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Ultrafast electronic deactivation dynamics of the inosine dimer — a model case for H-bonded purine bases

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Abstract

The structural properties and ultrafast electronic deactivation dynamics of the inosine dimer in CHCl3 have been investigated by two-dimensional 1H NMR and static FTIR spectroscopy and by femtosecond time-resolved transient absorption spectroscopy, respectively. The 1H NMR and IR spectra show the formation of a well-defined, symmetric dimer with an association equilibrium constant of KI·I = 690 ± 100 M-1. The excited-state dynamics after photoexcitation at λpump = 260 nm monitored by ultrafast absorption spectroscopy show great similarity with those of the monomer inosine in an aqueous solution and are governed by a decay time of t = 90 ± 10 fs, which is one of the shortest electronic lifetimes of all nucleobases and nucleobase dimers studied so far. On the basis of these observations, the inosine dimer is expected to follow a similar relaxation pathway as the monomer, involving an out-of-plane deformation of the six-membered ring. The importance of the C(2) position for the electronic deactivation of hypoxanthine and guanine is discussed. The obtained well-determined structure and straightforward dynamics qualify the inosine dimer as an excellent reference case for more complicated systems such as the G·G dimer and the G·C and A·T Watson-Crick pairs.

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Authors and Affiliations

  1. Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstr. 40, D-24098, Kiel, Germany

    Katharina Röttger & Friedrich Temps

  2. Otto Diels-Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, D-24118, Kiel, Germany

    Frank D. Sönnichsen

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  1. Katharina Röttger
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  2. Frank D. Sönnichsen
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Röttger, K., Sönnichsen, F.D. & Temps, F. Ultrafast electronic deactivation dynamics of the inosine dimer — a model case for H-bonded purine bases. Photochem Photobiol Sci 12, 1466–1473 (2013). https://doi.org/10.1039/c3pp50093d

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