Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry
We investigated the fragmentation of the eudesmanolide-type sesquiterpene lactones 1α-(4-hydroxymethacryloyloxy)-3α,4α-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (1) and 1α-(2,3-epoxyangeloyloxy)-4α,15-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (2) by electrospray ionization tandem mass spectrometry (...
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| Language: | English |
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Wiley
2017-01-01
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| Series: | Journal of Analytical Methods in Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2017/7921867 |
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| author | Herbert Júnior Dias Ricardo Stefani José Carlos Tomaz Ricardo Vessecchi Antônio Eduardo Miller Crotti |
| author_facet | Herbert Júnior Dias Ricardo Stefani José Carlos Tomaz Ricardo Vessecchi Antônio Eduardo Miller Crotti |
| author_sort | Herbert Júnior Dias |
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| description | We investigated the fragmentation of the eudesmanolide-type sesquiterpene lactones 1α-(4-hydroxymethacryloyloxy)-3α,4α-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (1) and 1α-(2,3-epoxyangeloyloxy)-4α,15-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (2) by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The elimination of the different ester substituent at C(1) directly from protonated 1 and 2 (A) led to the formation of two regioisomer product ions B (A − RCO2H). Further fragmentation of B resulted from consecutive eliminations of H2O and CO molecules. However, we identified four product ions that allowed for the differentiation between 3,4- and 4,15-epoxyeudesmanolides. The formation of these diagnostic ions was associated with the C(3)–O bond of compound 1, which propitiates the participation of the lone pair of the oxygen epoxide in the formation of B through a Grob-Wharton-type fragmentation, then resulting in an alternative fragmentation pathway. These data can be useful for the fast differentiation between epoxyeudesmanolide regioisomers directly from Dimerostemma extracts by liquid chromatography-tandem mass spectrometry (LC-MS/MS), as an alternative to NMR, or even for quantitation studies of these compounds using multiple reaction monitoring (MRM) scan. |
| format | Article |
| id | doaj-art-fedd32becf8c4c40bf73d9c03e3ba733 |
| institution | Kabale University |
| issn | 2090-8865 2090-8873 |
| language | English |
| publishDate | 2017-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Journal of Analytical Methods in Chemistry |
| spelling | doaj-art-fedd32becf8c4c40bf73d9c03e3ba7332025-02-03T01:23:31ZengWileyJournal of Analytical Methods in Chemistry2090-88652090-88732017-01-01201710.1155/2017/79218677921867Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass SpectrometryHerbert Júnior Dias0Ricardo Stefani1José Carlos Tomaz2Ricardo Vessecchi3Antônio Eduardo Miller Crotti4Departamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, BrazilInstituto de Ciências Exatas e da Terra, Universidade Federal do Mato Grosso, Campus Universitário do Araguaia, Araguaia, MT, BrazilDepartamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, BrazilDepartamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, BrazilDepartamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, BrazilWe investigated the fragmentation of the eudesmanolide-type sesquiterpene lactones 1α-(4-hydroxymethacryloyloxy)-3α,4α-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (1) and 1α-(2,3-epoxyangeloyloxy)-4α,15-epoxy-8α-hydroxyeudesm-11(13)-6α,12-olide (2) by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The elimination of the different ester substituent at C(1) directly from protonated 1 and 2 (A) led to the formation of two regioisomer product ions B (A − RCO2H). Further fragmentation of B resulted from consecutive eliminations of H2O and CO molecules. However, we identified four product ions that allowed for the differentiation between 3,4- and 4,15-epoxyeudesmanolides. The formation of these diagnostic ions was associated with the C(3)–O bond of compound 1, which propitiates the participation of the lone pair of the oxygen epoxide in the formation of B through a Grob-Wharton-type fragmentation, then resulting in an alternative fragmentation pathway. These data can be useful for the fast differentiation between epoxyeudesmanolide regioisomers directly from Dimerostemma extracts by liquid chromatography-tandem mass spectrometry (LC-MS/MS), as an alternative to NMR, or even for quantitation studies of these compounds using multiple reaction monitoring (MRM) scan.http://dx.doi.org/10.1155/2017/7921867 |
| spellingShingle | Herbert Júnior Dias Ricardo Stefani José Carlos Tomaz Ricardo Vessecchi Antônio Eduardo Miller Crotti Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry Journal of Analytical Methods in Chemistry |
| title | Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry |
| title_full | Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry |
| title_fullStr | Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry |
| title_full_unstemmed | Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry |
| title_short | Differentiation between 3,4- and 4,15-Epoxyeudesmanolides by Electrospray Ionization Tandem Mass Spectrometry |
| title_sort | differentiation between 3 4 and 4 15 epoxyeudesmanolides by electrospray ionization tandem mass spectrometry |
| url | http://dx.doi.org/10.1155/2017/7921867 |
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