Cargando…

Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR

Among the phencyclidine (PCP) and synthetic cathinone analogs present on the street market, 3-methoxyphencyclidine (3-MeO-PCP) is one of the most popular dissociative hallucinogen drugs, while 3-methylmethcathinone (3-MMC) is a commonly encountered psychostimulant. Numerous 3-MeO-PCP- and 3-MMC-rela...

Descripción completa

Detalles Bibliográficos
Autores principales: Frison, Giampietro, Zancanaro, Flavio, Frasson, Samuela, Quadretti, Laura, Agnati, Michele, Vlassich, Francesca, Gagliardi, Giuseppe, Salerno, Tania Maria Grazia, Donato, Paola, Mondello, Luigi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7897676/
https://www.ncbi.nlm.nih.gov/pubmed/33628763
http://dx.doi.org/10.3389/fchem.2020.618339
_version_ 1783653715441352704
author Frison, Giampietro
Zancanaro, Flavio
Frasson, Samuela
Quadretti, Laura
Agnati, Michele
Vlassich, Francesca
Gagliardi, Giuseppe
Salerno, Tania Maria Grazia
Donato, Paola
Mondello, Luigi
author_facet Frison, Giampietro
Zancanaro, Flavio
Frasson, Samuela
Quadretti, Laura
Agnati, Michele
Vlassich, Francesca
Gagliardi, Giuseppe
Salerno, Tania Maria Grazia
Donato, Paola
Mondello, Luigi
author_sort Frison, Giampietro
collection PubMed
description Among the phencyclidine (PCP) and synthetic cathinone analogs present on the street market, 3-methoxyphencyclidine (3-MeO-PCP) is one of the most popular dissociative hallucinogen drugs, while 3-methylmethcathinone (3-MMC) is a commonly encountered psychostimulant. Numerous 3-MeO-PCP- and 3-MMC-related intoxication cases have been reported worldwide. Identification of the positional isomers of MeO-PCP and MMC families are particularly challenging for clinical and forensic laboratories; this is mostly due to their difficult chromatographic separation (particularly when using liquid chromatography–LC) and similar mass spectrometric behaviors. 3-MeO-PCP and 3-MMC were identified in two powders, detained by two subjects and seized by the police, by different analytical techniques, including liquid chromatography-high-resolution accurate-mass Orbitrap mass spectrometry (LC-HRAM-Orbitrap-MS), and solid deposition gas chromatography-Fourier transform infrared spectroscopy (sd-GC-FTIR). LC-HRAM-Orbitrap-MS allowed us to assign the elemental formulae C(18)H(27)NO (MeO-PCP) and C(11)H(15)NO (MMC) through accurate mass measurement of the two MH(+) ions, and the comparison of experimental and calculated MH(+) isotopic patterns. However, MH(+) collision-induced product ions spectra were not conclusive in discriminating between the positional isomers [(3-MeO-PCP vs. 4-MeO-PCP) and (3-MMC vs. 4-MMC and 2-MMC)]. Likewise, sd-GC-FTIR easily allowed us to differentiate between the MeO-PCP and MMC positional isomers unambiguously, confirming the presence of 3-MeO-PCP and 3-MMC, due to the high-quality match factor of the experimental FTIR spectra against the target FTIR spectra of MeO-PCP and MMC isomers in a dedicated library. 3-MeO-PCP (in contrast to 3-MMC) was also detected in blood and urine samples of both subjects and analyzed in the context of routine forensic casework by LC-HRAM-Orbitrap-MS following a simple deproteinization step. In addition, this untargeted approach allowed us to detect dozens of phase I and phase II 3-MeO-PCP metabolites in all biological specimens. Analysis of the extracted samples by sd-GC-FTIR revealed the presence of 3-MeO-PCP, thus confirming the intake of such specific methoxy-PCP isomer in both cases. These results highlight the effectiveness of LC-HRAM-Orbitrap-MS and sd-GC-FTIR data in attaining full structural characterization of the psychoactive drugs, even in absence of reference standards, in both non-biological and biological specimens.
format Online
Article
Text
id pubmed-7897676
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher Frontiers Media S.A.
record_format MEDLINE/PubMed
