Iuliano, James N., Hall, Christopher, Green, Dale, Jones, Garth, Lukacs, Andras, Illarionov, Boris, Bacher, Adelbert, Fischer, M, French, Jarrod B., Tonge, Peter J. and Meech, Steve (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

PDF (Accepted_Manuscript) - Submitted Version Restricted to Repository staff only until 27 July 2021. Download (710kB) | Request a copy

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
Depositing User:	LivePure Connector
Date Deposited:	03 Sep 2020 23:56
Last Modified:	02 Dec 2020 00:47
URI:	https://ueaeprints.uea.ac.uk/id/eprint/76752
DOI:	10.1021/acs.jpcb.0c04943

Actions (login required)

View Item