The effect of Self-Aggregation on the Determination of the Kinetic and Thermodynamic Constants of the Network of Chemical Reactions in 3-Glucoside Anthocyanins

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Abstract

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 x 10(-6) M up to 8 x 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 H-1 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-OGI-petunidin (1 -OH, 1 -OCH3), kuromanin (1 -OH), 3-OGI-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. (C) 2012 Elsevier Ltd. All rights reserved.
Original languageUnknown
Pages (from-to)125-135
JournalPhytochemistry
Volume83
Issue numberNA
DOIs
Publication statusPublished - 1 Jan 2012

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