Fragmentation pathways of drugs of abuse and their metabolites based on QTOF MS/MS and MSE accurate-mass spectra

A study of the fragmentation pathways of several classes of drugs of abuse (cannabinoids, ketamine, amphetamine and amphetamine-type stimulants (ATS), cocaine and opiates) and their related substances has been made. The knowledge of the fragmentation is highly useful for specific fragment selection or for recognition of related compounds when developing MS-based analytical methods for the trace-level determination of these compounds in complex matrices. In this work, accurate-mass spectra of selected compounds were obtained using liquid chromatography coupled to quadrupole time-of-flight mass spectrometry, performing both MS/MS and MSE experiments. As regards fragmentation behavior, the mass spectra of both approaches were quite similar and were useful to study the fragmentation of the drugs investigated. Accurate-mass spectra of 37 drugs of abuse and related compounds, including metabolites and deuterated analogues, were studied in this work, and structures of fragment ions were proposed. The accurate-mass data obtained allowed to confirm structures and fragmentation pathways previously proposed based on nominal mass measurements, although new insights and structure proposals were achieved in some particular cases, especially for amphetamine and ATS, 11-nor-9-carboxy-Delta(9)-tetrahydrocannabinol (THC-COOH) and opiates. Copyright (C) 2011 John Wiley & Sons, Ltd.