Distance-Dependent Diffusion-Controlled Reaction of •NO and O2•- at Chemical Equilibrium with ONOO-

被引:34
作者
Botti, Horacio [1 ,2 ]
Moeller, Matias N. [2 ,3 ,4 ,5 ]
Steinmann, Daniel [6 ]
Nauser, Thomas [6 ]
Koppenol, Willem H. [6 ]
Denicola, Ana [2 ,3 ]
Radi, Rafael [2 ,7 ]
机构
[1] Inst Pasteur Montevideo, Unidad Cristalog Prot, Montevideo 11400, Uruguay
[2] Ctr Free Rad & Biomed Res, Montevideo 11800, Uruguay
[3] Univ Republica, Fac Ciencias, Inst Quim Biol, Lab Fis Quim Biol, Montevideo 11400, Uruguay
[4] Vanderbilt Univ, Dept Chem, Nashville, TN 37240 USA
[5] Vanderbilt Univ, Vanderbilt Inst Chem Biol, Nashville, TN 37240 USA
[6] ETH, Inst Inorgan Chem, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland
[7] Univ Republica, Fac Med, Dept Bioquim, Montevideo 11800, Uruguay
关键词
NEGATIVE ACTIVATION-ENERGY; FLUCTUATION-INDUCED KINETICS; CURVED ARRHENIUS PLOTS; NITRIC-OXIDE; GIBBS ENERGY; BIMOLECULAR REACTIONS; REVERSIBLE-REACTIONS; PEROXYNITROUS ACID; PULSE-RADIOLYSIS; AQUEOUS-SOLUTION;
D O I
10.1021/jp105606b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The fast reaction of (NO)-N-center dot and O-2(center dot-) to give ONOO- has been extensively studied at irreversible conditions, but the reasons for the wide variations in observed forward rate constants (3.8 <= k(f) <= 20 x 10(9) M-1 s(-1)) remain unexplained. We characterized the diffusion-dependent aqueous (pH > 12) chemical equilibrium of the form (NO)-N-center dot + O-2(center dot-) = ONOO- with respect to its dependence on temperature, viscosity, and [ONOO-](eq) by determining [ONOO-](eq) and [(NO)-N-center dot](eq). The equilibrium forward reaction rate constant (k(f)(eq)) has negative activation energy, in contrast to that found under irreversible conditions. In contradiction to the law of mass action, we demonstrate that the equilibrium constant depends on ONOO- concentration. Therefore, a wide range of k(f)(eq) values could be derived (7.5-21 x 10(9) M-1 s(-1)). Of general interest, the variations in k(f) can thus be explained by its dependence on the distance between ONOO- particles (sites of generation of (NO)-N-center dot and O-2(center dot-)).
引用
收藏
页码:16584 / 16593
页数:10
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