Activation of Superoxide Ion by Reactions with Protons, Electrophiles, Secondary Amines, Radicals, and Reduced Metal· Ions
Activation of Superoxide Ion by Reactions with Protons, Electrophiles, Secondary Amines, Radicals, and Reduced Metal· Ions
复制标题
通过与质子、亲电子试剂、仲胺、自由基和还原金属离子的反应活化超氧离子
DOI：
--
复制
发表时间：
1983
期刊：
影响因子：
--
通讯作者：
D. T. Sawyer
中科院分区：
文献类型：
--
作者：
Julian L. Roberts;D. T. Sawyer
在非质子和水介质中，质子诱导的超氧离子（O - 2）歧化产生多种反应物质（HO2·、H2O2、HO - 2和·OH）。在非质子介质中，O - 2迅速降解多氯烃类（CCl4、HCCl3和DDT）为氧化产物（CCl4 Cl3COO·；HCCl3 Cl2C：和Cl2C=O）。烷基卤化物反应较慢（bul BuOO·和BuOO−）。在甲基紫素（MV2+）、还原黄素、酯和低价过渡金属配合物的存在下，O−2的形成导致氧化酶的活性氧助剂和反应模拟物的形成[MV+-OO-、4a-氢过氧黄素、RC(O)OO−和Zn11（O2·）+]。质子诱导的O−2在水中歧化反应和O−2在非质子溶剂中的亲核反应的动力学数据表明，后者对生物氧合反应可能意义不大。
In aprotic and aqueous media the proton-induced disproportionation of superoxide ion (O−2) yields a variety of reactive species (HO2·, H2O2, HO−2, and · OH). In aprotic media O−2 rapidly degrades polychlorinated hydrocarbons (CCl4, HCCl3, and DDT) to oxygenated products (CCl4 Cl3COO·; HCCl3 Cl2C: and Cl2C=O). Alkyl halides react more slowly (BuCl BuOO· and BuOO−). Formation of O−2 in the presence of methyl viologen (MV2+), reduced flavins, esters, and low-valent transition metal complexes results in the formation of reactive oxygenating agents and reaction mimics for oxygenases [MV+-OO-, 4a-hydroperoxyflavins, RC(O)OO−, and Zn11(O2 ·)+]. Kinetic data for the proton-induced disproportionation of O−2 in water and the nucleophilic reactions of O−2 in aprotic solvents lead to the conclusion that the latter are probably of little significance for biological oxygenation reactions.