Volume 127, 2004

Strickler–Berg analysis of excited singlet state dynamics in DNA and RNA nucleosides

Abstract

The excited singlet state lifetime of the ribonucleoside uridine was found to be 210 ± 30 fs by femtosecond transient absorption spectroscopy. This value is considerably shorter than all previous time-domain measurements. This result and our previous lifetime measurements [see J.-M. L. Pecourt, J. Peon and B. Kohler, J. Am. Chem. Soc., 2001, 123, 10 370] for the other common nucleosides are compared with lifetimes calculated from available photophysical data using the Strickler–Berg (SB) equation. The calculated lifetimes for pyrimidine nucleosides are 10–25% lower than the lifetimes measured in femtosecond transient absorption experiments. For the purine nucleosides, guanosine and adenosine, consideration of just the lowest 1π → π* transition led to predicted lifetimes that are three times greater than experimental ones. On the other hand, inclusion of both of the lowest energy 1π → π* absorption bands in the SB equation resulted in much better agreement with the experimental values. This suggests that both 1ππ* states of the purine nucleosides contribute to their emission. Decay by the bright 1ππ* state (or states, in the case of the purines) is believed to be responsible for the experimentally observed lifetimes.

Article information

Article type
Paper
Submitted
24 Dec 2003
Accepted
12 Jan 2004
First published
27 May 2004

Faraday Discuss., 2004,127, 137-147

Strickler–Berg analysis of excited singlet state dynamics in DNA and RNA nucleosides

B. Cohen, C. E. Crespo-Hernández and B. Kohler, Faraday Discuss., 2004, 127, 137 DOI: 10.1039/B316939A

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