Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass Spectrometry
Organophosphorus flame retardants (OPFRs) have been widely used in polymeric materials owing to their flame retardant and plasticizing effects. Investigating the fragmentation pathway of OPFRs is of great necessity for further discovering and identifying novel pollutants using orbitrap-based high-re...
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| Format: | Article |
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MDPI AG
2024-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/29/3/680 |
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| author | Kangcong Li Yan Gao Xiuqin Li Yan Zhang Benfeng Zhu Qinghe Zhang |
| author_facet | Kangcong Li Yan Gao Xiuqin Li Yan Zhang Benfeng Zhu Qinghe Zhang |
| author_sort | Kangcong Li |
| collection | DOAJ |
| description | Organophosphorus flame retardants (OPFRs) have been widely used in polymeric materials owing to their flame retardant and plasticizing effects. Investigating the fragmentation pathway of OPFRs is of great necessity for further discovering and identifying novel pollutants using orbitrap-based high-resolution mass spectrometry (HRMS). A total of 25 OPFRs, including alkyl, halogenated, and aromatic types, were analyzed in this study. The fragmentation pathways of the OPFRs were investigated using orbitrap-based HRMS with high-energy collision dissociation (HCD) in positive mode. The major fragmentation pathways for the three types of OPFRs are greatly affected by the substituents. In detail, the alkyl and halogenated OPFRs underwent three McLafferty hydrogen rearrangements, wherein the substituents were gradually cleaved to form the structurally stable [H<sub>4</sub>PO<sub>4</sub>]<sup>+</sup> (<i>m</i>/<i>z</i> = 98.9845) ions. In contrast, the aromatic OPFRs would cleave not only the C-O bond but also the P-O bond, depending on the substituents, to form fragment ions such as [C<sub>6</sub>H<sub>7</sub>O]<sup>+</sup> (<i>m</i>/<i>z</i> = 95.0495) or [C<sub>7</sub>H<sub>7</sub>]<sup>+</sup> (<i>m</i>/<i>z</i> = 91.0530), among others. Using HRMS improved the accuracy of fragment ion identification, and the pathway became more evident. These fragmentation laws can provide identification information in pollutant screening work and theoretical references for the structural characterization of compounds with diverse substituent structures. |
| first_indexed | 2024-03-08T03:51:41Z |
| format | Article |
| id | doaj.art-59b99b0d58c54e8293241fd6b1f15e88 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-08T03:51:41Z |
| publishDate | 2024-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-59b99b0d58c54e8293241fd6b1f15e882024-02-09T15:19:04ZengMDPI AGMolecules1420-30492024-02-0129368010.3390/molecules29030680Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass SpectrometryKangcong Li0Yan Gao1Xiuqin Li2Yan Zhang3Benfeng Zhu4Qinghe Zhang5Division of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, ChinaDivision of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, ChinaDivision of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, ChinaDivision of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, ChinaCollege of Materials and Chemistry, China Jiliang University, Hangzhou 310018, ChinaDivision of Chemical Metrology and Analytical Science, National Institute of Metrology, Beijing 100029, ChinaOrganophosphorus flame retardants (OPFRs) have been widely used in polymeric materials owing to their flame retardant and plasticizing effects. Investigating the fragmentation pathway of OPFRs is of great necessity for further discovering and identifying novel pollutants using orbitrap-based high-resolution mass spectrometry (HRMS). A total of 25 OPFRs, including alkyl, halogenated, and aromatic types, were analyzed in this study. The fragmentation pathways of the OPFRs were investigated using orbitrap-based HRMS with high-energy collision dissociation (HCD) in positive mode. The major fragmentation pathways for the three types of OPFRs are greatly affected by the substituents. In detail, the alkyl and halogenated OPFRs underwent three McLafferty hydrogen rearrangements, wherein the substituents were gradually cleaved to form the structurally stable [H<sub>4</sub>PO<sub>4</sub>]<sup>+</sup> (<i>m</i>/<i>z</i> = 98.9845) ions. In contrast, the aromatic OPFRs would cleave not only the C-O bond but also the P-O bond, depending on the substituents, to form fragment ions such as [C<sub>6</sub>H<sub>7</sub>O]<sup>+</sup> (<i>m</i>/<i>z</i> = 95.0495) or [C<sub>7</sub>H<sub>7</sub>]<sup>+</sup> (<i>m</i>/<i>z</i> = 91.0530), among others. Using HRMS improved the accuracy of fragment ion identification, and the pathway became more evident. These fragmentation laws can provide identification information in pollutant screening work and theoretical references for the structural characterization of compounds with diverse substituent structures.https://www.mdpi.com/1420-3049/29/3/680organophosphorus flame retardantfragmentation pathwayliquid chromatographyhigh resolution mass spectrometry |
| spellingShingle | Kangcong Li Yan Gao Xiuqin Li Yan Zhang Benfeng Zhu Qinghe Zhang Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass Spectrometry Molecules organophosphorus flame retardant fragmentation pathway liquid chromatography high resolution mass spectrometry |
| title | Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass Spectrometry |
| title_full | Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass Spectrometry |
| title_fullStr | Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass Spectrometry |
| title_full_unstemmed | Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass Spectrometry |
| title_short | Fragmentation Pathway of Organophosphorus Flame Retardants by Liquid Chromatography–Orbitrap-Based High-Resolution Mass Spectrometry |
| title_sort | fragmentation pathway of organophosphorus flame retardants by liquid chromatography orbitrap based high resolution mass spectrometry |
| topic | organophosphorus flame retardant fragmentation pathway liquid chromatography high resolution mass spectrometry |
| url | https://www.mdpi.com/1420-3049/29/3/680 |
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