QM/MM Study of the Formation of the Dioxetanone Ring in Fireflies through a Superoxide Ion

The bioluminescence emission from fireflies is an astounding tool to mark and view cells. However, the bioluminescent mechanism is not completely deciphered, limiting the comprehension of key processes. We use a theoretical approach to study for the first time the arrival of a dioxygen molecule insi...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2018-05, Vol.122 (20), p.5173-5182
Main Authors: Berraud-Pache, Romain, Lindh, Roland, Navizet, Isabelle
Format: Article
Language:English
Subjects:
Chemical Sciences
or physical chemistry
Theoretical and
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Summary:The bioluminescence emission from fireflies is an astounding tool to mark and view cells. However, the bioluminescent mechanism is not completely deciphered, limiting the comprehension of key processes. We use a theoretical approach to study for the first time the arrival of a dioxygen molecule inside the fireflies protein and one path of the formation of the dioxetanone ring, the high-energy intermediate precursor of the bioluminescence. To describe this reaction step, a joint approach combining classical molecular dynamics (MD) simulations and hybrid quantum mechanics/molecular mechanics (QM/MM) calculations is used. The formation of the dioxetanone ring has been studied for both singlet and triplet states with the help of MS-CASPT2 calculations. We also emphasize the role played by the proteinic environment in the formation of the dioxetanone ring. The results obtained shed some light on an important reaction step and give new insights concerning the bioluminescence in fireflies.
ISSN:1520-6106
1520-5207
1520-5207
DOI:10.1021/acs.jpcb.8b00642