The relationship between antioxidant activity, first electrochemical oxidation potential, and spin population of flavonoid radicals

Abstract I have shown that by averaging antioxidant activity (AA) values measured by different methods it is possible to obtain an excellent correlation ( R 2 =0.960) between the first electrochemical oxidation potential, E p1 , and AA. Separate correlations using the AA values obtained with each of the four methods [ R 2 were 0.561 for diphenyl-1-picrylhydrazyl (DPPH), 0.849 for Folin Ciocalteu reagent (FCR), 0.848 for the ferric-reducing ability of plasma (FRAP), and 0.668 for the Trolox equivalent antioxidant capacity (TEAC)] were all worse, and in some cases not useful at all, such as the one for DPPH. Also, the sum of atomic orbital spin populations on the carbon atoms in the skeleton of radicals ( s(C) Σ AOSP Rad ), calculated with the semi-empirical parameterisation method 6 (PM6) in water, was used to correlate both E p1 and AA, yielding R2=0.926 and 0.950, respectively. This showed to be a much better variable for the estimation of E p1 and AA than the bond dissociation energy (BDE), R 2 =0.854 and 0.901 for E p1 and AA, respectively, and especially the ionisation potential (IP), R 2 =0.445 and 0.435 for E p1 and AA, respectively.