spelling pubmed-78976762021-02-23 Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR Frison, Giampietro Zancanaro, Flavio Frasson, Samuela Quadretti, Laura Agnati, Michele Vlassich, Francesca Gagliardi, Giuseppe Salerno, Tania Maria Grazia Donato, Paola Mondello, Luigi Front Chem Chemistry Among the phencyclidine (PCP) and synthetic cathinone analogs present on the street market, 3-methoxyphencyclidine (3-MeO-PCP) is one of the most popular dissociative hallucinogen drugs, while 3-methylmethcathinone (3-MMC) is a commonly encountered psychostimulant. Numerous 3-MeO-PCP- and 3-MMC-related intoxication cases have been reported worldwide. Identification of the positional isomers of MeO-PCP and MMC families are particularly challenging for clinical and forensic laboratories; this is mostly due to their difficult chromatographic separation (particularly when using liquid chromatography–LC) and similar mass spectrometric behaviors. 3-MeO-PCP and 3-MMC were identified in two powders, detained by two subjects and seized by the police, by different analytical techniques, including liquid chromatography-high-resolution accurate-mass Orbitrap mass spectrometry (LC-HRAM-Orbitrap-MS), and solid deposition gas chromatography-Fourier transform infrared spectroscopy (sd-GC-FTIR). LC-HRAM-Orbitrap-MS allowed us to assign the elemental formulae C(18)H(27)NO (MeO-PCP) and C(11)H(15)NO (MMC) through accurate mass measurement of the two MH(+) ions, and the comparison of experimental and calculated MH(+) isotopic patterns. However, MH(+) collision-induced product ions spectra were not conclusive in discriminating between the positional isomers [(3-MeO-PCP vs. 4-MeO-PCP) and (3-MMC vs. 4-MMC and 2-MMC)]. Likewise, sd-GC-FTIR easily allowed us to differentiate between the MeO-PCP and MMC positional isomers unambiguously, confirming the presence of 3-MeO-PCP and 3-MMC, due to the high-quality match factor of the experimental FTIR spectra against the target FTIR spectra of MeO-PCP and MMC isomers in a dedicated library. 3-MeO-PCP (in contrast to 3-MMC) was also detected in blood and urine samples of both subjects and analyzed in the context of routine forensic casework by LC-HRAM-Orbitrap-MS following a simple deproteinization step. In addition, this untargeted approach allowed us to detect dozens of phase I and phase II 3-MeO-PCP metabolites in all biological specimens. Analysis of the extracted samples by sd-GC-FTIR revealed the presence of 3-MeO-PCP, thus confirming the intake of such specific methoxy-PCP isomer in both cases. These results highlight the effectiveness of LC-HRAM-Orbitrap-MS and sd-GC-FTIR data in attaining full structural characterization of the psychoactive drugs, even in absence of reference standards, in both non-biological and biological specimens. Frontiers Media S.A. 2021-02-08 /pmc/articles/PMC7897676/ /pubmed/33628763 http://dx.doi.org/10.3389/fchem.2020.618339 Text en Copyright © 2021 Frison, Zancanaro, Frasson, Quadretti, Agnati, Vlassich, Gagliardi, Salerno, Donato and Mondello. http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY) (http://creativecommons.org/licenses/by/4.0/) . The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
Frison, Giampietro
Zancanaro, Flavio
Frasson, Samuela
Quadretti, Laura
Agnati, Michele
Vlassich, Francesca
Gagliardi, Giuseppe
Salerno, Tania Maria Grazia
Donato, Paola
Mondello, Luigi
Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR
title Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR
title_full Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR
title_fullStr Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR
title_full_unstemmed Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR
title_short Analytical Characterization of 3-MeO-PCP and 3-MMC in Seized Products and Biosamples: The Role of LC-HRAM-Orbitrap-MS and Solid Deposition GC-FTIR
title_sort analytical characterization of 3-meo-pcp and 3-mmc in seized products and biosamples: the role of lc-hram-orbitrap-ms and solid deposition gc-ftir
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7897676/
https://www.ncbi.nlm.nih.gov/pubmed/33628763
http://dx.doi.org/10.3389/fchem.2020.618339
work_keys_str_mv AT frisongiampietro analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT zancanaroflavio analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT frassonsamuela analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT quadrettilaura analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT agnatimichele analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT vlassichfrancesca analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT gagliardigiuseppe analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT salernotaniamariagrazia analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT donatopaola analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir
AT mondelloluigi analyticalcharacterizationof3meopcpand3mmcinseizedproductsandbiosamplestheroleoflchramorbitrapmsandsoliddepositiongcftir