过氧亚硝酸盐的分解动力学：pH 值和缓冲液的影响。
Decomposition kinetics of peroxynitrite: influence of pH and buffer.
机构信息
Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, 8093 Zurich, Switzerland.
出版信息
Dalton Trans. 2013 Jul 21;42(27):9898-905. doi: 10.1039/c3dt50945a. Epub 2013 May 23.
The decay of ONOOH near neutral pH has been examined as a function of isomerization to H(+) and NO3(-), and decomposition to NO2(-) and O2via O2NOO(-). We find that in phosphate buffer k(isomerization) = 1.11 ± 0.01 s(-1) and k(disproportionation) = (1.3 ± 0.1) × 10(3) M(-1) s(-1) at 25 °C and I = 0.2 M. In the presence of 0.1 M tris(hydroxymethyl)aminomethane (Tris), the decay proceeds more rapidly: k(disproportionation) = 9 × 10(3) M(-1) s(-1). The measured first half-life of the absorbance of peroxynitrite correlates with [Tris]0·([ONOO(-)]0 + [ONOOH]0)(2), where the subscript 0 indicates initial concentrations; if this function exceeds 6.3 × 10(-12) M(3), then Tris significantly accelerates the decomposition of peroxynitrite.
在中性 pH 条件下，我们研究了过氧亚硝酸（ONOOOH）的衰减，考察了其向 H(+)和 NO3(-)异构化以及通过 O2NOO(-)分解为 NO2(-)和 O2 的过程。结果表明，在 25°C 和 I = 0.2 M 条件下，磷酸盐缓冲液中异构化反应的速率常数 k(isomerization) = 1.11 ± 0.01 s(-1)，歧化反应的速率常数 k(disproportionation) = (1.3 ± 0.1) × 10(3) M(-1) s(-1)。在 0.1 M 三羟甲基氨基甲烷（Tris）存在下，衰减反应进行得更快：k(disproportionation) = 9 × 10(3) M(-1) s(-1)。过氧亚硝酸吸光度的半衰期与 [Tris]0·([ONOO(-)]0 + [ONOOH]0)(2)相关，其中下标 0 表示初始浓度；如果该函数超过 6.3 × 10(-12) M(3)，则 Tris 会显著加速过氧亚硝酸的分解。
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