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Photo-induced proton-coupled electron transfer and dissociation of isolated flavin adenine dinucleotide mono-anions

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Abstract

The intrinsic optical absorption spectrum and photo-dissociation pathways of flavin adenine dinucleotide (FAD) mono-anions isolated in vacuo are probed using photo-induced dissociation (PID) action spectroscopy. The main photo-products are lumichrome and formylmethylflavin. Evidence is presented that the dissociation pathway leading to these products is non-statistical i.e. occurs during the excited state lifetime. This suggests that the stacking of the adenine and alloxazine chromophores, which enables ultra-fast quenching of the flavin excited state by photo-induced electron transfer in aqueous solution, is inhibited in vacuo. These results provide firm experimental confirmation that lumichrome formation from flavins proceeds via photo-induced, intra-molecular proton-coupled electron transfer.

Graphical abstract: Photo-induced proton-coupled electron transfer and dissociation of isolated flavin adenine dinucleotide mono-anions

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Publication details

The article was received on 16 Jun 2017, accepted on 19 Jul 2017 and first published on 20 Jul 2017


Article type: Communication
DOI: 10.1039/C7CP04068G
Citation: Phys. Chem. Chem. Phys., 2017, Advance Article
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    Photo-induced proton-coupled electron transfer and dissociation of isolated flavin adenine dinucleotide mono-anions

    M. H. Stockett, Phys. Chem. Chem. Phys., 2017, Advance Article , DOI: 10.1039/C7CP04068G

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