Synthesis of New Vitamin E Derivatives and Mechanism of the Protection of Oxygen Toxicity in Biological System.

新型维生素E衍生物的合成及生物系统氧中毒防护机制。

• 批准号: 02640396
• 负责人: MUKAI Kazuo
• 金额: $ 1.28万
• 依托单位: Ehime Univesity
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640396/
• 关键词: Antioxidant; Vitamin E; Active Oxygen; Lipid Peroxidation; Reaction Rates; Singlet Oxygen; Stopped-Flow; Ubiquinol; ビタミンC; 抗酸化活性; ユビキノン; エストロゲン; 活性酸素

About 30 kinds of new tocopherol derivatives have been synthesized, and the rates of scavenging of substituted phenoxyl radical (PhO^<. >), k_2 and quenching of singlet oxygen ( ^1O_2), k_Q, by these tocopherols have been measured spectrophotometrically in ethanol. Both the log of the rate constants, k_2 and k_Q, were found to correlate with their peak oxidation potential, E_p. The quenching rates, k_Q, were found to be related linearly to the rates k_1 and k_2 of scavenging of peroxyl (LOO^<. >) (reported by Burton et al.) and phenoxyl (PhO^<. >) radicals by these tocopherols, respectively. Vitamin K_1-and K_3- hydroquinone and some estrogens were found to be several times more active than -tocopherol, respectively, which has the highest antioxidant activity among natural tocopherols Further, the second-order rate constants, k_<-1>, k_3, k_4, and k_6 for the reaction of vitamin E radical with i) lipid hydroperoxides (LOOH), ii) vitamin C, iii) ubiquinol, and iv) unsaturated fatty acid esters (LH), respectively, in solution have been measured. By comparing these rate constants, the mechanism of antioxidant and prooxidant actions of tocopherols in biomembranes and edible oils has been discussed.

本文合成了30多种新的生育酚衍生物，并在乙醇中测定了它们清除取代苯氧基自由基（PhO_2<. >）和猝灭单线态氧（^1O_2）的速率k_0。速率常数k_2和k_Q的对数均与其氧化峰电位E_p有关，猝灭速率k_Q与清除过氧化氢（LOO^）的速率k_1和k_2呈线性关系<. >。和苯氧基（PhO^<. >）自由基。维生素K_1-、K_3-氢醌和一些雌激素的抗氧化活性分别比天然生育酚中抗氧化活性最高的-生育酚高出数倍<-1>。此外，还测定了维生素E自由基与i）脂质过氧化氢（LOOH），ii）维生素C，iii）泛酚，和iv）不饱和脂肪酸酯（LH）。通过比较这些速率常数，探讨了生育酚在生物膜和食用油中的抗氧化和促氧化作用机理。

项目成果

K.Mukai: "Stopped-Flow Investigation of Antioxidant Activity of Estrogens in Solution." Biochim.Biophys.Acta. 1035. 348-352 (1990)

K.Mukai：“溶液中雌激素抗氧化活性的停流研究”。

K. Mukai: "Stopped-Flow Kinetic Study of the Regeneration Reaction of Tocopheroxyl Radical by Reduced Ubiquinone-10 in Solution" Biochem. Biophys. Acta. 1035. 77-82 (1990)

K. Mukai：“溶液中还原型泛醌 10 的生育酚自由基再生反应的停流动力学研究”Biochem。

K.Mukai: "Vitamin E:Biochemistry and Clinical Applications" Marcel Dekker Inc., 23 (1992)

K.Mukai：“维生素 E：生物化学和临床应用”Marcel Dekker Inc.，23 (1992)

S.Nagaoka: "Mechanism of Antioxidant Reaction of Vitamin E.Charge Transfer and Tenneling Effect in Proton Transfer Reaction." J.Phys.Chem.(1992)

S.Nagaoka：“维生素 E 的抗氧化反应机制。质子转移反应中的电荷转移和隧道效应。”

K.Mukai (分担執筆): "Vitamin E:Biochemistry and Clinical Applications." Marcel Dekker Inc., 30 (1991)

K.Mukai（撰稿人）：“维生素 E：生物化学和临床应用。”Marcel Dekker Inc.，30 (1991)