期刊
JOURNAL OF MASS SPECTROMETRY
卷 51, 期 12, 页码 1105-1110出版社
WILEY
DOI: 10.1002/jms.3843
关键词
ketotifen; double bond cleavage; ion-neutral complex; DFT calculation; proton transfer; hydride transfer
资金
- National Natural Science Foundation of China [21405137, 21605002]
- Public Welfare Technology Application Research Project of Zhejiang Province [2016C32025]
- Innovative Research Team in Chinese Academy of Agricultural Sciences
In the literature, it is reported that the protonated ketotifen mainly undergoes C=C double bond cleavage in electrospray ionization tandem mass spectrometry (ESI-MS/MS); however, there is no explanation on the mechanism of this fragmentation reaction. Therefore, we carried out a combined experimental and theoretical study on this interesting fragmentation reaction. The fragmentation of protonated ketotifen (m/z 310) always generated a dominant fragment ion at m/z 96 in different electrospray ionization mass spectrometers (ion trap, triple quadrupole and linear trap quadrupole (LTQ)-orbitrap). The mechanism of the generation of this product ion (m/z 96) through the C=C double bond cleavage was proposed to be a sequential hydrogen migration process (including proton transfer, continuous two-step 1,2-hydride transfer and ion-neutral complex-mediated hydride transfer). This mechanism was supported by density functional theory (DFT) calculations and a deuterium labeling experiment. DFT calculations also showed that the formation of the product ion m/z 96 was most favorable in terms of energy. This study provides a reasonable explanation for the fragmentation of protonated ketotifen in ESI-MS/MS, and the fragmentation mechanism is suitable to explain other C=C double bond cleavage reactions in mass spectrometry. Copyright (C) 2016 John Wiley & Sons, Ltd.
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