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Ultrafast ring closing of a diarylethene-based photoswitchable nucleoside

Deoxyuridine nucleosides embodied into diarylethenes form an especial class of photoswitchable compounds that are designed to stack and pair with DNA bases. The molecular geometry can be switched between “open” and “closed” isomers by a pericyclic reaction that affects the stability of the surroundi...

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Bibliographic Details
Main Authors: Li, Yang (Author) , Pérez Lustres, José Luis (Author) , Volpp, Hans-Robert (Author) , Buckup, Tiago (Author) , Kolmar, Theresa (Author) , Jäschke, Andres (Author) , Motzkus, Marcus (Author)
Format: Article (Journal)
Language:English
Published: [2018]
In: Physical chemistry, chemical physics
Year: 2018, Volume: 20, Issue: 35, Pages: 22867-22876
ISSN:1463-9084
DOI:10.1039/C8CP03549K
Online Access:Verlag, Volltext: https://doi.org/10.1039/C8CP03549K
Verlag, Volltext: https://pubs.rsc.org/en/content/articlelanding/2018/cp/c8cp03549k
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Author Notes:Yang Li, J. Luis Pérez Lustres, Hans-Robert Volpp, Tiago Buckup, Theresa Kolmar, Andres Jäschke, Marcus Motzkus
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Summary:Deoxyuridine nucleosides embodied into diarylethenes form an especial class of photoswitchable compounds that are designed to stack and pair with DNA bases. The molecular geometry can be switched between “open” and “closed” isomers by a pericyclic reaction that affects the stability of the surrounding double helix. This potentially enables light-induced control of DNA hybridization at microscopic resolution. Despite its importance for the optimization of DNA photoswitches, the ultrafast photoisomerization mechanism of these diarylethenes is still not well understood. In this work, femtosecond transient absorption spectroscopy is applied to study the ring closing reaction upon UV excitation with 45 fs pulses. Excited-state absorption decays rapidly and gives rise to the UV-Vis difference spectrum of the “closed” form within ≈15 ps. Time constants of 0.09, 0.49 and 6.6 ps characterize the multimodal dynamics, where a swift recurrence in the signal anisotropy indicates transient population of the intermediate 21A—like state.
Item Description:Gesehen am 11.02.2020
Physical Description:Online Resource
ISSN:1463-9084
DOI:10.1039/C8CP03549K

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