{"title":"用4-三氟甲基-2,3,5,6-四氟苯基吡啶“温度计离子”表征碰撞诱导解离激活离子的碰撞能量高达30 eV。","authors":"Daiki Asakawa","doi":"10.1021/jasms.4c00461","DOIUrl":null,"url":null,"abstract":"<p><p>To facilitate the assessment of the internal energy distribution of ions activated by collision-induced dissociation with collision energy in the laboratory frame exceeding 20 eV, the screening of fluorine-containing benzylpyridiniums was performed by evaluating their dissociation energies through quantum chemistry calculations at the CCSD(T)/6-311++G(d,p)//M06-2X-D3/6-311++G(d,p) level of theory. The dissociation energy increased with the presence of a trifluoromethyl group at the 4-position and fluorine atoms at positions 2, 3, 5, and 6 of benzylpyridinium. However, the fluorine atom at the 4-position in benzylpyridinium slightly reduced the dissociation energy, suggesting its electron-donating nature. 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium (CF<sub>3</sub>,F<sub>4</sub>-BnPy<sup>+</sup>) has the highest dissociation energy among the reported benzylpyridiniums and is a suitable thermometer ion for characterizing the internal energy distributions of ions activated by collision-induced dissociation (CID) during tandem mass spectrometry. Using CF<sub>3</sub>,F<sub>4</sub>-BnPy<sup>+</sup> allowed the evaluation of the internal energy distribution of CID-activated ions up to a collision energy of 30 eV in the laboratory frame. The survival yield method using fluorine-substituted benzylpyridiniums and 4-methylbenzylpyridiniums facilitates the optimization of tandem mass spectrometry parameters for the analysis of small molecules, such as metabolites.</p>","PeriodicalId":672,"journal":{"name":"Journal of the American Society for Mass Spectrometry","volume":" ","pages":"787-793"},"PeriodicalIF":3.1000,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Characterization of Ions Activated by Collision-Induced Dissociation with Collision Energy Up to 30 eV Using 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium \\\"Thermometer Ion\\\".\",\"authors\":\"Daiki Asakawa\",\"doi\":\"10.1021/jasms.4c00461\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>To facilitate the assessment of the internal energy distribution of ions activated by collision-induced dissociation with collision energy in the laboratory frame exceeding 20 eV, the screening of fluorine-containing benzylpyridiniums was performed by evaluating their dissociation energies through quantum chemistry calculations at the CCSD(T)/6-311++G(d,p)//M06-2X-D3/6-311++G(d,p) level of theory. The dissociation energy increased with the presence of a trifluoromethyl group at the 4-position and fluorine atoms at positions 2, 3, 5, and 6 of benzylpyridinium. However, the fluorine atom at the 4-position in benzylpyridinium slightly reduced the dissociation energy, suggesting its electron-donating nature. 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium (CF<sub>3</sub>,F<sub>4</sub>-BnPy<sup>+</sup>) has the highest dissociation energy among the reported benzylpyridiniums and is a suitable thermometer ion for characterizing the internal energy distributions of ions activated by collision-induced dissociation (CID) during tandem mass spectrometry. Using CF<sub>3</sub>,F<sub>4</sub>-BnPy<sup>+</sup> allowed the evaluation of the internal energy distribution of CID-activated ions up to a collision energy of 30 eV in the laboratory frame. The survival yield method using fluorine-substituted benzylpyridiniums and 4-methylbenzylpyridiniums facilitates the optimization of tandem mass spectrometry parameters for the analysis of small molecules, such as metabolites.</p>\",\"PeriodicalId\":672,\"journal\":{\"name\":\"Journal of the American Society for Mass Spectrometry\",\"volume\":\" \",\"pages\":\"787-793\"},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2025-04-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Society for Mass Spectrometry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jasms.4c00461\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/3/4 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q2\",\"JCRName\":\"BIOCHEMICAL RESEARCH METHODS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Society for Mass Spectrometry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jasms.4c00461","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/3/4 0:00:00","PubModel":"Epub","JCR":"Q2","JCRName":"BIOCHEMICAL RESEARCH METHODS","Score":null,"Total":0}
Characterization of Ions Activated by Collision-Induced Dissociation with Collision Energy Up to 30 eV Using 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium "Thermometer Ion".
To facilitate the assessment of the internal energy distribution of ions activated by collision-induced dissociation with collision energy in the laboratory frame exceeding 20 eV, the screening of fluorine-containing benzylpyridiniums was performed by evaluating their dissociation energies through quantum chemistry calculations at the CCSD(T)/6-311++G(d,p)//M06-2X-D3/6-311++G(d,p) level of theory. The dissociation energy increased with the presence of a trifluoromethyl group at the 4-position and fluorine atoms at positions 2, 3, 5, and 6 of benzylpyridinium. However, the fluorine atom at the 4-position in benzylpyridinium slightly reduced the dissociation energy, suggesting its electron-donating nature. 4-Trifluoromethyl-2,3,5,6-tetrafluorobenzylpyridinium (CF3,F4-BnPy+) has the highest dissociation energy among the reported benzylpyridiniums and is a suitable thermometer ion for characterizing the internal energy distributions of ions activated by collision-induced dissociation (CID) during tandem mass spectrometry. Using CF3,F4-BnPy+ allowed the evaluation of the internal energy distribution of CID-activated ions up to a collision energy of 30 eV in the laboratory frame. The survival yield method using fluorine-substituted benzylpyridiniums and 4-methylbenzylpyridiniums facilitates the optimization of tandem mass spectrometry parameters for the analysis of small molecules, such as metabolites.
期刊介绍:
The Journal of the American Society for Mass Spectrometry presents research papers covering all aspects of mass spectrometry, incorporating coverage of fields of scientific inquiry in which mass spectrometry can play a role.
Comprehensive in scope, the journal publishes papers on both fundamentals and applications of mass spectrometry. Fundamental subjects include instrumentation principles, design, and demonstration, structures and chemical properties of gas-phase ions, studies of thermodynamic properties, ion spectroscopy, chemical kinetics, mechanisms of ionization, theories of ion fragmentation, cluster ions, and potential energy surfaces. In addition to full papers, the journal offers Communications, Application Notes, and Accounts and Perspectives