Formation of Carbon Dioxide Attached Fragment Ions in the Fragmentation of Deprotonated Tolfenpyrad and Tebufenpyrad

文献类型： 外文期刊

第一作者： Chai, Yunfeng

作者： Chai, Yunfeng;Chen, Hongping;Liu, Xin;Lu, Chengyin;Chai, Yunfeng;Chen, Hongping;Liu, Xin;Lu, Chengyin;Chai, Yunfeng;Chen, Hongping;Liu, Xin;Lu, Chengyin

作者机构：

关键词： Carbon dioxide addition; Tebufenpyrad; Tolfenpyrad; Fragmentation

期刊名称：JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY （ 影响因子：3.109； 五年影响因子：3.323 ）

ISSN： 1044-0305

年卷期： 2019 年 30 卷 10 期

页码：

收录情况： SCI

摘要： The in-source collision-induced dissociation (CID) and MS/MS mass spectra of deprotonated tolfenpyrad and tebufenpyrad both showed an unusual fragment ion at m/z 187, but its fragmentation pattern and structure could not be explained by logical neutral losses. Accurate mass measurement indicated that the mass difference between this fragment ion and the dominant fragment ion at m/z 143 equaled to a carbon dioxide (CO2) molecule. The isolation of the fragment ion m/z 143 in the mass analyzer could spontaneously give rise to the ion m/z 187. The Gibbs free energy of carbon dioxide addition to deprotonated pyrazole ion was significantly negative from the computational results. According to these results, we derived a proposal for the formation and structure of the ion m/z 187, which was an attachment of molecular carbon dioxide to the fragment ion m/z 143 to produce a carboxylate anion. The trace carbon dioxide was speculated to be derived from the residual atmosphere or collision gas in the instrument. This study is valuable for the qualitative and quantitative mass spectrometry analysis of pesticides containing the pyrazole functional group.

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