Evaluation of color and stability of ethyl-linked anthocyanin-flavanol pigments in model wine solutions using combined chemical analysis and 3D molecular simulations

Ethyl-linked anthocyanin-flavanol pigments are one of the most important condensation products formed during the red winemaking and ageing period. They have great contribution to the color characteristics and stability of aged red wines. In this study, the color characteristics and stability of ethyl-linked anthocyanin-flavanol pigments and their precursor anthocyanins were evaluated by combined spectrophotometry and 3D molecular simulations. In model wine solutions, the condensation reactions between three anthocyanins and (-)-epicatechin, mediated by acetaldehyde, were conducted to produce ethyl-linked anthocyanin-flavanol pigments. The color was assessed by the CIELab method, and the concentration changes were analyzed by HPLC-DAD. On the other hand, the stability of these pigmented compounds was also calculated by the three 3D molecular simulation methods, that is molecular mechanics, molecular dynamics, and quantum chemistry simulation. The results obtained from CIELab analysis indicated that the formation of ethyl-linked anthocyanin-flavanol pigments resulted in a decrease of L*, a*, b* and C* values, and conversely, a rising of h* value. The 3D molecular simulations revealed that the stability of anthocyanins was as follows: Mv-3-O-glu > Pn-3-O-glu > Cy-3-O-glu. The cis or trans ethyl-linked anthocyanin-flavanol pigments were much more stable than their precursor anthocyanins. Among the pigments, ethyl-linked malvidin-3-O-glucoside-flavanol was more stable than ethyl-linked cyanidin-3-O-glucoside-flavanol and ethyl-linked peonidin-3-O-glucoside-flavanol