The reduction potential of nitric oxide (NO) and its importance to NO biochemistry

Michael D. Bartberger, Wei Liu, Eleonora Ford, Katrina M Miranda, Christopher Switzer, Jon M. Fukuto, Patrick J. Farmer, David A. Wink, Kendall N. Houk

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Abstract

A potential of about-0.8 (±0.2) V (at 1 M versus normal hydrogen electrode) for the reduction of nitric oxide (NO) to its one-electron reduced species, nitroxyl anion (3NO-) has been determined by a combination of quantum mechanical calculations, cyclic voltammetry measurements, and chemical reduction experiments. This value is in accord with some, but not the most commonly accepted, previous electrochemical measurements involving NO. Reduction of NO to 1NO- is highly unfavorable, with a predicted reduction potential of about -1.7 (±0.2) V at 1 M versus normal hydrogen electrode. These results represent a substantial revision of the derived and widely cited values of +0.39 V and -0.35 V for the NO/3NO-and NO/1NO- couples, respectively, and provide support for previous measurements obtained by electrochemical and photoelectrochemical means. With such highly negative reduction potentials, NO is inert to reduction compared with physiological events that reduce molecular oxygen to superoxide. From these reduction potentials, the pKa of 3NO- has been reevaluated as 11.6 (±3.4). Thus, nitroxyl exists almost exclusively in its protonated form, HNO, under physiological conditions. The singlet state of nitroxyl anion, 1NO-, is physiologically inaccessible. The significance of these potentials to physiological and pathophysiological processes involving NO and O2 under reductive conditions is discussed.

Original languageEnglish (US)
Pages (from-to)10958-10963
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume99
Issue number17
DOIs
StatePublished - Aug 20 2002
Externally publishedYes

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Biochemistry
Nitric Oxide
Anions
Hydrogen
Electrodes
Physiological Phenomena
Superoxides
Electrons
Oxygen
nitroxyl

ASJC Scopus subject areas

  • Genetics
  • General

Cite this

The reduction potential of nitric oxide (NO) and its importance to NO biochemistry. / Bartberger, Michael D.; Liu, Wei; Ford, Eleonora; Miranda, Katrina M; Switzer, Christopher; Fukuto, Jon M.; Farmer, Patrick J.; Wink, David A.; Houk, Kendall N.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 99, No. 17, 20.08.2002, p. 10958-10963.

Research output: Contribution to journalArticle

Bartberger, Michael D. ; Liu, Wei ; Ford, Eleonora ; Miranda, Katrina M ; Switzer, Christopher ; Fukuto, Jon M. ; Farmer, Patrick J. ; Wink, David A. ; Houk, Kendall N. / The reduction potential of nitric oxide (NO) and its importance to NO biochemistry. In: Proceedings of the National Academy of Sciences of the United States of America. 2002 ; Vol. 99, No. 17. pp. 10958-10963.
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