p-Hydroxyphenyl-pyranoanthocyanins: An Experimental and Theoretical Investigation of Their Acid—Base Properties and Molecular Interactions
AbstractThe physicochemical properties of the wine pigments catechyl-pyranomalvidin-3-O-glucoside (PA1) and guaiacyl-pyranomalvidin-3-O-glucoside (PA2) are extensively revisited using ultraviolet (UV)-visible spectroscopy, dynamic light scattering (DLS) and quantum chemistry density functional theory (DFT) calculations. In mildly acidic aqueous solution, each cationic pigment undergoes regioselective deprotonation to form a single neutral quinonoid base and water addition appears negligible. Above pH = 4, both PA1 and PA2 become prone to aggregation, which is manifested by the slow build-up of broad absorption bands at longer wavelengths (λ ≥ 600 nm), followed in the case of PA2 by precipitation. Some phenolic copigments are able to inhibit aggregation of pyranoanthocyanins (PAs), although at large copigment/PA molar ratios. Thus, chlorogenic acid can dissociate PA1 aggregates while catechin is inactive. With PA2, both chlorogenic acid and catechin are able to prevent precipitation but not self-association. Calculations confirmed that the noncovalent dimerization of PAs is stronger with the neutral base than with the cation and also stronger than π–π stacking of PAs to chlorogenic acid (copigmentation). For each type of complex, the most stable conformation could be obtained. Finally, PA1 can also bind hard metal ions such as Al3+ and Fe3+ and the corresponding chelates are less prone to self-association. View Full-Text
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Vallverdú-Queralt, A.; Biler, M.; Meudec, E.; Guernevé, C.L.; Vernhet, A.; Mazauric, J.-P.; Legras, J.-L.; Loonis, M.; Trouillas, P.; Cheynier, V.; Dangles, O. p-Hydroxyphenyl-pyranoanthocyanins: An Experimental and Theoretical Investigation of Their Acid—Base Properties and Molecular Interactions. Int. J. Mol. Sci. 2016, 17, 1842.
Vallverdú-Queralt A, Biler M, Meudec E, Guernevé CL, Vernhet A, Mazauric J-P, Legras J-L, Loonis M, Trouillas P, Cheynier V, Dangles O. p-Hydroxyphenyl-pyranoanthocyanins: An Experimental and Theoretical Investigation of Their Acid—Base Properties and Molecular Interactions. International Journal of Molecular Sciences. 2016; 17(11):1842.Chicago/Turabian Style
Vallverdú-Queralt, Anna; Biler, Michal; Meudec, Emmanuelle; Guernevé, Christine L.; Vernhet, Aude; Mazauric, Jean-Paul; Legras, Jean-Luc; Loonis, Michèle; Trouillas, Patrick; Cheynier, Véronique; Dangles, Olivier. 2016. "p-Hydroxyphenyl-pyranoanthocyanins: An Experimental and Theoretical Investigation of Their Acid—Base Properties and Molecular Interactions." Int. J. Mol. Sci. 17, no. 11: 1842.
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