Profiling of Resveratrol Oligomers, Important Stress Metabolites, Accumulating in the Leaves of Hybrid Vitis vinifera (Merzling × Teroldego) Genotypes Infected with Plasmopara viticola

Abstract

In the Vitaceae, viniferins represent a relatively restricted group of trans-resveratrol oligomers with antifungal properties, thus enabling plants to cope with pathogen attack. The aim of this study was to perform isolation and structural characterization of the whole class of viniferins accumulating in the leaves of hybrid Vitis vinifera (Merzling × Teroldego) genotypes infected with Plasmopara viticola . Infected leaves of resistant plants were collected 6 days after infection, extracted with methanol, and prepurified by flash chromatography using ENV+ and Toyopearl HW 40S resins. Further fractionation using normal-phase preparative chromatography and then reversed-phase preparative chromatography allowed isolation of 14 peaks. The isolated compounds were identified using advanced mass spectrometry techniques and extensive one- and two-dimensional nuclear magnetic resonance measurements, UV, CD, optical properties, and molecular mechanic calculations. The results demonstrated the presence in infected leaves of seven dimers (six stilbenes and one stilbenoid), of which four were new in grapevine (ampelopsin D, quadrangularin A, E-ω-viniferin, and Z-ω-viniferin), four trimers (three stilbenes and one stilbenoid), of which two (Z-miyabenol C and E-cis-miyabenol C) were new in grapevine, three tetramer stilbenoids, all new in grapevine, isohopeaphenol, ampelopsin H, and a vaticanol C-like isomer. The isolation of a dimer deriving from the condensation of (+)-catechin with trans-caffeic acid also indicated that other preformed phenolics are structurally modified in tissues infected with P. viticola.

Isorhapontigenin: A novel bioactive stilbene from wine grapes

“…Fraction 5 (FF5) mainly presented piceatannol, a-viniferin (Püssa et al, 2006) and also a resveratrol dimer, tentatively ampelopsin D, in agreement with mass data (Vergara et al, 2012). Ampelopsin D had been previously described in Vitaceae (Jeandet et al, 2002;Mattivi et al, 2011). Ampelopsin D had been suggested to be synthesized in the Vitaceae from its precursor e-viniferin and also d-viniferin (Püssa et al, 2006).…”

Advanced Knowledge of Three Important Classes of Grape Phenolics: Anthocyanins, Stilbenes and Flavonols

“…ɛ-Viniferins and ω-viniferins (E and Z isomers) and resveratrol trimers and tetramers (ampelopsin D, quadrangularin A, α-viniferin, E- and Z-miyabenol C, isohopeaphenol, ampelopsin H, vaticanol C-like) have been found in various parts of the plant, such as leaves, roots, clusters and stems, from oxidative coupling of resveratrol or resveratrol derivatives [72]. In Vitis grapevine canes, E-ampelopsin E, Eamurensin B, E-resveratroloside, E-3,5,4′-trihydroxystilbene 2-C-glucoside, Z-ampelopsin E, scirpusin A, E- and Z-vitisin B have also been found [73].…”

MALDI Mass Spectrometry Imaging for the Simultaneous Location of Resveratrol, Pterostilbene and Viniferins on Grapevine Leaves

“…MSI allowed the identification and mapping of resveratrol and pterostilbene but the biosynthesis of some other stilbenes is also expected to be induced in grapevine leaves and even berries in response to pathogen infection or UV irradiation [19][20][21]. Besides the glycosylation of stilbenes (e.g., piceids), oxidative oligomerization of resveratrol catalyzed by plant peroxidases may occur and several of them have been identified in stressed grapevine leaves [22][23][24].…”