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

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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.

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

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Publication details

The article was received on 22 May 2018, accepted on 09 Jul 2018 and first published on 09 Jul 2018


Article type: Paper
DOI: 10.1039/C8CP03244K
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
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    Ion mobility action spectroscopy of flavin dianions reveals deprotomer-dependent photochemistry

    J. N. Bull, E. Carrascosa, L. Giacomozzi, E. J. Bieske and M. H. Stockett, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP03244K

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