Kinetic and Thermodynamic Study of the Thermally Induced (E/Z)-Isomerization of the retro-Carotenoid Rhodoxanthin.

Abstract

The hitherto scarcely investigated retro-carotenoid rhodoxanthin possesses high potential for coloration in the food and beverage industry using technofunctional formulations prepared thereof. Hence, we studied (E/Z)-isomerization pathways of rhodoxanthin, including seven (E/Z)-isomers comprising (Z)-configured double bonds at unusual exocyclic and inner polyene chain positions. A mathematical approach was developed to deduce kinetic and thermodynamic parameters of six parallel equilibrium reactions interconnecting (all-E)-rhodoxanthin with mono-, di-, and tri-(Z)-isomers using multiresponse modeling. At 40-70 °C in ethyl acetate, reaction rate constants regarding the rotation from (all-E)- to (6Z)-rhodoxanthin were 11-14 times higher than those of the common (E/Z)-isomerization reaction at C-13,14 of the non-retro-structured carotenoid canthaxanthin. Moreover, the equilibrium reaction between (all-E)- and (6Z)-rhodoxanthin was strongly product favored as indicated by negative Gibbs energies (-1.6 to -2.2 kJ mol-1), which is unusual for carotenoids within the studied temperatures. Overall, this study provides novel insights into structure-related dependencies of (E/Z)-isomerization reaction kinetics and thermodynamics of polyenes.