Catalytic Mechanism of Fatty Acid Photodecarboxylase: On the Detection and Stability of the Initial Carbonyloxy Radical Intermediate.
In: Angewandte Chemie, Jg. 136 (2024-05-06), Heft 19, S. 1-5
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Zugriff:
In fatty acid photodecarboxylase (FAP), light‐induced formation of the primary radical product RCOO⋅ from fatty acid RCOO− occurs in 300 ps, upon which CO2 is released quasi‐immediately. Based on the hypothesis that aliphatic RCOO⋅ (spectroscopically uncharacterized because unstable) absorbs in the red similarly to aromatic carbonyloxy radicals such as 2,6‐dichlorobenzoyloxy radical (DCB⋅), much longer‐lived linear RCOO⋅ has been suggested recently. We performed quantum chemical reaction pathway and spectral calculations. These calculations are in line with the experimental DCB⋅ decarboxylation dynamics and spectral properties and show that in contrast to DCB⋅, aliphatic RCOO⋅ radicals a) decarboxylate with a very low energetic barrier and on the timescale of a few ps and b) exhibit little red absorption. A time‐resolved infrared spectroscopy experiment confirms very rapid, ≪300 ps RCOO⋅ decarboxylation in FAP. We argue that this property is required for the observed high quantum yield of hydrocarbons formation by FAP. [ABSTRACT FROM AUTHOR]
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Catalytic Mechanism of Fatty Acid Photodecarboxylase: On the Detection and Stability of the Initial Carbonyloxy Radical Intermediate.
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Autor/in / Beteiligte Person: | Aleksandrov, Alexey ; Bonvalet, Adeline ; Müller, Pavel ; Sorigué, Damien ; Beisson, Fred ; Antonucci, Laura ; Solinas, Xavier ; Joffre, Manuel ; Vos, Marten H. |
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Zeitschrift: | Angewandte Chemie, Jg. 136 (2024-05-06), Heft 19, S. 1-5 |
Veröffentlichung: | 2024 |
Medientyp: | academicJournal |
ISSN: | 0044-8249 (print) |
DOI: | 10.1002/ange.202401376 |
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