Electrospray tandem mass spectrometric investigations of morphinans

Abstract

In this study positive ESI tandem mass spectra of the [M ϩ H] ϩ ions of morphinan alkaloids obtained using an ion trap MS were compared with those from a triple quadrupole MS. This allows to assess the differences of the tandem-in-time versus the tandem-in-space principle, often hampering the development of ESI MS/MS libraries. Fragmentation pathways and possible fragment ion structures were discussed. In order to obtain elemental composition, accurate mass measurements were performed. According to the MS/MS fragmentation pathway, the investigated compounds can be grouped into 4 subsets: (1) morphine and codeine, (2) morphinone, codeinone, and neopinone, (3) thebaine and oripavine, (4) -7] or CE/ESI-MS [8,9], mostly from a forensic point of view. Frequently fragmentation by CID is described and applied as LC/MS/MS. Two reviews highlight the field [10,11]. Some systematic approaches to the setup of libraries have been undertaken, including data for morphine and codeine [12][13][14]. However, none of these studies compared data of ion trap and triple quad systems. Most of the morphinan type substances have been investigated before by electron impact ionization MS [15][16][17]. Tandem MS instrumentation and the principles of operation have been extensively discussed in the literature [18]. In contrast to magnetic sector instruments, triple quadrupole, quadrupole ion trap, and quadrupole time-of-flight are all considered to perform low collision energy fragmentation. Nevertheless, the obtained tandem mass spectra can look remarkably different. Although the structure elucidation potential of CID was early recognized [19], the setup of ESI-MS/MS libraries was hampered by lacking reproducibility. This article provides comparable ion trap and triple quadrupole MS/MS data of all discussed substances. Accurate mass data of selected morphinans were obtained by quadrupole time-of-flight and FT-ICR mass spectrometry, respectively.

How human neuroblastoma cells make morphine

“…In a similar application experiment, the neuroblastoma cells were cultured in the presence of 20 M [2,2-2 H 2 ]dopamine, resulting in a 22% isotopic enrichment of this precursor in morphine. According to the characteristic MS fragmentation pattern of morphine, as investigated in our laboratory (18,19), the dopamine molecule resided exclusively in the cyclohexene ring of morphine together with C-15, C-16, and the nitrogen atom ( Table 1 (Fig. 2).…”

Characterization of Three O-Methyltransferases Involved in Noscapine Biosynthesis in Opium Poppy

“…The putative characterization of BIAs according to compound class was based on the generation of certain fragment ions. The fragmentation patterns and mechanisms of benzylisoquinoline-type alkaloids have been investigated extensively (Gioacchini et al, 2000;Schmidt et al, 2005Schmidt et al, , 2007 using ESI[+]-CID (Raith et al, 2003;Schmidt et al, 2005Schmidt et al, , 2007. Generally, fragmentation at the a-carbon linking the isoquinoline and benzyl moieties yields both an isoquinoline and a benzyl ion (Schmidt et al, , 2007.…”

Morphine Biosynthesis in Opium Poppy Involves Two Cell Types: Sieve Elements and Laticifers

“…Electrospray ionization, full-scan mass analyses (mass-to-charge ratio range 200 to 700), and collisional MS/MS experiments were performed as described previously . Collision-induced dissociation spectra of morphinan alkaloids were acquired at 25 eV, and fragmentation patterns were matched with those of authentic standards and/or published spectra (Raith et al, 2003) to confirm compound identities.…”