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Mapping the ultrafast dynamics of adenine onto its nucleotide and oligonucleotides by time-resolved photoelectron imaging.

Chatterley, A.S. and West, C.W. and Roberts, G.M. and Stavros, V.G. and Verlet, J.R.R. (2014) 'Mapping the ultrafast dynamics of adenine onto its nucleotide and oligonucleotides by time-resolved photoelectron imaging.', Journal of physical chemistry letters., 5 (5). pp. 843-848.


The intrinsic photophysics of nucleobases and nucleotides following UV absorption presents a key reductionist step toward understanding the complex photodamage mechanisms occurring in DNA. The decay mechanism of adenine in particular has been the focus of intense investigation, as has how these correlate to those of its more biologically relevant nucleotide and oligonucleotides in aqueous solution. Here, we report on time-resolved photoelectron imaging of the deprotonated 3′-deoxy-adenosine-5′-monophosphate nucleotide and the adenosine di- and trinucleotides. Through a comparison of gas- and solution-phase experiments and available theoretical studies, the dynamics of the base are shown to be relatively insensitive to the surrounding environment. The decay mechanism primarily involves internal conversion from the initially populated 1ππ* states to the ground state. The relaxation dynamics of the adenosine oligonucleotides are similar to those of the nucleobase, in contrast to the aqueous oligonucleotides, where a fraction of the ensemble forms long-lived excimer states.

Item Type:Article
Keywords:DNA damage, Excited-state dynamics, Anion photoelectron spectroscopy, Nonradiative decay, Photophysics, Conical intersections.
Full text:(AM) Accepted Manuscript
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Publisher statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Date accepted:11 February 2014
Date deposited:22 April 2014
Date of first online publication:11 February 2014
Date first made open access:No date available

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