Quercetin and daidzein β-apo-14'-carotenoic acid esters as membrane antioxidants

Esterification by β-apo-14'-carotenoic acid was found to have opposite effects on antioxidant activity of quercetin (at B4', B3' hydroxyl) as of daidzein (at A7 hydroxyl) in phosphatidylcholine liposomes. The daidzein ester had increased activity, while quercetin had a significant decreased activity. Quantum mechanical calculations using density function theory (DFT) indicate a modest decrease in bond dissociation enthalpy, BDE, for (weakest) hydrogen-oxygen phenolic bond in daidzein from 368.4 kJ · mol(- 1) to 367.7 kJ · mol(- 1) compared to a significant increase in quercetin from 329.5 kJ · mol(- 1) to 356.6 kJ · mol(- 1) upon derivatization. These opposite changes in tendency for hydrogen atom transfer from phenolic groups to lipid radicals combined with an increase in A-to-B dihedral angle from 0.0° to 36.4° and in dipole moment from 0.40 D to 6.01 D for quercetin upon derivatization, while less significant for daidzein (36.4°-36.7° and 3.26 D-7.87 D, respectively), together provide a rationale for the opposite effect of esterification on antioxidation.