Fingerprinting of 3, 4-Methylenedioxymethamphetamine Markers by Desorption/Ionization on Porous Silicon

Abstract

Desorption/ionization on porous silicon (DIOS) is a method which extends the application range of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. This technique eliminates matrix background in the low mass range; DIOS is especially advantageous in research on small organic molecules and their metabolites in biological samples. DIOS mass spectrometry was applied for 3, 4-methylenedioxymethamphetamine, (MDMA, Ecstasy) impurities identification. Trace components profiling enables the identification of by-products characteristics for the synthesis route of MDMA. Ecstasy, a synthetic psychoactive drug, is highly popular among young people, and often used as a recreational drug, most commonly used during disco parties. MDMA enhances feeling of euphoria by increasing the level of neurotransmitters such as serotonin, dopamine and norepinephrine, and causes acute behavioral and psychological effects. MDMA is almost exclusively produced illegally, primarily in Western Europe. The new method for MDMA impurities profiling has been developed to trace the origin of MDMA pills. For comparison and classification of the impurity profiles, the principal components analysis was used.

A Review of Recent Advances in Impurity Profiling of Illicit MDMA Samples

“…While impurity profiles are most commonly generated by GC‐MS, the technique is limited for the analysis of nonvolatile impurities and components (64). However, the sensitivity and definitive identification capabilities offered by MS warrant further research in this area, potentially using different methods of sample introduction, for example desorption ionization on porous silicon (DIOS) and desorption electrospray ionization (DESI) (64,65).…”

“…In 2006, Kraj et al. synthesized MDMA by four different synthetic routes (reductive amination with two different reducing agents, bromosafrole, and Leuckart routes) and analyzed the final product using DIOS‐MS (64). The ionization method is similar to matrix‐assisted laser desorption ionization (MALDI) except that DIOS does not require a matrix.…”

“…The ionization method is similar to matrix‐assisted laser desorption ionization (MALDI) except that DIOS does not require a matrix. Hence, resultant spectra are not overwhelmed with matrix fragments, which can limit MALDI‐MS, particularly in the spectral region below m/z 500 (64). Using DIOS, ions were identified that were specific to each of the synthetic routes investigated, for example, the presence of a fragment ion at m/z 149.1 was due to α‐cleavage of piperonal, indicating this aldehyde as a precursor for the synthesis.…”

“…Using DIOS, ions were identified that were specific to each of the synthetic routes investigated, for example, the presence of a fragment ion at m/z 149.1 was due to α‐cleavage of piperonal, indicating this aldehyde as a precursor for the synthesis. Although numerous ions were found to be common to different impurities, significant differences in spectra in the range m/z 300–550 were sufficient for distinction of the synthetic route (64). While the potential of this technique is not in doubt, the authors did not apply DIOS‐MS to the analysis of illicitly produced ecstasy tablets and hence, further investigation is necessary.…”

Development of Nanomaterials for SALDI‐MS Analysis in Forensics

“…It also shields the analyte from direct laser impact, reducing analyte fragmentation and aids in the ionization of the analyte enabling detection. In forensics, SALDI was used to determine the synthetic route of 3,4‐methylenedioxymethamphetamine (MDMA) 21. MDMA has no legitimate medical use and is illegally sold in tablet form as the party drug, ‘ecstasy’.…”