Excited state vibrations of isotopically labeled FMN free and bound to a light–oxygen–voltage (LOV) protein

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Iuliano, James N., Hall, Christopher, Green, Dale ORCID: https://orcid.org/0000-0002-2549-0486, Jones, Garth, Lukacs, Andras, Illarionov, Boris, Bacher, Adelbert, Fischer, M, French, Jarrod B., Tonge, Peter J. and Meech, Steve ORCID: https://orcid.org/0000-0001-5561-2782 (2020) Excited state vibrations of isotopically labeled FMN free and bound to a light–oxygen–voltage (LOV) protein. Journal of Physical Chemistry B, 124 (33). 7152–7165. ISSN 1520-6106

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Abstract

Flavoproteins are important blue light sensors in photobiology and play a key role in optogenetics. The characterization of their excited state structure and dynamics is thus an important objective. Here, we present a detailed study of excited state vibrational spectra of flavin mononucleotide (FMN), in solution and bound to the LOV-2 (Light-Oxygen-Voltage) domain of Avena sativa phototropin. Vibrational frequencies are determined for the optically excited singlet state and the reactive triplet state, through resonant ultrafast femtosecond stimulated Raman spectroscopy (FSRS). To assign the observed spectra, vibrational frequencies of the excited states are calculated using density functional theory, and both measurement and theory are applied to four different isotopologues of FMN. Excited state mode assignments are refined in both states, and their sensitivity to deuteration and protein environment are investigated. We show that resonant FSRS provides a useful tool for characterizing photoactive flavoproteins and is able to highlight chromophore localized modes and to record hydrogen/deuterium exchange.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User: LivePure Connector
Date Deposited: 03 Sep 2020 23:56
Last Modified: 09 Feb 2023 13:48
URI: https://ueaeprints.uea.ac.uk/id/eprint/76752
DOI: 10.1021/acs.jpcb.0c04943

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