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Volumn 121, Issue 46, 1999, Pages 10695-10701

Cage-escape of geminate radical pairs can produce peroxynitrate from peroxynitrite under a wide variety of experimental conditions

Author keywords

[No Author keywords available]

Indexed keywords

PEROXYNITRITE; RADICAL; SUPEROXIDE; TETRANITROMETHANE;

EID: 0033601102     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991077u     Document Type: Article
Times cited : (127)

References (69)
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    • note
    • As has become convention, the term "peroxynitrite" is used here to mean the sum of both the peroxynitrous acid and the peroxynitrite anion.
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    • note
    • 14N NMR spectrum of the peroxynitrite anion (1 M, pH 12) showed a very broad band (590 Hz) at 173 ppm (relative to nitromethane at zero ppm), which was not shifted, nor were any new bands observed between -60 and 280 ppm (scan width 9800 Hz) on addition of ethanol (up to 1 M).
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    • 2.
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    • -1 had neither its intensity nor its position affected by the addition of ethanol (up to 200 mM).
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    • note
    • -OONO], a similar explanation for our results can be ruled out.
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    • 29 this reaction can be ignored because our experiments were done in dioxygen-saturated (1.4 mM) solutions (both buffer and peroxynitrite). Most of the carbon-centered radicals formed will react with dioxygen rather than with (0.2 mM) TNM.
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    • 9a
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    • note
    • There is a direct reaction between aldehydes and TNM, but it is insignificant on the 1 s time scale of our experiments.
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    • note
    • a 5.9) to (short-lived) peroxynitrate anion.
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    • note
    • For reasons we did not explore, the rate constant for peroxynitrate decay was about 50% larger than the value found in all other experiments.
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    • 2-containing systems.
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    • • radicals were undoubtedly produced, their yield was clearly underestimated for reasons we do not yet understand.
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