Cations Derived from Fentanyls Generated by Atmospheric Pressure Photoionization in the Presence of Ammonia: An IMS-MS Study

Autor: Udo H. Verkerk, Stefan Lukow, Justin Kai-Chi Lau, Alan C. Hopkinson, Vladimir Romanov
Rok vydání: 2021
Předmět:
Zdroj: Journal of the American Society for Mass Spectrometry. 32:1700-1706
ISSN: 1879-1123
1044-0305
DOI: 10.1021/jasms.1c00083
Popis: A set of fentanyl molecules when subjected to vacuum UV atmospheric pressure photoionization (VUV-APPI) in the presence of dopants (ammonia and anisole) shows two major bands in the ion mobility-mass spectrometry (IMS-MS) spectrum corresponding to (a) the protonated fentanyl, [M+H]+ and (b) a unique [M-74]+ ion. For the parent fentanyl, the [M-74]+ ion is at m/z 262 but, in the absence of ammonia, the product ion is shifted to m/z 245, corresponding to a difference of NH3. Collision-induced dissociations (CID) of the [M-74]+ ions for all the different fentanyls examined here show the same pattern of neutral losses, namely NH3 and HN=CH2, and the dominant product ion is at m/z 84 (shifted to m/z 98 for 3-methylfentanyl and m/z 142 and 231 for carfentanyl). Dissociation of the [M-74-NH3]+ ion derived from the fentanyls yields the same product ions as found in the electron impact (EI) ionization spectra of the fentanyls. The dissociation products of the [M-74-HN=CH2]+ ion are different, include the ion at m/z 84, and correspond to the fragmentation products of protonated norfentanyls. Theoretical modeling supports the opening of new fragmentation channels as a result of the reaction of the initially formed iminium cation with ammonia at atmospheric pressure.
Databáze: OpenAIRE