Is UV-Induced Electron-Driven Proton Transfer Active in a Chemically Modified A•T DNA Base Pair?

Autor: Arsène F. M. Chemin, Hugo J. B. Marroux, M. Carmen Galan, Thomas A. A. Oliver, Andrew J. Orr-Ewing, Steven T. G. Street, Gareth M. Roberts, Katharina Röttger, Alexander S. Henderson, Emma Elsdon
Jazyk: angličtina
Rok vydání: 2017
Předmět:
Zdroj: Roettger, K, Marroux, H, Chemin, A, Elsdon, E, Oliver, T A A, Street, S, Henderson, A S J, Galan, C, Orr-Ewing, A & Roberts, G 2017, ' Is UV-Induced Electron-Driven Proton Transfer Active in a Chemically Modified A•T DNA Base Pair? ', Journal of Physical Chemistry B, vol. 121, no. 17, pp. 4448-4455 . https://doi.org/10.1021/acs.jpcb.7b02679
The Journal of Physical Chemistry B
Popis: Transient electronic and vibrational absorption spectroscopies have been used to investigate whether UV-induced electron-driven proton transfer (EDPT) mechanisms are active in a chemically modified adenine-thymine (A·T) DNA base pair. To enhance the fraction of biologically relevant Watson-Crick (WC) hydrogen-bonding motifs and eliminate undesired Hoogsteen structures, a chemically modified derivative of A was synthesized, 8-(tert-butyl)-9-ethyladenine (8tBA). Equimolar solutions of 8tBA and silyl-protected T nucleosides in chloroform yield a mixture of WC pairs, reverse WC pairs, and residual monomers. Unlike previous transient absorption studies of WC guanine-cytosine (G·C) pairs, no clear spectroscopic or kinetic evidence was identified for the participation of EDPT in the excited-state relaxation dynamics of 8tBA·T pairs, although ultrafast (sub-100 fs) EDPT cannot be discounted. Monomer-like dynamics are proposed to dominate in 8tBA·T.
Databáze: OpenAIRE