title: Study of the fragmentation pattern of ketamine-heptafluorobutyramide by gas chromatography/electron ionization mass spectrometry.
abstract: Ketamine is an anaesthetic compound used in human and veterinary medicine with hallucinogen properties that have resulted in its increased illicit use by teenagers at rave parties. Although several gas chromatography/mass spectrometry (GC/MS) methods have been reported for the quantification of the drug both in urine and in hair, its electron ionization (EI) fragmentation after derivatization with different reagents has been not yet fully investigated. The present work reports the study of the fragmentation of ketamine, derivatized with heptafluorobutyric anhydride (HFBA-Ket), using gas chromatography/electron ionization mass spectrometry (GC/EI-MS). The complete characterization of the fragmentation pattern represented an intriguing exercise and required tandem mass spectrometry (MS(n)) experiments, high-resolution accurate mass measurements and the use of deuterated d(4)-ketamine to corroborate the proposed structures and to characterize the fragment ions carrying the unchanged aromatic moiety. Extensive fragmentation was observed, mainly located at the cyclohexanone ring followed by rearrangement of the fragment ions, as confirmed by the mass spectra obtained from the deuterated molecule. The GC/EI-MS analysis of HFBA-Ket will represent a useful tool in forensic science since high-throughput analyses are enabled, preserving both the GC stationary phase and the cleanliness of the mass spectrometer ion optics.
authors: Department of Public Medicine and Social Safety, University of Naples Federico II, Via Pansini, 5, 80131 Naples, Italy. maria.pieri@unina2.it
authors: Maria
authors: M
authors: Pieri
authors: Loredana
authors: L
authors: Castiglia
authors: Nadia
authors: N
authors: Miraglia
authors: Rossella
authors: R
authors: Guadagni
authors: Livia
authors: L
authors: Malorni
authors: Nicola
authors: N
authors: Sannolo
authors: Antonio
authors: A
authors: Acampora
authors: Elvira
authors: E
authors: Della Casa
mesh_terms: D000465:Algorithms; D005466:Fluorocarbons / Q000032:analysis* / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D005740:Gases / Q000032:analysis / Q000737:chemistry; D007649:Ketamine / Q000032:analysis* / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
chemical_list: D005466:Fluorocarbons; D005740:Gases; C014581:heptafluorobutyramides; D007649:Ketamine