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氧自由基反应:从键离解能到还原电位

Oxyradical reactions: from bond-dissociation energies to reduction potentials.

作者信息

Koppenol W H

机构信息

Biodynamics Institute, Louisiana State University, Baton Rouge 70803-1800.

出版信息

FEBS Lett. 1990 May 21;264(2):165-7. doi: 10.1016/0014-5793(90)80239-f.

DOI:10.1016/0014-5793(90)80239-f
PMID:2358063
Abstract

Destructive radical reactions involve alkyl, alkoxyl and alkylperoxyl radicals, as well as alkylhydroperoxides. From bond energies the following reduction potentials vs NHE at neutral pH are derived: E0'(RO./ROH) = 1.6 V, E0'(ROO./ROOH) = 1.0 V, E0(ROOH/RO., H2O) = 1.9 V, and the two-electron reduction potential E0'(ROOH/ROH, H2O) = 1.7 V. Hydrogen abstraction from a bis-allylic methylene group by alkoxyl and alkylperoxyl radicals is favourable with Gibbs energies of -23 and -9 kcal/mol, respectively. Similarly, alkoxyl radicals can oxidize alkylhydroperoxides, delta G0' = -14 kcal/mol.

摘要

破坏性自由基反应涉及烷基、烷氧基和烷基过氧自由基以及烷基氢过氧化物。根据键能,在中性pH条件下相对于标准氢电极(NHE)可得出以下还原电位:E0'(RO./ROH) = 1.6 V,E0'(ROO./ROOH) = 1.0 V,E0(ROOH/RO., H2O) = 1.9 V,以及双电子还原电位E0'(ROOH/ROH, H2O) = 1.7 V。烷氧基和烷基过氧自由基从双烯丙基亚甲基夺取氢是有利的,吉布斯自由能分别为-23和-9 kcal/mol。同样,烷氧基自由基可以氧化烷基氢过氧化物,ΔG0' = -14 kcal/mol。

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