Detection and Quantification of Psychoactive N,N-Dimethyltryptamine in Ayahuasca Brews by Ambient Ionization High-Resolution Mass Spectrometry.

The United Nations Office on Drugs and Crime designated twenty psychoactive botanical species as "plants of concern" because of their increased recreational abuse. Four of these are used to prepare ayahuasca brews. The complexity of the plant matrices, as well as the beverage itself, make the identification and quantification of the Schedule I component, N,N-dimethyltryptamine (DMT), a time-consuming and resource-intensive endeavor when performed using conventional approaches previously reported. Reported here is the development of a rapid validated method for the quantification of DMT in ayahuasca by direct analysis in real time-high-resolution mass spectrometry (DART-HRMS). This ambient ionization approach also enables identification of ayahuasca through detection of the secondary metabolites associated with its plant constituents. Analysis of six ayahuasca brews created using different combinations of DMT/harmala alkaloid-containing plants resulted in beverages with DMT levels of 45.7-230.5 mg/L. The detected amounts were consistent with previously reported values determined by conventional approaches.

An Efficient Ambient Ionization Mass Spectrometric Approach to Detection and Quantification of the Mescaline Content of Commonly Abused Cacti from the Echinopsis Genus.

Unregulated cacti from the genus Echinopsis are used recreationally as mescaline-containing alternatives to the outlawed peyote. Echinopsis-derived plant materials appear in a variety of nondescript forms, making rapid assessment of whether they are mescaline-containing materials or simply innocuous plant-derived food products, very challenging. Reported here is a DART-HRMS approach for the rapid detection of mescaline in whole plant material and a validated method for the quantification of mescaline in cactus tissue, using mescaline-d9 as the internal standard. Calibration curves exhibited R2 values of ≥0.995, and the method exhibited a LLOQ and a linear range of 1 ppm and 1-100 ppm, respectively. Application of the method to commercially available Echinopsis spp. yielded results consistent with previous studies performed by GC- and LC-MS, with mescaline levels of <2% dry weight in all cases. Therefore, DART-HRMS is a suitable technique for the rapid screening of mescaline and its subsequent quantification within complex plant-derived matrices.

Detection of Diagnostic Plant-Derived Psychoactive Biomarkers in Fingerprints by MALDI-SpiralTOF-Mass Spectrometry Imaging.

One of the current challenges in forensics is establishment of a connection between an individual and substances to which they have been exposed, and which might have relevance in crime scene investigation. An example of a situation in which this arises is when an individual has handled, and is under the influence of any one of a large number of currently unscheduled plant-based mind-altering substances. In such instances as a medical emergency or a crime scene investigation , one way to establish a connection between an individual and their exposure to such substances is to take advantage of the high information content of their fingerprint. The fingerprint pattern not only establishes the identity of the individual, but also contains rarely exploited chemical information about molecules to which they have been exposed that might have a bearing on a crime. If the fingerprint image is based on the spatial distribution of diagnostic molecular markers indicative of a substance, then an individual's identity can be definitively tied to exposure to the substance. The fingerprint image derived from the spatial distribution of diagnostic molecules can be obtained by mass spectrometry imaging (MSI). Here, we demonstrate how the handling by an individual of a plant-derived psychoactive brew called ayahuasca can be established through determination, by matrix-assisted laser desorption ionization (MALDI) MSI, of ion images featuring biomarkers from the plants from which the brew is made.

Species Identification of Necrophagous Insect Eggs Based on Amino Acid Profile Differences Revealed by Direct Analysis in Real Time-High Resolution Mass Spectrometry.

The colonization of decomposing remains by necrophagous insects such as blow flies is of forensic importance because the progression through the various stages of insect development can be correlated to time of death. The ability to infer this information hinges on accurate determination of the fly species that are associated with the entomological evidence collected. This evidence can include eggs, larvae, pupae, and puparial casings. Determination of the egg's identity is particularly challenging because the eggs of multiple species are morphologically very similar. We report here that the species identity of fly eggs can be determined from their chemical fingerprint signatures acquired by direct analysis in real time high-resolution mass spectrometry (DART-HRMS). Thus, freshly laid eggs were collected and readily distinguished from multiple necrophagous fly species in the Manhattan area of New York City. These species included representatives from the blow fly family (Calliphoridae), specifically Calliphora vicina, Lucilia sericata, L. coeruleiviridis, and Phormia regina species as well as the Phoridae and Sarcophagidae families. Multivariate statistical analysis of their observed DART-HRMS spectra revealed intraspecies similarities and interspecies differences that were the basis of species differentiation. The chemical basis of discrimination was differences in amino acid profiles. This represents the first chemically based fly egg identification approach with applications to forensic entomology. The rapidity of the method makes feasible the generation of a fly egg chemical profile database against which the DART-HRMS spectra of unknown eggs can be screened to rapidly assess species identity without needing to rear the eggs to adulthood.