The effect of self-aggregation on the determination of the kinetic and thermodynamic constants of the network of chemical reactions in 3-glucoside anthocyanins.
The six most common 3-glucoside anthocyanins, pelargonidin-3-glucoside, peonidin-3-glucoside, delphinidin-3-glucoside, malvidin-3-glucoside, cyanidin-3-glucoside and petunidin-3-glucoside were studied in great detail by NMR, UV-vis absorption and stopped flow. For each anthocyanin, the thermodynamic and kinetic constants of the network of chemical reactions were calculated at different anthocyanin concentration, from 6 × 10⁻⁶ M up to 8 × 10⁻⁴ M; an increasing of the flavylium cation acidity constant to give quinoidal base and a decreasing of the flavylium cation hydration constant to give hemiketal were observed by increasing the anthocyanin concentration. These effects are attributed to the self-aggregation of the flavylium cation and quinoidal base, which is stronger in the last case. The UV-vis and ¹H NMR spectral variations resulting from the increasing of the anthocyanin concentration were discussed in terms of two aggregation models; monomer-dimer and isodesmic, the last one considering the formation of higher order aggregates possessing the same aggregation constant of the dimer. The self-aggregation constant of flavylium cation at pH=1.0, calculated by both models increases by increasing the number of methoxy (-OCH₃) or hydroxy (-OH) substituents following the order: myrtillin (2 -OH), oenin (2 -OCH₃), 3-OGl-petunidin (1 -OH, 1 -OCH₃), kuromanin (1 -OH), 3-OGl-peonidin (1 -OCH₃) and callistephin (none). Evidence for flavylium aggregates possessing a shape between J and H was achieved, as well as for the formation of higher order aggregates.
REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Monte de Caparica, Portugal.
Yoann
Y
Leydet
Raquel
R
Gavara
Vesselin
V
Petrov
Ana M
AM
Diniz
A
A
Jorge Parola
João C
JC
Lima
Fernando
F
Pina
D000872:Anthocyanins / Q000737:chemistry*; D005960:Glucosides / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D013816:Thermodynamics
D000872:Anthocyanins; D005960:Glucosides