title: Oxovitisins: a new class of neutral pyranone-anthocyanin derivatives in red wines.
abstract: A new class of stable yellowish pigments with similar unique spectral features, displaying only a pronounced broad band around 370 nm in the UV-vis spectrum, was detected in an aged Port wine fraction obtained by a combination of chromatography on TSK Toyopearl HW-40(s) and Polyamide resins. These compounds were identified by liquid chromatography-diode array detector/electrospray ionization mass spectrometry (LC-DAD/ESI/MS) and shown to be direct oxidative derivatives of carboxy-pyranoanthocyanins (vitisins A) by synthesis experiments performed in a wine model solution. Their structures were fully characterized by MS and NMR spectroscopy ((1)H, gCOSY, gHSQC, and gHMBC) and found to correspond to alpha-pyranone-anthocyanins (lactone or pyran-2-one-anthocyanins). Their formation involves first the nucleophilic attack of water into the positively charged C-10 position of vitisins, followed by decarboxylation, oxidation, and dehydration steps, yielding a new and neutral pyranone structure. The occurrence of these novel pigments in aged wines points to a new pathway involving anthocyanin secondary products (vitisins A) as precursors of new pigments in subsequent stages of wine aging that may contribute to its color evolution.
authors.affiliation: Centro de Investigação em Química, Departamento de Química, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto, Portugal.
authors.forename: Jingren
authors.initials: J
authors.lastname: He
authors.forename: Joana
authors.initials: J
authors.lastname: Oliveira
authors.forename: Artur M S
authors.initials: AM
authors.lastname: Silva
authors.forename: Nuno
authors.initials: N
authors.lastname: Mateus
authors.forename: Victor
authors.initials: V
authors.lastname: De Freitas
mesh_terms: D000872:Anthocyanins / Q000737:chemistry*; D005511:Food Handling; D010084:Oxidation-Reduction; D014920:Wine / Q000032:analysis*
chemical_list: D000872:Anthocyanins