The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution.

The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution.
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过氧亚硝酸盐在水溶液中分解为硝酰阴离子(NO-)和单线态氧。

DOI:
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发表时间:
2000
影响因子:
11.1
通讯作者:
N. Geacintov
N. Geacintov
中科院分区:
综合性期刊1区
文献类型:
--
作者:
A. U. Khan;D. Kovacic;A. Kolbanovskiy;M. Desai;K. Frenkel;N. Geacintov

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研究了过氧亚硝基阴离子(OONO(-))在中性磷酸钠缓冲溶液中的分解机理。在pH 13的条件下,一氧化氮与超氧阴离子直接反应生成OONO(-)。假设OONO(-)在pH 7.0质子化为HOONO后,按照自旋守恒的单分子机理分解为(1)O(2)和HNO。将小等份的浓缩碱性OONO(-)溶液加入缓冲溶液(最终pH 7.0-7.2)中,观察到高产率的(1)O(2)和NO(-)的形成。生成的(1)O(2)以9,10-二苯基蒽(DPA)的跨环过氧化物(DPAO(2))的形式被捕获。由HNO(pKa 4.5)形成的硝酰基阴离子(NO-)在高铁血红蛋白(MetHb)水溶液中被捕获为亚硝基血红蛋白(HbNO)。在25 mM碳酸氢钠存在下,已知碳酸氢钠可加速OONO(-)的分解速率,捕获的单线态氧的量减少约2倍,而高铁血红蛋白捕获NO(-)的产率保持不受影响。由于已知NO(3)(-)是OONO(-)的最终分解产物,因此这些结果表明硝酸根阴离子不是通过OONO(-)的直接异构化形成的,而是通过源自NO(-)的间接途径形成的。
The mechanism of decomposition of peroxynitrite (OONO(-)) in aqueous sodium phosphate buffer solution at neutral pH was investigated. The OONO(-) was synthesized by directly reacting nitric oxide with superoxide anion at pH 13. The hypothesis was explored that OONO(-), after protonation at pH 7.0 to HOONO, decomposes into (1)O(2) and HNO according to a spin-conserved unimolecular mechanism. Small aliquots of the concentrated alkaline OONO(-) solution were added to a buffer solution (final pH 7.0-7.2), and the formation of (1)O(2) and NO(-) in high yields was observed. The (1)O(2) generated was trapped as the transannular peroxide (DPAO(2)) of 9, 10-diphenylanthracene (DPA) dissolved in carbon tetrachloride. The nitroxyl anion (NO-) formed from HNO (pKa 4.5) was trapped as nitrosylhemoglobin (HbNO) in an aqueous methemoglobin (MetHb) solution. In the presence of 25 mM sodium bicarbonate, which is known to accelerate the rate of decomposition of OONO(-), the amount of singlet oxygen trapped was reduced by a factor of approximately 2 whereas the yield of trapping of NO(-) by methemoglobin remained unaffected. Because NO(3)(-) is known to be the ultimate decomposition product of OONO(-), these results suggest that the nitrate anion is not formed by a direct isomerization of OONO(-), but by an indirect route originating from NO(-).
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发表时间: 1996-03
影响因子: 3.9
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