Issue 3, 2015

Excited-state hydrogen atom abstraction initiates the photochemistry of β-2′-deoxycytidine

Abstract

Understanding the effects of ultraviolet radiation on nucleotides in solution is an important step towards a comprehensive description of the photochemistry of nucleic acids and their constituents. Apart from having implications for mutagenesis and DNA photoprotection mechanisms, the photochemistry of cytidines is a central element in UV-assisted syntheses of pyrimidine nucleotides under prebiotically plausible conditions. In this contribution, we present UV-irradiation experiments of β-2′-deoxycytidine in aqueous solution involving H–D exchange followed by NMR spectroscopic analysis of the photoproducts. We further elucidate the outcome of these experiments by means of high-level quantum chemical calculations. In particular, we show that prolonged UV-irradiation of cytidine may lead to H–C1′ hydrogen atom abstraction by the carbonyl oxygen atom of cytosine. This process may enable photoanomerisation and nucleobase loss, two previously unexplained photoreactions observed in pyrimidine nucleotides.

Graphical abstract: Excited-state hydrogen atom abstraction initiates the photochemistry of β-2′-deoxycytidine

Supplementary files

Article information

Article type
Edge Article
Submitted
04 12 2014
Accepted
07 1 2015
First published
07 1 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 2035-2043

Author version available

Excited-state hydrogen atom abstraction initiates the photochemistry of β-2′-deoxycytidine

R. Szabla, J. Campos, J. E. Šponer, J. Šponer, R. W. Góra and J. D. Sutherland, Chem. Sci., 2015, 6, 2035 DOI: 10.1039/C4SC03761H

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