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

James N Bull; Eduardo Carrascosa; Linda Giacomozzi; Evan J Bieske; Mark H Stockett

Journal article

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

James N Bull, Eduardo Carrascosa, Linda Giacomozzi, Evan J Bieske, Mark H Stockett

Physical Chemistry Chemical Physics | Royal Society of Chemistry | Published : 2018

DOI: 10.1039/c8cp03244k

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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 s..

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University of Melbourne Researchers

Evan Bieske Author

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Grants

Awarded by Swedish Research Council

Awarded by Australian Research Council Discovery Project scheme

Awarded by Austrian Science Fund (FWF) through a Schrodinger Fellowship

Funding Acknowledgements

The authors thank Steen Brondsted Nielsen, for the use of the SepI instrument, and Lars H Andersen, for supplying the FAD sample, both at Aarhus University (Department of Physics and Astronomy). LG thanks Henning Zettergren of Stockholm University for travel support. This work was supported by the Swedish Research Council (grant numbers 2016-03675 and 2016-04181) and the Australian Research Council Discovery Project scheme (DP150101427 and DP160100474). JNB acknowledges resources from the Australian National Computational Infrastructure (NCI) through Early Career Allocation ya1 and a Microsoft Azure Research Award. EC acknowledges support by the Austrian Science Fund (FWF) through a Schrodinger Fellowship (No. J4013-N36).