures of two individual plants used in the Ayahuasca preparation. For this purpose, a phytochemical characterization was performed, determining the content of flavonoids, total phenolic compounds, and analyzing the phenolic profile. Besides, 48 secondary metabolites were investigated by ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-Q/TOF-MS) and their concentration estimated with real standards when present. The antioxidant activity was evaluated by both the β-carotene bleaching test and DPPH free radical scavenging assay, and the anti-inflammatory activity was determined by a protein denaturation method. Finally, the antimicrobial properties were evaluated using the disc diffusion assay, resazurin microtiter method, anti-quorum sensing and anti-biofilm activity assays. The obtained results showed that, in general, the samples have a high content of phenolic compounds and flavonoids with noticeable differences, reflecting on remarkable antioxidant and anti-inflammatory activities. Significant antimicrobial properties were also observed, with emphasis on the effect of B. caapi and P. harmala on planktonic and biofilm cells of A. baumannii, inhibiting both the biofilm formation and the production of violacein pigment.

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Section: Resultsmentioning

confidence: 99%

Ayahuasca Beverages: Phytochemical Analysis and Biological Properties

et al. 2020

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“…In forensic investigations, it is important to determine the alkaloid content of the concoctions, allowing the application of suitable protocols for overdose investigation. Taxonomic identification of the botanical species used in the preparation of ayahuasca is also important in tracking the source of the product and giving information about the vendor/manufacturer [ 224 ]. Identification of an ayahuasca preparation is manly performed by the confirmation of DMT in samples of the herbal preparation or botanical samples, which is however insufficient to identify the specific psychoactive plant species.…”

Section: Toxicological Analysis and Forensic Relevancementioning

confidence: 99%

Toxicokinetics and Toxicodynamics of Ayahuasca Alkaloids N,N-Dimethyltryptamine (DMT), Harmine, Harmaline and Tetrahydroharmine: Clinical and Forensic Impact

et al. 2020

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Ayahuasca is a hallucinogenic botanical beverage originally used by indigenous Amazonian tribes in religious ceremonies and therapeutic practices. While ethnobotanical surveys still indicate its spiritual and medicinal uses, consumption of ayahuasca has been progressively related with a recreational purpose, particularly in Western societies. The ayahuasca aqueous concoction is typically prepared from the leaves of the N,N-dimethyltryptamine (DMT)-containing Psychotria viridis, and the stem and bark of Banisteriopsis caapi, the plant source of harmala alkaloids. Herein, the toxicokinetics and toxicodynamics of the psychoactive DMT and harmala alkaloids harmine, harmaline and tetrahydroharmine, are comprehensively covered, particularly emphasizing the psychological, physiological, and toxic effects deriving from their concomitant intake. Potential therapeutic utility, particularly in mental and psychiatric disorders, and forensic aspects of DMT and ayahuasca are also reviewed and discussed. Following administration of ayahuasca, DMT is rapidly absorbed and distributed. Harmala alkaloids act as potent inhibitors of monoamine oxidase A (MAO-A), preventing extensive first-pass degradation of DMT into 3-indole-acetic acid (3-IAA), and enabling sufficient amounts of DMT to reach the brain. DMT has affinity for a variety of serotonergic and non-serotonergic receptors, though its psychotropic effects are mainly related with the activation of serotonin receptors type 2A (5-HT2A). Mildly to rarely severe psychedelic adverse effects are reported for ayahuasca or its alkaloids individually, but abuse does not lead to dependence or tolerance. For a long time, the evidence has pointed to potential psychotherapeutic benefits in the treatment of depression, anxiety, and substance abuse disorders; and although misuse of ayahuasca has been diverting attention away from such clinical potential, research onto its therapeutic effects has now strongly resurged.

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“…DART is a rapid, non-contact, ambient ionization technique that produces ions through gas-phase reactions of hot gas effluent from an atmospheric corona-to-glow discharge with reagent molecules and polar or nonpolar analytes [140,141]. The most common applications of DART-TOF with in-source CID are for the analysis of drugs, including synthetic cathinones [32,136,142,143], opioids [144], cannabinoids [145], stimulants [146], and botanicals [147,148]. DART with in-source CID and HRMS provides both molecular weight information from the pseudo-molecular ion and structural information from the in-source CID [149,150].…”

Section: Discussionmentioning

confidence: 99%

Structural Characterization of Emerging Synthetic Drugs

Davidson¹

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Structural Characterization of Emerging Synthetic Drugs J. Tyler Davidson The identification of well-characterized seized drugs is performed thousands of times a day in the United States; however, the expanding use of emerging synthetic drugs is creating a growing problem for both toxicological and seized drug analyses. Two of the most rapidly growing areas of emerging synthetic drugs are synthetic cathinones and fentanyl-related compounds (FRCs). In this work we demonstrate the combination of multi-stage mass spectrometry (MS n), accurate mass measurements with high-resolution mass spectrometry (HRMS), and isotopic labeling for the structural characterization of synthetic cathinones and fentanyl analogs. The deliverables of this research include the identification of conserved fragmentation pathways for synthetic cathinones and fentanyl analogs, proposed mechanisms for the formation of characteristic ions through both protonated tandem mass spectrometry (MS/MS) and electron ionization mass spectrometry (EI-MS), and a discussion about how to apply the broadened understanding of the fragmentation behavior to the identification of novel synthetic cathinones and fentanyl analogs. The first major finding about the fragmentation behavior of synthetic cathinones is that the tropylium ion (m/z 91), or substituted derivative thereof, forms through different oxygencontaining intermediates that do not contain a formal C=O bond but instead contain a phthalanelike core structure. The phthalane-like intermediates were elucidated through gas-phase ion spectroscopy measurements and density functional theory (DFT) calculations. Likewise, the use of stable isotope labeling revealed the unprecedented finding that, during collision-induced dissociation (CID) of α-pyrrolidinophenone synthetic cathinones, the α-carbon is retained almost exclusively in the tropylium ion and the carbonyl carbon is not retained in the tropylium ion. Isotope labeling also identified competitive pathways for the loss of CO and ethylene (C2H4) from a primary intermediate ion, which provides support for the direct loss of CO from the alkyl side chain. A second major finding was the identification of characteristic protonated MS/MS fragmentation pathways and proposed mechanistic origins for both protonated MS/MS and EI-MS fragmentation for α-pyrrolidinophenone and N-alkylated synthetic cathinones. For MS/MS spectra of protonated α-pyrrolidinophenone synthetic cathinones the dominant fragmentation pathways are through 4-center hydrogen rearrangements to produce pyrrolidine ring cleavage, characteristic iminium ions and diagnostic ions at m/z 91 and m/z 105. For EI mass spectra, radical-directed αcleavages result in dominant iminium ions. In contrast to α-pyrrolidinophenone synthetic cathinones, MS/MS of protonated N-alkylated synthetic cathinones provided abundant radical losses from both the N-alkylated and aliphatic side chains, a dominant loss of H2O for 2° amines and the formation of abundant alkylphenones for 3° amines. These findings help advance our cu...

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Application of ambient ionization high resolution mass spectrometry to determination of the botanical provenance of the constituents of psychoactive drug mixtures

Cited by 29 publications

References 33 publications

Ayahuasca Beverages: Phytochemical Analysis and Biological Properties

Ayahuasca Beverages: Phytochemical Analysis and Biological Properties

Toxicokinetics and Toxicodynamics of Ayahuasca Alkaloids N,N-Dimethyltryptamine (DMT), Harmine, Harmaline and Tetrahydroharmine: Clinical and Forensic Impact

Structural Characterization of Emerging Synthetic Drugs

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