Sandra Silva1, Ana A. Matias1, Ana Nunes 1, Catarina Duarte1, Ana V. Coelho 3,4*, M. Rosário Bronze 1,2*
1 Instituto de Biologia Experimental e Tecnológica, Apartado 12, 2780 – 901 Oeiras, Portugal.
2 Faculdade de Farmácia de Lisboa, Av.das Forças Armadas 1649 – 019 Lisboa, Portugal.
3 Universidade de Évora, Departamento de Química 7000 – Évora, Portugal.
4 Instituto de Tecnologia Química e Biológica, Apartado 127 2780 – 901 Oeiras, Portugal.
* The work was equally performed in both laboratories.
(Manuscrito recebido em 25.05.05. Aceite para publicação em 01.07.05.)
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SUMMARY
The recovery of high added-value products from waste plant material has been an important issue with economic relevance for the pharmaceutical and food industries. The recovery of antioxidants from wine industry by-products is of great importance in the nutraceutical field. The aim of this study was to identify the main flavonol glycosides, present in winemaking by-products from two white grape varieties: ‘Arinto’ and ‘Moscatel’ using liquid chromatography with diode array and electrochemical detection. Liquid chromatography with electrospray and atmospheric pressure chemical ionization, in negative and positive modes, were also used to characterize the structures of the compounds detected by means of MS2and MS 3. In the by-products analysed quercetin-3-glucoside and quercetin-3-glucuronide were identified as well as kaempferol-3-glucoside. By-products from ‘Arinto’ variety showed higher levels of quercetin glycosides and kaempferol-3-glucoside than the by-products of ‘Moscatel variety’.
Key words: flavonol glycosides, winemaking by-products, HPLC – DAD/ED, HPLC – MS, MSn
RESUMO
Identificação de glicósidos de flavonóis em subprodutos da vinificação por HPLC com diferentes detectores e hifenado com espectrometria de massa
Uvas, vinho e subprodutos da vinificação contêm diversos compostos fenólicos pertencentes ao grupo dos flavonóides, em elevadas concentrações. Os glicósidos de flavonóis estão entre os compostos fenólicos presentes nas uvas. A sua actividade biológica é de grande interesse para as indústrias farmacêutica, cosmética e alimentar, não só pela actividade antioxidante, mas também pelas suas propriedades anti-inflamatórias e anti-cancerígenas. O objectivo deste estudo foi identificar glicósidos de flavonóis maioritários em subprodutos da vinificação em branco das variedades ‘Arinto’ e ‘Moscatel’. Foram utilizadas metodologias analíticas que incluiram a cromatografia líquida acoplada a detectores de díodos e electroquímico. Cromatografia líquida com espectrometria de massa foi ainda utilizada com duas fontes de ionização à pressão atmosférica: electrospray (ESI) e ionização química (APCI), nas polaridades positiva e negativa no sentido de comparar resultados. Foram também efectuados ensaios MS2e MS3 para caracterizar as estruturas químicas dos glicósidos de flavonóis detectados. Nas amostras analisadas foi identificada a quercetina-3-glucósido e a quercetina-3-glucuronido e também o quempferol-3-glucósido. Os subprodutos da variedade ‘Arinto’ mostraram, proporcionalmente, maior teor de glicósidos de quercetina que quempferol-3-glucósido, quando comparados com os resíduos da variedade ‘Moscatel’.
]]> Palavras chave: glicósidos de flavonóis, subprodutos da vinificação, HPLC – DAD/ED, HPLC – MS, MSn
RÉSUMÉ
Identification de glycosides de flavonol dans les sous-produits de la vinification par HPLC avec différents détecteurs et couplé par spectrométrie de masse
Le rétablissement de produits de haute valeur obtenue de la matière végétale est une question importante avec la pertinence économique pour les industries pharmaceutique, cosmétique et alimentaire, à cause de son activité antioxydant mais aussi pour ces propriétés antiinflammatoire et anti-cancérigène. Le rétablissement des antioxydants des sous-produits d’industrie vinicole est de grande importance dans le domaine nutraceutique. Le but de cette étude était d’identifier les principaux glycosides de flavonol dans les sousproduits de la vinification de deux variétés blanches de raisin: ‘Arinto’ et ‘ Moscatel’. La chromatographie liquide avec la detection par diode et électrochimique on été employées en tandem. La chromatographie liquide était également employée pour caractériser les structures des composés détectés par MS2et MS3en utilisant electrospray et l’ionisation chimique de pression atmosphérique, en modes négative et positive. Dans les sous-produits analysés quercétine-3-glucoside, quercétine-3-glucuronide et kaempférol-3-glucoside ont été identifiés. Les sous-produits de la variété d’ ‘Arinto’ ont des proportions plus élevée des glycosides de quercétine et kaempférol-3-glucoside en comparaison avec les sous-produits de variété ‘Moscatel ‘.
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