On the Limits of Anthocyanins Co-Pigmentation Models and Respective Equations

Anthocyanins co-pigmentation models with application on 1:1 complexes were revisited, and their limitations were critically commented. The flavylium multistate of species is dramatically simplified to a single acid-base equilibrium between flavylium cation and its conjugated base CB, equal to the sum of quinoidal base, hemiketal, and cis and trans-chalcones. Bearing this, a new equation that simultaneously allows calculation of the co-pigmentation constant with flavylium cation (K-AH+(CP)) and with its conjugated base CB (K-CBCP) was deduced. This equation can be used at a fixed co-pigment concentration with pH as a variable or at fixed pH and co-pigment concentration variable. A global fitting of all data allows us to calculate both association constants with good accuracy. The model was applied to the co-pigmentation of malvidin-3-glucoside with caffeine and pentagalloyl glucose (PGG). Caffeine gives rise to complexes not only with flavylium cation K-AH+(CP) = 125 +/- 7 M-1 but also with CB with K-CBCP = 23 +/- 3 M-1. PGG complexes exclusively with flavylium cation, K-AH+(CP) = 914 +/- 10 M-1, and the possible interaction with quinoidal base is lower than the detection limits that the inherent experimental error permits.

Automated summary

The study revisited anthocyanins co-pigmentation models with new equation allowing calculation of co-pigmentation constant. The model was successfully applied to the co-pigmentation of malvidin-3-glucoside with caffeine and pentagalloyl glucose.