Oxidative transformation of Leucocyanidin by anthocyanidin synthase from Vitis vinifera leads only to quercetin
| Autor: | Jia-rong Zhang, Claudine Trossat-Magnin, Katell Bathany, Jean Chaudiere, Serge Delrot |
|---|---|
| Přispěvatelé: | Université de Bordeaux (UB), Ecophysiologie et Génomique Fonctionnelle de la Vigne (UMR EGFV), Institut National de la Recherche Agronomique (INRA)-Université de Bordeaux (UB)-Institut des Sciences de la Vigne et du Vin (ISVV)-Ecole Nationale Supérieure des Sciences Agronomiques de Bordeaux-Aquitaine (Bordeaux Sciences Agro) |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
0106 biological sciences
leucoanthocyanidin dioxygenase Reaction mechanism Stereochemistry [SDV]Life Sciences [q-bio] Cyanidin anthocyanidin synthase 01 natural sciences Mass Spectrometry chemistry.chemical_compound Isomerism [SDV.BV]Life Sciences [q-bio]/Vegetal Biology Vitis leucocyanidin Biotransformation Plant Proteins Flavonoids Leucocyanidin Chemistry 010401 analytical chemistry 2-oxoglutarate Substrate (chemistry) General Chemistry ascorbate Tautomer 0104 chemical sciences Anthocyanidins Vitis vinifera [SDE]Environmental Sciences Biocatalysis Oxygenases Quercetin reaction mechanism General Agricultural and Biological Sciences Oxidation-Reduction Cis–trans isomerism 010606 plant biology & botany |
| Zdroj: | Journal of Agricultural and Food Chemistry Journal of Agricultural and Food Chemistry, American Chemical Society, 2019, 67 (13), pp.3595-3604. ⟨10.1021/acs.jafc.8b06968⟩ |
| ISSN: | 0021-8561 1520-5118 |
| DOI: | 10.1021/acs.jafc.8b06968⟩ |
| Popis: | International audience; Anthocyanidin synthase from Vitis vinifera (VvANS) catalyzes the in vitro transformation of the natural isomer of leucocyanidin, 2R,3S,4S-cis-leucocyanidin, into 2R,4S-flavan-3,3,4-triol ([M + H]+, m/z 323) and quercetin. The C3-hydroxylation product 2R,4S-flavan-3,3,4-triol is first produced and its C3,C4-dehydration product is in tautomeric equilibrium with (+)-dihydroquercetin. The latter undergoes a second VvANS-catalyzed C3-hydroxylation leading to a 4-keto-2R-flavan-3,3-gem-diol which upon dehydration gives quercetin. The unnatural isomer of leucocyanidin, 2R,3S,4R-trans-leucocyanidin, is similarly transformed into quercetin upon C3,C4-dehydration, but unlike 3,4-cis-leucocyanidin, it also undergoes some C2,C3-dehydration followed by an acid-catalyzed hydroxyl group extrusion at C4 to give traces of cyanidin. Overall, the C3,C4-trans isomer of leucocyanidin is transformed into 2R,4R-flavan-3,3,4-triol (M + 1, m/z 323), (+)-DHQ, (−)-epiDHQ, quercetin, and traces of cyanidin. Our data bring the first direct observation of 3,4-cis-leucocyanidin- and 3,4-trans-leucocyanidin-derived 3,3-gem-diols, supporting the idea that the generic function of ANS is to catalyze the C3-hydroxylation of its substrates. No cyanidin is produced with the natural cis isomer of leucocyanidin, and only traces with the unnatural trans isomer, which suggests that anthocyanidin synthase requires other substrate(s) for the in vivo formation of anthocyanidins. |
| Databáze: | OpenAIRE |
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