Publication details
Excited-state hydrogen atom abstraction initiates the photochemistry of beta-2 '-deoxycytidine
| Authors | |
|---|---|
| Year of publication | 2015 |
| Type | Article in Periodical |
| Magazine / Source | CHEMICAL SCIENCE |
| MU Faculty or unit | |
| Citation | |
| Web | http://pubs.rsc.org/en/content/articlepdf/2015/SC/C4SC03761H |
| Doi | http://dx.doi.org/10.1039/c4sc03761h |
| Field | Physical chemistry and theoretical chemistry |
| Keywords | ULTRAFAST IR SPECTROSCOPY; CONICAL INTERSECTIONS; CYTOSINE DERIVATIVES; PREBIOTIC SYNTHESIS; BUILDING-BLOCKS; NUCLEIC-ACIDS; GAS-PHASE; DYNAMICS; NUCLEOSIDES; DNA |
| Description | 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 beta-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. |
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