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Investigating the ultrafast dynamics and long-term photostability of an isomer pair, Usujirene and Palythene, from the Mycosporine-like amino acid family
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Whittock, Abigail L., Woolley, Jack Matthew, Auckloo, Nazia, Corre, Christophe and Stavros, Vasilios G. (2022) Investigating the ultrafast dynamics and long-term photostability of an isomer pair, Usujirene and Palythene, from the Mycosporine-like amino acid family. Molecules, 27 (7). 2272. doi:10.3390/molecules27072272 ISSN 1420-3049.
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Official URL: http://dx.doi.org/10.3390/molecules27072272
Abstract
Mycosporine-like amino acids are a prevalent form of photoprotection in micro- and macro-organisms. Using a combination of natural product extraction/purification and femtosecond transient absorption spectroscopy, we studied the relaxation pathway for a common mycosporine-like amino acid pair, usujirene and its geometric isomer palythene, in the first few nanoseconds following photoexcitation. Our studies show that the electronic excited state lifetimes of these molecules persist for only a few hundred femtoseconds before the excited state population is funneled through an energetically accessible conical intersection with subsequent vibrational energy transfer to the solvent. We found that a minor portion of the isomer pair did not recover to their original state within 3 ns after photoexcitation. We investigated the long-term photostability using continuous irradiation at a single wavelength and with a solar simulator to mimic a more real-life environment; high levels of photostability were observed in both experiments. Finally, we employed computational methods to elucidate the photochemical and photophysical properties of usujirene and palythene as well as to reconcile the photoprotective mechanism.
Item Type: | Journal Article | |||||||||||||||
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Subjects: | Q Science > QD Chemistry Q Science > QR Microbiology |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||
Library of Congress Subject Headings (LCSH): | Mycosporine-like amino acids, Spectrum analysis, Photochemistry | |||||||||||||||
Journal or Publication Title: | Molecules | |||||||||||||||
Publisher: | MDPI | |||||||||||||||
ISSN: | 1420-3049 | |||||||||||||||
Official Date: | April 2022 | |||||||||||||||
Dates: |
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Volume: | 27 | |||||||||||||||
Number: | 7 | |||||||||||||||
Article Number: | 2272 | |||||||||||||||
DOI: | 10.3390/molecules27072272 | |||||||||||||||
Status: | Peer Reviewed | |||||||||||||||
Publication Status: | Published | |||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||
Date of first compliant deposit: | 5 April 2022 | |||||||||||||||
Date of first compliant Open Access: | 5 April 2022 | |||||||||||||||
RIOXX Funder/Project Grant: |
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