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The chemistry of peroxynitrite, a biological toxin

机译：过氧亚硝酸盐（一种生物毒素）的化学

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Oxyradicals play a tole in several diseases. While for several decades the hydroxyl radical - produced via the Fenton reaction - has been considered the species that initiates oxyradical damage, new findings suggest that much of this damage can be ascribed to peroxynitrite, O=NOO-, formed from the reaction of the superoxide anion with nitrogen monoxide near activated macrophages. The rate constant for the reaction of this reaction has been investigated by flash photolysis and was found to be significantly higher than previously described in the literature, 1.9 x 10(10) M-1s-1. Studies of the isomerization to nitrate resulted in the discovery of a complex between peroxynitrite and its protonated form with a stability constant of 1 x 10(4) M-1. Some of the harmful reaction of peroxynitrous acid have been ascribed to the hydroxyl radical as a product of homolysis of the O-O bond during the conversion to nitrate. Kinetics of the isomerization reaction as a function of pressure show that the activation volume is only +1.5+1.0 ml mol-1, which is inconsistent with homolysis. Instead, an intermediate, possibly a distorted trans-isomer of O=NOOH could be responsible for the harmful reactions of peroxynitrite.
机译：氧自由基在多种疾病中起着重要作用。尽管几十年来，通过芬顿反应产生的羟基被认为是引发氧自由基损害的物种，但新发现表明，这种损害的大部分归因于由超氧化物反应形成的过氧亚硝酸盐（O = NOO-）。阴离子与一氧化氮接近活化的巨噬细胞。已经通过快速光解研究了该反应的反应速率常数，发现该速率常数显着高于先前文献中所述的1.9×10（10）M-1s-1。异构化为硝酸盐的研究导致发现过氧亚硝酸盐与其质子化形式之间的复合物，其稳定常数为1 x 10（4）M-1。过氧亚硝酸的一些有害反应已归因于羟基自由基，该自由基是在转化为硝酸盐期间O-O键均化的产物。异构化反应动力学作为压力的函数表明，活化体积仅为+ 1.5 + 1.0 ml mol-1，与均质相矛盾。取而代之的是，O = NOOH的中间体，可能是扭曲的反式异构体，可能导致过亚硝酸盐的有害反应。

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