Collision-induced dissociation of stable nitroxides: A combined tandem mass spectrometry and computational study of TEMPO center dot and SG1(center dot) - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue European Journal of Mass Spectrometry Année : 2019

Collision-induced dissociation of stable nitroxides: A combined tandem mass spectrometry and computational study of TEMPO center dot and SG1(center dot)

Anouk Gaudel-Siri
Didier Gigmes
Didier Siri
Laurence Charles

Résumé

The dissociation behavior of two stable nitroxides, namely 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO center dot) and N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide (SG1(center dot)), subjected as protonated molecules to collisional activation was investigated using a combination of different mass spectrometry experiments and theoretical calculations. Elemental composition of reaction products was derived from accurate mass data measured in high resolution tandem mass spectrometry experiments, primary fragments were distinguished from secondary ions based on both breakdown curves and MS3 data, and H/D exchange experiments were performed to support proposed structures. Postulated fragmentation pathways were then studied in terms of energetic, using the standard B3LYP/6-31G(d) method. While protonation of TEMPO center dot mainly occurred on the oxygen atom of the nitroxyl function, a series of protomers were found for SG1(center dot) with the adducted proton preferentially located onto the P=O group of this phosphorylated species. For both protonated nitroxides, major product ions measured in tandem mass spectrometry arose from reactions occurring at low energy costs via elimination of radical species. Formation of secondary fragments that were detected with low abundance when raising the activation level of both precursor ions could be rationalized with pathways proceeding via high energy transition states.
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Dates et versions

hal-02171528 , version 1 (03-07-2019)

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Anouk Gaudel-Siri, Cathie Marchal, Vincent Ledentu, Didier Gigmes, Didier Siri, et al.. Collision-induced dissociation of stable nitroxides: A combined tandem mass spectrometry and computational study of TEMPO center dot and SG1(center dot). European Journal of Mass Spectrometry, 2019, 25 (2), pp.229--238. ⟨10.1177/1469066718793247⟩. ⟨hal-02171528⟩
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