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Reaction of CO2 with ONOO-: One Molecule of CO2 Is Not Enough.

Abstract：

:With CO2 present in excess, ONOO- reacts to form an adduct in solution and in the solid state, most likely ONOOCO2-. In solution, the adduct appears within 2 ms and absorbs at 300 with an extinction coefficient, which is either 50% or 100% (preferred) of that of ONOO-, 1.70 × 103 M-1 cm-1, and at 685 nm with an extinction coefficient of 85 M-1 cm-1. When solid [(CH3)4N][ONOO] is treated with CO2, these two maxima are red-shifted by 30-50 nm. The equilibrium constant for adduct formation in solution is (4.5 ± 0.5) × 103 M. The adduct reacts further with another CO2 at a rate of (2.6 ± 0.8) × 104 M-1 s-1 and produces 2 CO2 and NO3-. Thermochemical calculations show that ΟΝΟΟCO2- is a strong two-electron oxidizing agent, E°(ONOOCO2-, H+/NO2-, HCO3-) = +1.28 V at pH 7 and an even stronger one-electron oxidizing agent E°'(ONOOCO2-, H+/NO2•, HCO3-) = +1.51 V at pH 7. The extent of homolysis, that is formation of NO2• and CO3•-, is small, slightly less than 1% relative to ONOO- at the physiological concentration of CO2 of 1.3 mM in plasma. Thus, ONOOCO2- is more relevant than CO3•- under in vivo conditions.

journal_name

Chem Res Toxicol

journal_title

Chemical research in toxicology

authors

Serrano-Luginbuehl S,Kissner R,Koppenol WH

doi

10.1021/acs.chemrestox.8b00068

subject

Has Abstract

pub_date

2018-08-20 00:00:00

pages

721-730

issue

8

eissn

0893-228X

issn

1520-5010

journal_volume

31

pub_type

杂志文章

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