Ultrafast transient mid IR to visible spectroscopy of fully reduced flavins

Zhao, Rui-Kun, Lukacs, Andras, Haigney, Allison, Brust, Richard, Greetham, Gregory M., Towrie, Michael, Tonge, Peter J. and Meech, Stephen R. ORCID: https://orcid.org/0000-0001-5561-2782 (2011) Ultrafast transient mid IR to visible spectroscopy of fully reduced flavins. Physical Chemistry Chemical Physics, 13 (39). pp. 17642-17648. ISSN 1463-9076

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Abstract

The light sensing apparatus of many organisms includes a flavoprotein. In any spectroscopic analysis of the photocycle of flavoproteins a detailed knowledge of the spectroscopy and excited state dynamics of potential intermediates is required. Here we correlate transient vibrational and electronic spectra of the two fully reduced forms of flavin adenine dinucleotide (FAD): FADH- and FADH2. Ground and excited state frequencies of the characteristic carbonyl modes are observed and assigned with the aid of DFT calculations. Excited state decay and ground state recovery dynamics of the two states are reported. Excited state decay occurs on the picosecond timescale, in agreement with the low fluorescence yield, and is markedly non single exponential in FADH-. Further, an unusual ‘inverse’ isotope effect is observed in the decay time of FADH-, suggesting the involvement in the radiationless relaxation coordinate of an NH or hydrogen bond mode that strengthens in the excited electronic state. Ground state recovery also occurs on the picosecond time scale, consistent with radiationless decay by internal conversion, but is slower than the excited state decay.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry
UEA Research Groups:	Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Physical and Analytical Chemistry (former - to 2017) Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User:	Users 2731 not found.
Date Deposited:	18 Jan 2012 10:41
Last Modified:	09 Feb 2023 13:34
URI:	https://ueaeprints.uea.ac.uk/id/eprint/36233
DOI:	10.1039/c1cp22097g

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