Ion mobility action spectroscopy of flavin dianions reveals deprotomer-dependent photochemistry

Bull, James N., Carrascosa, Eduardo, Giacomozzi, Linda, Bieske, Evan J. and Stockett, Mark H. (2018) Ion mobility action spectroscopy of flavin dianions reveals deprotomer-dependent photochemistry. Physical Chemistry Chemical Physics, 20 (29). pp. 19672-19681. ISSN 1463-9076

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    Abstract

    The intrinsic optical properties and photochemistry of flavin adenine dinucleotide (FAD) dianions are investigated using a combination of tandem ion mobility spectrometry and action spectroscopy. Two principal isomers are observed, the more stable form being deprotonated on the isoalloxazine group and a phosphate (N-3,PO4 deprotomer), and the other on the two phosphates (PO4,PO4 deprotomer). Ion mobility data and electronic action spectra suggest that photo-induced proton transfer occurs from the isoalloxazine group to a phosphate group, converting the PO4,PO4 deprotomer to the N-3,PO4 deprotomer. Comparisons of the isomer selective action spectra of FAD dianions and flavin monoanions with solution spectra and gas-phase photodissociation action spectra suggests that solvation shifts the electronic absorption of the deprotonated isoalloxazine group to higher energy. This is interpreted as evidence for significant charge transfer in the lowest optical transition of deprotonated isoalloxazine. Overall, this work demonstrates that the site of deprotonation of flavin anions strongly affects their electronic absorptions and photochemistry.

    Item Type: Article
    Uncontrolled Keywords: physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100
    Faculty \ School: Faculty of Science > School of Chemistry
    Related URLs:
    Depositing User: LivePure Connector
    Date Deposited: 04 Feb 2019 13:30
    Last Modified: 10 Jul 2019 15:36
    URI: https://ueaeprints.uea.ac.uk/id/eprint/69831
    DOI: 10.1039/c8cp03244k

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