Oxidation of hemoglobin and myoglobin by alkyl nitrites inhibition by oxygen.
Open accessAbstract
The reactions of human hemoglobin and sperm whale myoglobin with ethyl nitrite under aerobic conditions have been examined in kinetic detail. Ethyl nitrite converts two equivalents of oxyhemoglobin or oxymyoglobin to their oxidized counterparts with concurrent production of one equivalent each of molecular oxygen, nitrate ion, and ethyl alcohol. Inverse first order kinetic dependence on the concentration of molecular oxygen has been observed and is interpreted by a mechanism in which oxygen dissociation from the oxyhemoprotein occurs prior to rate-limiting oxidation by ethyl nitrite. The rate constant for ethyl nitrite oxidation of hemoglobin from which the fourth oxygen has dissociated is calculated to be 45 times greater than the corresponding rate constant for oxidation of deoxyhemoglobin. This rate enhancement is proposed to be a reflection of the oxidative susceptibility of the R and T conformational states of hemoglobin. Results obtained for the oxidation of myoglobin confirm this interpretation as do kinetic data for hemoglobin and myoglobin oxidations by iron(III) and copper(II) complexes. The effects of organic phosphates on rates for hemoglobin oxidations are interpreted in terms of oxidation inhibition by molecular oxygen.
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The reaction of nitrite with deoxyHb requires a proton and formally requires nitrous acid, making it faster at low pH.
“By studying the same reaction using alkyl nitrites, which do not show a pH dependence in their reaction rates with deoxyHb, it was established that the reaction of nitrite requires a proton and thus formally requires nitrous acid (247, 248). This property also makes the reaction faster in low pH conditions.”
From Sources of Vascular Nitric Oxide and Reactive Oxygen Species and Their Regulation (2019) · cites this paper as [247]
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References 31 · Cited by 29
- Authors
- Doyle, M. P., LePoire, D. M., & Pickering, R. A.
- Affiliations
- Hope College (US)
- ORCID
- Doyle, M.P.
- Venue
- Journal of Biological Chemistry
- Publisher
- Elsevier BV
- Published
- 1981-12
- Volume
- 256
- Issue
- 23
- Pages
- 12399-12404
- ISSN
- 0021-9258 (ISSN-L)
- OpenAlex
- W1594855139
- Cited by
- 29
- References
- 31
- Citations by year
- 2023: 1 · 2018: 2 · 2015: 1 · 2014: 1 · 2013: 5 · 2012: 1
- FWCI
- 0.51
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Journal of Biological Chemistry (publishedVersion, cc-by)
- PubMed (publishedVersion)
- Topics
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Cell Biology › Hemoglobin structure and function
- Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Catalyzed Oxygenation Mechanisms
- Health Sciences › Medicine › Surgery › Biomedical and Chemical Research
- Keywords
- hemoglobin oxidation, myoglobin oxidation, ethyl nitrite, alkyl nitrites, oxygen inhibition, oxygen dissociation, oxyhemoglobin, oxymyoglobin, deoxyhemoglobin, iron(III) complexes, copper(II) complexes, organic phosphates, reaction kinetics, molecular oxygen
- MeSH terms
- Hemoglobin A, Humans, Hydrogen-Ion Concentration, Kinetics, Methemoglobin, Nitrites, Oxygen, Oxyhemoglobins, Spectrophotometry
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