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Direct structural observation of ultrafast photoisomerization dynamics in sinapate esters
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Abiola, Temitope T., Toldo, Josene M., do Casal, Mariana T., Flourat, Amandine L., Rioux, Benjamin, Woolley, Jack Matthew, Murdock, Daniel, Allais, Florent, Barbatti, Mario and Stavros, Vasilios G. (2022) Direct structural observation of ultrafast photoisomerization dynamics in sinapate esters. Communications Chemistry, 5 (1). 141. doi:10.1038/s42004-022-00757-6 ISSN 2399-3669.
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Official URL: https://doi.org/10.1038/s42004-022-00757-6
Abstract
Sinapate esters have been extensively studied for their potential application in ‘nature-inspired’ photoprotection. There is general consensus that the relaxation mechanism of sinapate esters following photoexcitation with ultraviolet radiation is mediated by geometric isomerization. This has been largely inferred through indirect studies involving transient electronic absorption spectroscopy in conjunction with steady-state spectroscopies. However, to-date, there is no direct experimental evidence tracking the formation of the photoisomer in real-time. Using transient vibrational absorption spectroscopy, we report on the direct structural changes that occur upon photoexcitation, resulting in the photoisomer formation. Our mechanistic analysis predicts that, from the photoprepared ππ* state, internal conversion takes place through a conical intersection (CI) near the geometry of the initial isomer. Our calculations suggest that different CI topographies at relevant points on the seam of intersection may influence the isomerization yield. Altogether, we provide compelling evidence suggesting that a sinapate ester’s geometric isomerization can be a more complex dynamical process than originally thought.
Item Type: | Journal Article | |||||||||||||||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||||||||
SWORD Depositor: | Library Publications Router | |||||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Photoisomerization, Sunscreens (Cosmetics), Photochemistry | |||||||||||||||||||||
Journal or Publication Title: | Communications Chemistry | |||||||||||||||||||||
Publisher: | Nature Publishing Group UK | |||||||||||||||||||||
ISSN: | 2399-3669 | |||||||||||||||||||||
Official Date: | 31 October 2022 | |||||||||||||||||||||
Dates: |
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Volume: | 5 | |||||||||||||||||||||
Number: | 1 | |||||||||||||||||||||
Article Number: | 141 | |||||||||||||||||||||
DOI: | 10.1038/s42004-022-00757-6 | |||||||||||||||||||||
Status: | Peer Reviewed | |||||||||||||||||||||
Publication Status: | Published | |||||||||||||||||||||
Reuse Statement (publisher, data, author rights): | ** From Springer Nature via Jisc Publications Router ** History: received 12-08-2022; accepted 13-10-2022; registration 14-10-2022; pub-electronic 31-10-2022; online 31-10-2022; collection 12-2022. ** Licence for this article: http://creativecommons.org/licenses/by/4.0/ ** Acknowledgements: Acknowledgements: The authors acknowledge the FET-Open grant BoostCrop (Grant agreement 828753) and the Warwick Centre for Ultrafast Spectroscopy (WCUS) for the use of transient vibrational absorption spectroscopy (TVAS) and Fluorolog 3 apparatus. T.T.A. thanks the University of Warwick for a Ph.D. studentship through the Chancellor Scholarship. J.M.T., M.T.do.C. and M.B. acknowledge Centre de Calcul Intensif d’Aix-Marseille for granting access to its high-performance computing resources. This work was granted access to the HPC resources of TGCC under the allocation 2021-A0110813035 made by GENCI. B.R., A.L.F and F.A. thank the Agence Nationale de la Recherche (grant number ANR-17-CE07-0046), as well as the Grand Reims, Conseil Départemental de la Marne, and the Grand Est region for financial support. V.G.S. thanks the Royal Society for a Royal Society Industry Fellowship. The authors thank Dr Michael Grubb for guidance on the use of KOALA, suggestions and for proof reading. The authors thank Dr. Natércia d. N. Rodrigues and Ana González Moreno for proof reading. | |||||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||||||||
Date of first compliant deposit: | 24 November 2022 | |||||||||||||||||||||
Date of first compliant Open Access: | 24 November 2022 | |||||||||||||||||||||
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