Mapping the Ultrafast Dynamics of Adenine onto Its Nucleotide and Oligonucleotides by Time-Resolved Photoelectron Imaging

Chatterley, A.S.; West, C.W.; Roberts, G.M.; Stavros, V.G.; Verlet, J.R.R.

doi:10.1021/jz500264c

Mapping the Ultrafast Dynamics of Adenine onto Its Nucleotide and Oligonucleotides by Time-Resolved Photoelectron Imaging

Chatterley, A.S.; West, C.W.; Roberts, G.M.; Stavros, V.G.; Verlet, J.R.R.

Authors

A.S. Chatterley

C.W. West

G.M. Roberts

V.G. Stavros

Professor Jan Verlet j.r.r.verlet@durham.ac.uk
Head Of Department

Abstract

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.

Citation

Chatterley, A., West, C., Roberts, G., Stavros, V., & Verlet, J. (2014). Mapping the Ultrafast Dynamics of Adenine onto Its Nucleotide and Oligonucleotides by Time-Resolved Photoelectron Imaging. Journal of Physical Chemistry Letters, 5(5), 843-848. https://doi.org/10.1021/jz500264c

Journal Article Type	Article
Acceptance Date	Feb 11, 2014
Online Publication Date	Feb 11, 2014
Publication Date	Mar 6, 2014
Deposit Date	Apr 15, 2014
Publicly Available Date	Apr 22, 2014
Journal	Journal of Physical Chemistry Letters
Electronic ISSN	1948-7185
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	5
Issue	5
Pages	843-848
DOI	https://doi.org/10.1021/jz500264c
Keywords	DNA damage, Excited-state dynamics, Anion photoelectron spectroscopy, Nonradiative decay, Photophysics, Conical intersections.
Public URL	https://durham-repository.worktribe.com/output/1434527

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Copyright 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 http://pubs.acs.org/doi/abs/10.1021/jz500264c.