Study on the Synthesis, Antioxidant Properties, and Self-Assembly of Carotenoid–Flavonoid Conjugates

Abstract

Flavonoids and carotenoids possess beneficial physiological effects, such as high antioxidant capacity, anticarcinogenic, immunomodulatory, and anti-inflammatory properties, as well as protective effects against UV light. The covalent coupling of hydrophobic carotenoids with hydrophilic flavonoids, such as daidzein and chrysin, was achieved, resulting in new amphipathic structures. 7-Azidohexyl ethers of daidzein and chrysin were prepared in five steps, and their azide-alkyne [4 + 2] cycloaddition with pentynoates of 8′-apo-β-carotenol, zeaxanthin, and capsanthin afforded carotenoid−flavonoid conjugates. The trolox-equivalent antioxidant capacity against ABTS•+ radical cation and self-assembly of the final products were examined. The 1:1 flavonoid−carotenoid hybrids generally showed higher antioxidant activity than their parent flavonoids but lower than that of the corresponding carotenoids. The diflavonoid hybrids of zeaxanthin and capsanthin, however, were found to exhibit a synergistic enhancement in antioxidant capacities. ECD (electronic circular dichroism) and UV-vis analysis of zeaxanthin−flavonoid conjugates revealed that they form different optically active J-aggregates in acetone/water and tetrahydrofuran/water mixtures depending on the solvent ratio and type of the applied aprotic polar solvent, while the capsanthin derivatives showed no self-assembly. The zeaxanthin bis-triazole conjugates with daidzein and with chrysin, differing only in the position of a phenolic hydroxyl group, showed significantly different aggregation profile upon the addition of water.

Keywords

• carotenoids
• flavonoids
• click-reaction
• antioxidant capacity
• supramolecular chirality
• zeaxanthin–flavonoid conjugates
• electronic circular dichroism