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Molecules 2017, 22(1), 160; doi:10.3390/molecules22010160

Ultrafast Electronic Deactivation Dynamics of Xanthosine Monophosphate

1
Institute of Physical Chemistry, Christian-Albrechts-University Kiel, Olshausenstr. 40, 24098 Kiel, Germany
2
Centre for Process Innovation, Wilton Centre, Wilton, Redcar TS10 4RF, UK
Current address: TNG Technology Consulting GmbH, Betastraße 13a, 85774 Unterföhring, Germany.
*
Authors to whom correspondence should be addressed.
Academic Editor: Carlos E. Crespo-Hernández
Received: 30 November 2016 / Revised: 12 January 2017 / Accepted: 13 January 2017 / Published: 18 January 2017
(This article belongs to the Special Issue Experimental and Computational Photochemistry of Bioorganic Molecules)
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Abstract

Ultrafast energy dissipation is a crucial factor for the photostability of DNA and RNA, but even some of the key electronic deactivation pathways in monomeric nucleic acid building stones are still controversial. Here, we report on the excited-state dynamics of the rare nucleotide xanthosine monophosphate as a function of deprotonation state (XMP vs. XMP ) and excitation wavelength ( λ pump = 278–243 nm) by femtosecond time-resolved fluorescence and absorption spectroscopy. We show that the predominating relaxation channel leads to a return of the photo-excited molecules to the electronic ground state in τ∼1 ps. The mechanism likely involves an out-of-plane deformation of the five-membered ring, different from the main electronic deactivation pathways in the canonical purine bases adenine and guanine. The results are discussed in terms of the structural and electronic differences of XMP compared to the canonical nucleotides. View Full-Text
Keywords: biophysics; DNA; RNA; ultrafast photochemistry; xanthosine monophosphate; XMP; transient absorption; fluorescence up-conversion biophysics; DNA; RNA; ultrafast photochemistry; xanthosine monophosphate; XMP; transient absorption; fluorescence up-conversion
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Röttger, K.; Stellmacher, R.; Stuhldreier, M.C.; Temps, F. Ultrafast Electronic Deactivation Dynamics of Xanthosine Monophosphate. Molecules 2017, 22, 160.

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