Copigmentation between malvidin-3-glucoside and some wine constituents and its importance to colour expression in red wine

Thermodynamic parameters for intermolecular copigmentation interactions involving malvidin-3-glucoside were determined by UV/visible spectroscopy at wine pH (pH 3.6). These included associationmconstants, enthalpy and entropy changes, which were measured for chlorogenic acid, caffeic acid, quercetin, quercetin-3-glucoside, (_)-epicatechin, (+)-catechin, procyanidin dimer and seed tannin. Quercetin produced the strongest copigment (KCP = 2900 ± 1300), whilst the addition of glucose at position 3 (quercetin-3-glucoside) reduced its effect by almost 10-fold. Malvidin-3-glucoside self-association(KD = 3300 ± 300 mol_1 l) was thermodynamically favoured over intermolecular interaction with any of the copigments tested. No colour enhancement due to self-association was observed for malvidin-3-glucoside-derived pigments that cannot enter hydration reactions. In addition, malvidin-3-(6-O-p-coumaryl) glucoside did not show colour enhancement suggesting that the p-coumaryl group prevents self-association. The malvidin-3-glucoside circular dichroism (CD) spectrum was not affected by indicated changes in malvidin-3-glucoside concentration. These observations demonstrate that self-association of malvidin-3-glucoside is more important than copigmentation in young red wine.Stephanie G. Lambert, Robert E. Asenstorfer, Natalie M. Williamson, Patrick G. Iland, Graham P. Jone