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Shining light on the electronic structure and relaxation dynamics of the isolated oxyluciferin anion

Patel, AM; Henley, A; Parkes, MA; Assmann, M; Worth, GA; Anderson, JC; Fielding, HH; (2020) Shining light on the electronic structure and relaxation dynamics of the isolated oxyluciferin anion. Physical Chemistry Chemical Physics 10.1039/d0cp03276j. (In press). Green open access

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Abstract

Firefly bioluminescence is exploited widely in imaging in the biochemical and biomedical sciences; however, our fundamental understanding of the electronic structure and relaxation processes of the oxyluciferin that emits the light is still rudimentary. Here, we employ photoelectron spectroscopy and quantum chemistry calculations to investigate the electronic structure and relaxation of a series of model oxyluciferin anions. We find that changing the deprotonation site has a dramatic influence on the relaxation pathway following photoexcitation of higher lying electronically excited states. The keto form of the oxyluciferin anion is found to undergo internal conversion to the fluorescent S1 state, whereas we find evidence to suggest that the enol and enolate forms undergo internal conversion to a dipole bound state, possibly via the fluorescent S1 state. Partially resolved vibrational structure points towards the involvement of out-of-plane torsional motions in internal conversion to the dipole bound state, emphasising the combined electronic and structural role that the microenvironment plays in controlling the electronic relaxation pathway in the enzyme.

Type: Article
Title: Shining light on the electronic structure and relaxation dynamics of the isolated oxyluciferin anion
Location: England
Open access status: An open access version is available from UCL Discovery
DOI: 10.1039/d0cp03276j
Publisher version: https://doi.org/10.1039/D0CP03276J
Language: English
Additional information: © the Owner Societies 2020. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10108116
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