Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup>
Diterpenes from the <i>Euphorbia</i> genus are known for their ability to regulate the protein kinase C (PKC) family, which mediates their ability to promote the proliferation of neural precursor cells (NPCs) or neuroblast differentiation into neurons. In this work, we describe the isola...
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MDPI AG
2023-11-01
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| Series: | Plants |
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| Online Access: | https://www.mdpi.com/2223-7747/12/22/3846 |
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| author | Abdellah Ezzanad Carolina De los Reyes Antonio J. Macías-Sánchez Rosario Hernández-Galán |
| author_facet | Abdellah Ezzanad Carolina De los Reyes Antonio J. Macías-Sánchez Rosario Hernández-Galán |
| author_sort | Abdellah Ezzanad |
| collection | DOAJ |
| description | Diterpenes from the <i>Euphorbia</i> genus are known for their ability to regulate the protein kinase C (PKC) family, which mediates their ability to promote the proliferation of neural precursor cells (NPCs) or neuroblast differentiation into neurons. In this work, we describe the isolation from <i>E. resinifera</i> Berg latex of fifteen 12-deoxyphorbol esters (<b>1</b>–<b>15</b>). A triester of 12-deoxy-16-hydroxyphorbol (<b>4</b>) and a 12-deoxyphorbol 13,20-diester (<b>13</b>) are described here for the first time. Additionally, detailed structural elucidation is provided for compounds <b>3</b>, <b>5</b>, <b>6</b>, <b>14</b> and <b>15</b>. The absolute configuration for compounds <b>3</b>, <b>4</b>, <b>6</b>, <b>13</b>, <b>14</b> and <b>15</b> was established by the comparison of their theoretical and experimental electronic circular dichroism (ECD) spectra. Access to the above-described collection of 12-deoxyphorbol derivatives, with several substitution patterns and attached acyl moieties, allowed for the study of their fragmentation patterns in the collision-induced dissociation of multiple ions, without precursor ion isolation mass spectra experiments (HRMS<sup>E</sup>), which, in turn, revealed a correlation between specific substitution patterns and the fragmentation pathways in their HRMS<sup>E</sup> spectra. In turn, this allowed for a targeted UHPLC-HRMS<sup>E</sup> analysis and a biased non-targeted UHPLC-HRMS<sup>E</sup> analysis of 12-deoxyphorbols in <i>E. resinifera</i> latex which yielded the detection and identification of four additional 12-deoxyphorbols not previously isolated in the initial column fractionation work. One of them, identified as 12-deoxy-16-hydroxyphorbol 20-acetate 13-phenylacetate 16-propionate (<b>20</b>), has not been described before. |
| first_indexed | 2024-03-09T16:30:12Z |
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| institution | Directory Open Access Journal |
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| language | English |
| last_indexed | 2024-03-09T16:30:12Z |
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| spelling | doaj.art-3582d4aa389e4eec9092d92f979215562023-11-24T15:01:59ZengMDPI AGPlants2223-77472023-11-011222384610.3390/plants12223846Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup>Abdellah Ezzanad0Carolina De los Reyes1Antonio J. Macías-Sánchez2Rosario Hernández-Galán3Departamento de Química Orgánica, Facultad de Ciencias, Campus Universitario Puerto Real, Universidad de Cádiz, Puerto Real, 11510 Cádiz, SpainDepartamento de Química Orgánica, Facultad de Ciencias, Campus Universitario Puerto Real, Universidad de Cádiz, Puerto Real, 11510 Cádiz, SpainDepartamento de Química Orgánica, Facultad de Ciencias, Campus Universitario Puerto Real, Universidad de Cádiz, Puerto Real, 11510 Cádiz, SpainDepartamento de Química Orgánica, Facultad de Ciencias, Campus Universitario Puerto Real, Universidad de Cádiz, Puerto Real, 11510 Cádiz, SpainDiterpenes from the <i>Euphorbia</i> genus are known for their ability to regulate the protein kinase C (PKC) family, which mediates their ability to promote the proliferation of neural precursor cells (NPCs) or neuroblast differentiation into neurons. In this work, we describe the isolation from <i>E. resinifera</i> Berg latex of fifteen 12-deoxyphorbol esters (<b>1</b>–<b>15</b>). A triester of 12-deoxy-16-hydroxyphorbol (<b>4</b>) and a 12-deoxyphorbol 13,20-diester (<b>13</b>) are described here for the first time. Additionally, detailed structural elucidation is provided for compounds <b>3</b>, <b>5</b>, <b>6</b>, <b>14</b> and <b>15</b>. The absolute configuration for compounds <b>3</b>, <b>4</b>, <b>6</b>, <b>13</b>, <b>14</b> and <b>15</b> was established by the comparison of their theoretical and experimental electronic circular dichroism (ECD) spectra. Access to the above-described collection of 12-deoxyphorbol derivatives, with several substitution patterns and attached acyl moieties, allowed for the study of their fragmentation patterns in the collision-induced dissociation of multiple ions, without precursor ion isolation mass spectra experiments (HRMS<sup>E</sup>), which, in turn, revealed a correlation between specific substitution patterns and the fragmentation pathways in their HRMS<sup>E</sup> spectra. In turn, this allowed for a targeted UHPLC-HRMS<sup>E</sup> analysis and a biased non-targeted UHPLC-HRMS<sup>E</sup> analysis of 12-deoxyphorbols in <i>E. resinifera</i> latex which yielded the detection and identification of four additional 12-deoxyphorbols not previously isolated in the initial column fractionation work. One of them, identified as 12-deoxy-16-hydroxyphorbol 20-acetate 13-phenylacetate 16-propionate (<b>20</b>), has not been described before.https://www.mdpi.com/2223-7747/12/22/3846Euphorbiaceae<i>Euphorbia resinifera</i> Bergditerpenes12-deoxyphorbolsabsolute configurationUHPLC |
| spellingShingle | Abdellah Ezzanad Carolina De los Reyes Antonio J. Macías-Sánchez Rosario Hernández-Galán Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup> Plants Euphorbiaceae <i>Euphorbia resinifera</i> Berg diterpenes 12-deoxyphorbols absolute configuration UHPLC |
| title | Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup> |
| title_full | Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup> |
| title_fullStr | Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup> |
| title_full_unstemmed | Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup> |
| title_short | Isolation and Identification of 12-Deoxyphorbol Esters from <i>Euphorbia resinifera</i> Berg Latex: Targeted and Biased Non-Targeted Identification of 12-Deoxyphorbol Esters by UHPLC-HRMS<sup>E</sup> |
| title_sort | isolation and identification of 12 deoxyphorbol esters from i euphorbia resinifera i berg latex targeted and biased non targeted identification of 12 deoxyphorbol esters by uhplc hrms sup e sup |
| topic | Euphorbiaceae <i>Euphorbia resinifera</i> Berg diterpenes 12-deoxyphorbols absolute configuration UHPLC |
| url | https://www.mdpi.com/2223-7747/12/22/3846 |
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