Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry
Although dicofol has been widely banned all over the world as a kind of organochlorine contaminant, it still exists in the environment. This study developed a high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS) detection technique for dicofol, an environmental pollutan...
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| Format: | Article |
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MDPI AG
2023-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/9/3765 |
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| author | Jun Xie Yage Guo Yongqiang Ma Hongyun Jiang Lan Zhang Liangang Mao Lizhen Zhu Yongquan Zheng Xingang Liu |
| author_facet | Jun Xie Yage Guo Yongqiang Ma Hongyun Jiang Lan Zhang Liangang Mao Lizhen Zhu Yongquan Zheng Xingang Liu |
| author_sort | Jun Xie |
| collection | DOAJ |
| description | Although dicofol has been widely banned all over the world as a kind of organochlorine contaminant, it still exists in the environment. This study developed a high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS) detection technique for dicofol, an environmental pollutant, for the first time using in-source fragmentation. The results confirmed that <i>m</i>/<i>z</i> 251 was the only precursor ion of dicofol after in-source fragmentation, and <i>m</i>/<i>z</i> 139 and <i>m</i>/<i>z</i> 111 were reasonable product ions. The main factors triggering the in-source fragmentation were the H<sup>+</sup> content and solution conductivity when dicofol entered the mass spectrometer. Density functional theory can be used to analyze and interpret the mechanism of dicofol fragmentation reaction in ESI source. Dicofol reduced the molecular energy from 8.8 ± 0.05 kcal/mol to 1.0 ± 0.05 kcal/mol, indicating that the internal energy release from high to low was the key driving force of in-source fragmentation. A method based on HPLC-MS/MS was developed to analyze dicofol residues in environmental water. The LOQ was 0.1 μg/L, which was better than the previous GC or GC-MS methods. This study not only proposed an HPLC-MS/MS analysis method for dicofol for the first time but also explained the in-source fragmentation mechanism of compounds in ESI source, which has positive significance for the study of compounds with unconventional mass spectrometry behavior in the field of organic pollutant analysis and metabonomics. |
| first_indexed | 2024-03-11T04:12:12Z |
| format | Article |
| id | doaj.art-6ef3d0b152ee4fa99bc8b74176951e68 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T04:12:12Z |
| publishDate | 2023-04-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-6ef3d0b152ee4fa99bc8b74176951e682023-11-17T23:23:07ZengMDPI AGMolecules1420-30492023-04-01289376510.3390/molecules28093765Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass SpectrometryJun Xie0Yage Guo1Yongqiang Ma2Hongyun Jiang3Lan Zhang4Liangang Mao5Lizhen Zhu6Yongquan Zheng7Xingang Liu8State Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, ChinaState Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, ChinaDepartment of Applied Chemistry, College of Science, China Agricultural University, Beijing 100193, ChinaState Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, ChinaState Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, ChinaState Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, ChinaState Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, ChinaShandong Engineering Research Center for Environment-Friendly Agricultural Pest Management, College of Plant Health and Medicine, Qingdao Agricultural University, Qingdao 266109, ChinaState Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193, ChinaAlthough dicofol has been widely banned all over the world as a kind of organochlorine contaminant, it still exists in the environment. This study developed a high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS) detection technique for dicofol, an environmental pollutant, for the first time using in-source fragmentation. The results confirmed that <i>m</i>/<i>z</i> 251 was the only precursor ion of dicofol after in-source fragmentation, and <i>m</i>/<i>z</i> 139 and <i>m</i>/<i>z</i> 111 were reasonable product ions. The main factors triggering the in-source fragmentation were the H<sup>+</sup> content and solution conductivity when dicofol entered the mass spectrometer. Density functional theory can be used to analyze and interpret the mechanism of dicofol fragmentation reaction in ESI source. Dicofol reduced the molecular energy from 8.8 ± 0.05 kcal/mol to 1.0 ± 0.05 kcal/mol, indicating that the internal energy release from high to low was the key driving force of in-source fragmentation. A method based on HPLC-MS/MS was developed to analyze dicofol residues in environmental water. The LOQ was 0.1 μg/L, which was better than the previous GC or GC-MS methods. This study not only proposed an HPLC-MS/MS analysis method for dicofol for the first time but also explained the in-source fragmentation mechanism of compounds in ESI source, which has positive significance for the study of compounds with unconventional mass spectrometry behavior in the field of organic pollutant analysis and metabonomics.https://www.mdpi.com/1420-3049/28/9/3765dicofolin-source fragmentationorganic pollutantHPLC-MS/MSESI |
| spellingShingle | Jun Xie Yage Guo Yongqiang Ma Hongyun Jiang Lan Zhang Liangang Mao Lizhen Zhu Yongquan Zheng Xingang Liu Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry Molecules dicofol in-source fragmentation organic pollutant HPLC-MS/MS ESI |
| title | Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry |
| title_full | Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry |
| title_fullStr | Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry |
| title_full_unstemmed | Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry |
| title_short | Spontaneous In-Source Fragmentation Reaction Mechanism and Highly Sensitive Analysis of Dicofol by Electrospray Ionization Mass Spectrometry |
| title_sort | spontaneous in source fragmentation reaction mechanism and highly sensitive analysis of dicofol by electrospray ionization mass spectrometry |
| topic | dicofol in-source fragmentation organic pollutant HPLC-MS/MS ESI |
| url | https://www.mdpi.com/1420-3049/28/9/3765 |
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