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Experimental and theoretical study of the cytosine tautomerism through excited states

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Abstract 

Context

The irradiation of water solution of cytosine with UV light (λmax = 254 nm) shows oxo-hydroxy tautomerism with a rate constant of 6.297 × 10−3 min−1. The order of the reaction implies a tautomeric conversion. After removing the UV light source, we observed a dark reaction with a rate constant of 1.473 × 10−3 min−1 which leads to a restoration of the initial tautomer as before the irradiation. The mechanism of oxo-hydroxy tautomerism of cytosine in water solution was studied in the excited state. It was found that the transformations occur along the 1πσ* excited-state reaction paths which link the Franck–Condon geometries of the tautomers and the conical intersections S0/S1 connected with the H-detachment processes of the corresponding bonds. Furthermore, we established that the conical intersections S0/S1 are also mutually accessible along the 1πσ* excited-state reaction paths.

Methods

The ground-state equilibrium geometries were optimized at the B3LYP/aug-cc-pVDZ level of theory in water environment according to PCM as well as at the CC2/aug-cc-pVDZ level in the gas phase. The TD B3LYP and CC2 methods were applied for the study of the excited states. The tautomerization mechanisms were studied with the use of the linear interpolation in internal coordinates approach using the optimized geometries of tautomers minima and conical intersections S0/S1 at the CASSCF(6,6)/6-31G* level. All calculations were performed with the GAUSSIAN 16 commercial software.

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

We would like to thank the Bulgarian National Science Fund for the financial support of the research in the frames of the project No КP-06-N59/7. The authors gratefully acknowledge also (i) the Department of Scientific Research at the University of Plovdiv for administrating the project and (ii) the provided access to the e-infrastructure of the NCHDC â part of the Bulgarian National Roadmap on RIs, with the financial support by the Grant No D01-168/28.07.2022.

Funding

This work was supported by the Bulgarian National Science Fund, project No КP-06-N59/7.

Bulgarian National Science Fund,КP-06-N59/7,КP-06-N59/7,КP-06-N59/7,КP-06-N59/7,КP-06-N59/7,КP-06-N59/7

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Authors and Affiliations

  1. Faculty of Chemistry, University of Plovdiv, Tzar Assen 24 Str, 4000, Plovdiv, Bulgaria

    Tsvetina D. Cherneva, Mina M. Todorova, Rumyana I. Bakalska & Vassil B. Delchev

  2. Department of Inorganic and Physical Chemistry, University of Food Technologies, 4002, Plovdiv, Bulgaria

    Ivan G. Shterev

  3. Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9, 1060, Vienna, Austria

    Ernst Horkel

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  1. Tsvetina D. Cherneva
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  2. Mina M. Todorova
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  3. Rumyana I. Bakalska
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  4. Ivan G. Shterev
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  6. Vassil B. Delchev
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Contributions

Vassil Delchev and Ernst Horkel gave the idea of the research. Tsvertina Cherneva, Vassil Delchev, Ivan Shterev, and Ernst Horkel performed the calculations and simulations. Rumyana Bakalska, Mina Todorova, and Tsvetina Cherneva performed the experiments with the irradiation and analysis of the experimental spectra. All authors read and approved the manuscript.

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Correspondence to Vassil B. Delchev.

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Cherneva, T.D., Todorova, M.M., Bakalska, R.I. et al. Experimental and theoretical study of the cytosine tautomerism through excited states. J Mol Model 29, 303 (2023). https://doi.org/10.1007/s00894-023-05707-0

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