Finding of Synergistic and Cancel Effects on the Aroxyl Radical-Scavenging Rate and Suppression of Prooxidant Effect for Coexistence of α‑Tocopherol with β‑, γ‑, and δ‑Tocopherols (or -Tocotrienols)

Measurements of aroxyl radical (ArO•)-scavenging rate constants (k s AOH) of antioxidants (AOHs) [α-, β-, γ-, and δ-tocopherols (TocHs) and -tocotrienols (Toc-3Hs)] were performed in ethanol solution via stopped-flow spectrophotometry. k s AOH values of α-, β-, γ-, and δ-Toc-3Hs showed good agreement with those of the corresponding α-, β-, γ-, and δ- TocHs. k s AOH values were measured not only for each antioxidant but also for mixtures of two antioxidants: (i) α-TocH with β-, γ-, or δ-TocH and (ii) α-TocH with α-, β-, γ-, or δ-Toc-3H. A synergistic effect in which the k s AOH value increases by 12% for γ-TocH (or by 12% for γ-Toc-3H) was observed for solutions including α-TocH and γ-TocH (or γ-Toc-3H). On the other hand, a cancel effect in which the k s AOH value decreases (a) by 7% for β-TocH (or 11% for β-Toc-3H) and (b) by 24% for δ-TocH (or 25% for δ-Toc-3H) was observed for solutions including two kinds of antioxidants. However, only a synergistic effect may function in edible oils, because contents of β- and δ-TocHs (and β- and δ-Toc-3Hs) are much less than those of α- and γ-TocHs (and α- and γ-Toc-3Hs) in many edible oils. UV–vis absorption of α-Toc•, which was produced by reaction of α-TocH with ArO•, decreased remarkably for coexistence of α-TocH with β-, γ-, or δ-TocH (or β-, γ-, or δ-Toc-3H), indicating that the prooxidant effect of α-Toc• is suppressed by the coexistence of other TocHs and Toc-3Hs.