How does a C=C double bond cleave in the gas phase? Fragmentation of protonated ketotifen in mass spectrometry

文献类型： 外文期刊

第一作者： Chai, Yunfeng

作者： Chai, Yunfeng;Chai, Yunfeng;Wang, Lu;Wang, Lin

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关键词： ketotifen;double bond cleavage;ion-neutral complex;DFT calculation;proton transfer;hydride transfer

期刊名称：JOURNAL OF MASS SPECTROMETRY （ 影响因子：1.982； 五年影响因子：2.03 ）

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收录情况： SCI

摘要： 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.

分类号： O65

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