ABSTRACT
Grape pectic polysaccharides-malvidin-3-O- ß -d-glucoside binding was studied, aiming to unveil the impact of structural diversity of polysaccharides on anthocyanins-polysaccharides interactions. Polysaccharides were extracted with solutions of imidazole (ISP) and carbonate at 4 °C (CSP-4 °C) and room temperature (CSP-RT) and also recovered from the dialysis supernatant of the remaining cellulosic residue after the aqueous NAOH extraction of hemicellulosic polysaccharides (Sn-CR). Polysaccharides richer in homogalacturonan domains, like those present in the CSP-4 °C fraction had approximately 50-fold higher binding affinity to malvidin-3-O- ß-d-glucoside, than polysaccharides with side chains (as ISP and CSP-RT extractable polysaccharides). CSP-4 °C polysaccharides showed a positive effect on malvidin-3-O- ß-d-glucoside colour fading. Hydration equilibrium constant of malvidin-3-O- ß-d-glucoside in the presence of CSP-4 °C polysaccharides was higher, showing the preferential stabilization of the flavylium cation. The results showed that anthocyanins colour stabilization can be promoted by pectic polysaccharide structures such as those extracted by cold carbonate.
ABSTRACT
The impact of grape pectic polysaccharides on malvidin-3-O-ß-d-glucoside thermostability was evaluated in model solutions. Pectic polysaccharides richer in homogalacturonan domains, with less neutral sidechains (chelator fraction) showed higher binding with malvidin-3-O-ß-d-glucoside, by 1H NMR (Ka=505 M-1). Binding affinity with water soluble extract was estimated to be 10-fold lower, possibly due to the presence of neutral branched regions and more compacted structure, hampering the binding. Hydrophobic domains, such as rhamnogalacturonans-I domains in acid soluble polysaccharides, may participate in the formation of complexes with malvidin-3-O-ß-d-glucoside. The thermostability of anthocyanin-polysaccharides complexes was evaluated at different temperatures, assessing anthocyanins degradation by HPLC-DAD. Polysaccharides showed to improve anthocyanin thermostability, with chelator and acid extract having the highest impact at lowest temperatures. Electrostatic interactions, additionally stabilized by hydrophobic effect contribute to the anthocyanin-polysaccharides binding and to the consequent thermostabilization. The protection provided by grape pectic polysaccharides foresees innovative anthocyanin food products with improved thermostability and colour features.
