Ab Initio Study of the Prototropic Tautomerism of Cytosine and Guanine and Their Contribution to Spontaneous Point Mutations
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High-level quantum-chemical and quantum-dynamics calculations are reported on the tautomerization equilibria and rate constants of isolated and monohydrated cytosine and guanine molecules. The results are used to estimate the fraction of the bases present in the cell during DNA synthesis as the unwanted tautomers that forms irregular base pairs, thus giving rise to a spontaneous GC → AT point mutation. A comparison of the estimated mutation frequencies with the observed frequency in E. coli is used to analyze two proposed mechanisms, differing in the degree of equilibration reached in the tautomerization reaction. It was found that the fraction of the rare tautomer in monohydrated complex of cytosine as well as guanine significantly exceed the amount responsible for the observed values of the GC → AT mutations. In the absence of water the equilibrium concentration of tautomeric forms is relatively large, but the barrier to their formation is high. It is possible that the mechanism in which a high tautomerization barrier keeps the tautomeric transformation far from a state of equilibrium is more likely than a mechanism in which water and/or polymerases produce a low equilibrium concentration of the tautomeric forms.
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Computational studies suggest that the monomeric form of the tautomers are stable and extremely long-lived due to their prohibitively large reaction barriers.
“On the other hand, computational studies suggest that the monomeric form of the tautomers are stable and extremely longlived due to their prohibitively large reaction barriers 4,13,48,49 .”
From An open quantum systems approach to proton tunnelling in DNA (2022) · cites this paper as [49]
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Cited by
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An open quantum systems approach to proton tunnelling in DNA
Slocombe, L., Sacchi, M., & Al-Khalili, J. (2022) · Communications Physics · doi:10.1038/s42005-022-00881-8 · Cited by 122 · see citing works
- Authors
- Podolyan, Y., Gorb, L., & Leszczynski, J.
- Affiliations
- Jackson State University (US)
- Computational Center for Molecular Structure and Interactions, Jackson State University, Department of Chemistry, 1325 J.R. Lynch St., Jackson, MS 39217-0510, USA
- ORCID
- Gorb, Leonid
- Venue
- International Journal of Molecular Sciences
- Publisher
- MDPI AG
- Published
- 2003-06-25
- Volume
- 4
- Issue
- 7
- Pages
- 410-421
- ISSN
- 1422-0067 (ISSN-L)
- OpenAlex
- W2120619739
- Cited by
- 101
- References
- 0
- Citations by year
- 2025: 5 · 2024: 3 · 2023: 2 · 2022: 5 · 2021: 4 · 2020: 1 · 2019: 6 · 2018: 6 · 2017: 4 · 2016: 2 · 2015: 6 · 2014: 3 · 2013: 3 · 2012: 6
- FWCI
- 1.62
- Type
- journal article
- Language
- en
- Open access
- gold
- doi.org
- Licence
- Locations
- International Journal of Molecular Sciences (publishedVersion, cc-by)
- DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
- Funders
- National Science Foundation (9805465)
- Office of Naval Research (N00014)
- Topics
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › DNA and Nucleic Acid Chemistry
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › RNA and protein synthesis mechanisms
- Keywords
- prototropic tautomerism, cytosine, guanine, DNA synthesis, Escherichia coli, tautomerization mechanism
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