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Int. J. Mol. Sci. 2016, 17(11), 1842;

p-Hydroxyphenyl-pyranoanthocyanins: An Experimental and Theoretical Investigation of Their Acid—Base Properties and Molecular Interactions

Institut National de la Recherche Agronomique (INRA), UMR1083 Sciences pour l’œnologie, 2 place Pierre Viala, 34060 Montpellier CEDEX, France
CIBER Fisiopatología de la Obesidad y la Nutrición (CIBEROBN), Instituto de Salud Carlos III, 28903 Madrid, Spain
INSERM UMR 850, University of Limoges, School of Pharmacy, 2 rue du Dr. Marcland, F-87025 Limoges, France
Department of Biophysics, Centre of the Region Haná for Biotechnological and Agricultural Research, Palacký University, Šlechtitelů 27, 78371 Olomouc, Czech Republic
INRA, UMR408 SQPOV, University of Avignon, 84000 Avignon, France
Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacký University Olomouc, tř. 17. listopadu 12, 77146 Olomouc, Czech Republic
Author to whom correspondence should be addressed.
Academic Editor: Nuno Mateus
Received: 26 September 2016 / Revised: 27 October 2016 / Accepted: 31 October 2016 / Published: 5 November 2016
(This article belongs to the Special Issue Anthocyanins)
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The 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
Keywords: pyranoanthocyanins; acid-base; self-association; copigmentation; metal complexation; UV-visible absorption pyranoanthocyanins; acid-base; self-association; copigmentation; metal complexation; UV-visible absorption

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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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.

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