Nitrosation, thiols, and hemoglobin: energetics and kinetics
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Nitrosothiols are powerful vasodilators. Although the mechanism of their formation near neutral pH is an area of intense research, neither the energetics nor the kinetics of this reaction or of subsequent reactions have been addressed. The following considerations may help to guide experiments. (1) The standard Gibbs energy for the homolysis reaction RSNO → RS(•) + NO(•)(aq) is +110 ± 5 kJ mol(-1). (2) The electrode potential of the RSNO, H(+)/RSH, NO(•)(aq) couple is -0.20 ± 0.06 V at pH 7. (3) Thiol nitrosation by NO(2)(-) is favorable by 37 ± 5 kJ mol(-1) at pH 7. (4) N(2)O(3) is not involved in in vivo nitrosation mechanisms for thermodynamic--its formation from NO(2)(-) costs 59 kJ mol(-1)--or kinetic--the reaction being second-order in NO(2)(-)--reasons. (5) Hemoglobin (Hb) cannot catalyze formation of N(2)O(3), be it via the intermediacy of the reaction of Hb[FeNO(2)](2+) with NO(•) (+81 kJ mol(-1)) or reaction of Hb[FeNO](3+) with NO(2)(-) (+88 kJ mol(-1)). (6) Energetically and kinetically viable are nitrosations that involve HNO(2) or NO(•) in the presence of an electron acceptor with an electrode potential higher than -0.20 V. These considerations are derived from existing thermochemical and kinetics data.
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Others have questioned whether N2O3 can and does form.
“However, others have questioned whether this species can and does form [100, 101].”
From Mechanisms of nitrite bioactivation (2014) · cites this paper as [101]
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- Authors
- Koppenol, W. H.
- Affiliations
- ETH Zurich (CH)
- Corresponding author
- Koppenol, Willem H.
- ORCID
- Koppenol, Willem H.
- Venue
- Inorganic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-05-03
- Volume
- 51
- Issue
- 10
- Pages
- 5637-5641
- ISSN
- 0020-1669 (ISSN-L)
- 1520-510X
- PMC
- PMC3357094
- OpenAlex
- W130077361
- Cited by
- 54
- References
- 50
- Citations by year
- 2025: 2 · 2024: 1 · 2023: 2 · 2021: 1 · 2020: 4 · 2019: 1 · 2018: 3 · 2017: 8 · 2016: 8 · 2015: 5 · 2014: 8 · 2013: 8 · 2012: 3
- FWCI
- 5.14
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Inorganic Chemistry (publishedVersion, other-oa)
- Europe PMC (PubMed Central) (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Health Sciences › Medicine › Physiology › Nitric Oxide and Endothelin Effects
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Cell Biology › Hemoglobin structure and function
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Redox biology and oxidative stress
- Keywords
- S-nitrosothiols, nitric oxide, nitrite, nitrous acid, dinitrogen trioxide, hemoglobin, homolysis, Gibbs free energy, electrode potential, reaction kinetics, vasodilators, electron transfer
- MeSH terms
- Hemoglobins, Kinetics, Nitrates, Nitric Oxide, Nitrogen Oxides, Sulfhydryl Compounds, Thermodynamics, Vasodilator Agents, Nitrosation
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