Reactions of nitric oxide with nitronyl nitroxides and oxygen

Prediction of nitrite and nitrate formation by kinetic simulation

Neil Hogg, Ravinder Jit Singh, Joy Joseph, Frank Neese, B. Kalyanaraman

Research output: Contribution to journalArticle

67 Citations (Scopus)

Abstract

Nitric oxide reacts with nitronyl nitroxides (NNO) to form imino nitroxides (INO) and this transformation can be monitored using electron spin resonance spectroscopy. Recently, Akaike et al., reported that NNO such as 2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PTIO) and its derivatives (e.g., carboxy-PTIO) react with nitric oxide (·NO) in a 1: 1 stoichiometry forming 2-phenyl-4,4,5,5-tetra-methylimidazoline-1-oxyl (PTI) or the respective product (e.g., carboxy-PTI) together with nitrite and nitrate (Akaike et al., Biochemistry 32, 827-832, 1993). In this paper, we reevaluate their results and show that the stoichiometry of the reaction between PTIO and ·NO is 0.63 ± 0.06: 1.0. The reason for this discrepancy is due to an erroneous assumption by Akaike et al., that the stoichiometry for the reaction between ·NO and O2 is 2: 1 in aqueous solution. If the data reported by Akaike et al., were recalculated using a 4: 1 stoichiometry established for the aqueous oxidation of ·NO, the reaction between ·NO and PTIO would give a stoichiometry of 0.5: 1.0 in closer agreement with our data. We propose a mechanism for the reaction between PTIO and ·NO in aqueous solution. This mechanism predicts that the stoichiometry between carboxy-PTIO and ·NO is dependent on the rate of generation of ·NO and is 1: 1 only at low rates of ·NO generation (i.e., 10-13 M/s). However the stoichiometry approaches 0.5: 1.0 at higher rates of ·NO production or when it is added as a bolus. The ratio between nitrite and nitrate also varies as a function of the rate of generation of ·NO. The model agrees with previous experimental observations that the aqueous oxidation of ·NO in air saturated solutions will exclusively form nitrite and predicts that ·NO will only generate substantial amounts of nitrate if it is released at a rate less than 10-17 M/s. This may have important consequences in cellular systems where the concentration of ·NO is typically measured from nitrite production.

Original languageEnglish (US)
Pages (from-to)47-56
Number of pages10
JournalFree Radical Research
Volume22
Issue number1
DOIs
StatePublished - 1995

Fingerprint

Nitrites
Nitrates
Nitric Oxide
Oxygen
Kinetics
Stoichiometry
Electron spin resonance spectroscopy
Oxidation
Biochemistry
Electron Spin Resonance Spectroscopy

Keywords

  • Electron spin resonance
  • Nitric oxide
  • Nitronyl nitroxide

ASJC Scopus subject areas

  • Biochemistry

Cite this

Reactions of nitric oxide with nitronyl nitroxides and oxygen : Prediction of nitrite and nitrate formation by kinetic simulation. / Hogg, Neil; Singh, Ravinder Jit; Joseph, Joy; Neese, Frank; Kalyanaraman, B.

In: Free Radical Research, Vol. 22, No. 1, 1995, p. 47-56.

Research output: Contribution to journalArticle

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T1 - Reactions of nitric oxide with nitronyl nitroxides and oxygen

T2 - Prediction of nitrite and nitrate formation by kinetic simulation

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AU - Singh, Ravinder Jit

AU - Joseph, Joy

AU - Neese, Frank

AU - Kalyanaraman, B.

PY - 1995

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N2 - Nitric oxide reacts with nitronyl nitroxides (NNO) to form imino nitroxides (INO) and this transformation can be monitored using electron spin resonance spectroscopy. Recently, Akaike et al., reported that NNO such as 2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PTIO) and its derivatives (e.g., carboxy-PTIO) react with nitric oxide (·NO) in a 1: 1 stoichiometry forming 2-phenyl-4,4,5,5-tetra-methylimidazoline-1-oxyl (PTI) or the respective product (e.g., carboxy-PTI) together with nitrite and nitrate (Akaike et al., Biochemistry 32, 827-832, 1993). In this paper, we reevaluate their results and show that the stoichiometry of the reaction between PTIO and ·NO is 0.63 ± 0.06: 1.0. The reason for this discrepancy is due to an erroneous assumption by Akaike et al., that the stoichiometry for the reaction between ·NO and O2 is 2: 1 in aqueous solution. If the data reported by Akaike et al., were recalculated using a 4: 1 stoichiometry established for the aqueous oxidation of ·NO, the reaction between ·NO and PTIO would give a stoichiometry of 0.5: 1.0 in closer agreement with our data. We propose a mechanism for the reaction between PTIO and ·NO in aqueous solution. This mechanism predicts that the stoichiometry between carboxy-PTIO and ·NO is dependent on the rate of generation of ·NO and is 1: 1 only at low rates of ·NO generation (i.e., 10-13 M/s). However the stoichiometry approaches 0.5: 1.0 at higher rates of ·NO production or when it is added as a bolus. The ratio between nitrite and nitrate also varies as a function of the rate of generation of ·NO. The model agrees with previous experimental observations that the aqueous oxidation of ·NO in air saturated solutions will exclusively form nitrite and predicts that ·NO will only generate substantial amounts of nitrate if it is released at a rate less than 10-17 M/s. This may have important consequences in cellular systems where the concentration of ·NO is typically measured from nitrite production.

AB - Nitric oxide reacts with nitronyl nitroxides (NNO) to form imino nitroxides (INO) and this transformation can be monitored using electron spin resonance spectroscopy. Recently, Akaike et al., reported that NNO such as 2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PTIO) and its derivatives (e.g., carboxy-PTIO) react with nitric oxide (·NO) in a 1: 1 stoichiometry forming 2-phenyl-4,4,5,5-tetra-methylimidazoline-1-oxyl (PTI) or the respective product (e.g., carboxy-PTI) together with nitrite and nitrate (Akaike et al., Biochemistry 32, 827-832, 1993). In this paper, we reevaluate their results and show that the stoichiometry of the reaction between PTIO and ·NO is 0.63 ± 0.06: 1.0. The reason for this discrepancy is due to an erroneous assumption by Akaike et al., that the stoichiometry for the reaction between ·NO and O2 is 2: 1 in aqueous solution. If the data reported by Akaike et al., were recalculated using a 4: 1 stoichiometry established for the aqueous oxidation of ·NO, the reaction between ·NO and PTIO would give a stoichiometry of 0.5: 1.0 in closer agreement with our data. We propose a mechanism for the reaction between PTIO and ·NO in aqueous solution. This mechanism predicts that the stoichiometry between carboxy-PTIO and ·NO is dependent on the rate of generation of ·NO and is 1: 1 only at low rates of ·NO generation (i.e., 10-13 M/s). However the stoichiometry approaches 0.5: 1.0 at higher rates of ·NO production or when it is added as a bolus. The ratio between nitrite and nitrate also varies as a function of the rate of generation of ·NO. The model agrees with previous experimental observations that the aqueous oxidation of ·NO in air saturated solutions will exclusively form nitrite and predicts that ·NO will only generate substantial amounts of nitrate if it is released at a rate less than 10-17 M/s. This may have important consequences in cellular systems where the concentration of ·NO is typically measured from nitrite production.

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