Physico-Chemical and Chromatic Characterization of Malvidin 3-Glucoside-vinylcatechol and Malvidin 3-Glucoside-vinylguaiacol Wine Pigments

The physicochemical and chromatic features of malvidin 3-glucoside-vinylcatechol (PA1) and malvidin 3-glucoside-vinylguaiacol (PA2) adducts were investigated. Important differences between both pigments were observed. In the investigated pH range (2.0-4.5), our results suggest that PA1 could be considered as a noncovalent dimer of two pyranoflavylium ions (AH)(2) which undergo a hydration reaction in two successive steps, with no proton transfer. In contrast, only proton transfer equilibrium between the pyranoflavylium ion and the quinonoid bases was observed for PA2. The hydration and acidity thermodynamic constants of both pyranoanathocyanins were determined by UV-vis spectroscopy. Pigment PA1 was shown to be less sensitive to bisulfite addition than to water addition, and PA2 seems to be largely insensitive to both water and bisulfite additions. The binding constants for the interaction between the pigments and (+)-catechin in aqueous solution and the changes in the CIELAB parameters that it provoked were also determined. The huge increase in the absorption of the pyranoflavylium ion of PA2 when it binds catechin has no equivalent for anthocyanins and nicely outlines the potential of pyranoanthocyanins in the expression of natural colors.