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Absorption and luminescence spectroscopy of mass-selected flavin adenine dinucleotide mono-anions
Stockholm University, Faculty of Science, Department of Physics.
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Number of Authors: 62018 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 148, no 21, article id 214309Article in journal (Refereed) Published
Abstract [en]

We report the absorption profile of isolated Flavin Adenine Dinucleotide (FAD) mono-anions recorded using photo-induced dissociation action spectroscopy. In this charge state, one of the phosphoric acid groups is deprotonated and the chromophore itself is in its neutral oxidized state. These measurements cover the first four optical transitions of FAD with excitation energies from 2.3 to 6.0 eV (210-550 nm). The S-0 -> S-2 transition is strongly blue shifted relative to aqueous solution, supporting the view that this transition has a significant charge-transfer character. The remaining bands are close to their solution-phase positions. This confirms that the large discrepancy between quantum chemical calculations of vertical transition energies and solution-phase band maxima cannot be explained by solvent effects. We also report the luminescence spectrum of FAD mono-anions in vacuo. The gas-phase Stokes shift for S-1 is 3000 cm(-1), which is considerably larger than any previously reported for other molecular ions and consistent with a significant displacement of the ground and excited state potential energy surfaces. Consideration of the vibronic structure is thus essential for simulating the absorption and luminescence spectra of flavins.

Place, publisher, year, edition, pages
2018. Vol. 148, no 21, article id 214309
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Physical Sciences
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URN: urn:nbn:se:su:diva-158273DOI: 10.1063/1.5024028ISI: 000434837600018PubMedID: 29884035OAI: oai:DiVA.org:su-158273DiVA, id: diva2:1236601
Available from: 2018-08-03 Created: 2018-08-03 Last updated: 2018-08-03Bibliographically approved

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Giacomozzi, LindaStockett, Mark H.
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