Skip to main page content
Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2011 Oct 21;13(39):17642-8.
doi: 10.1039/c1cp22097g. Epub 2011 Sep 1.

Ultrafast Transient Mid IR to Visible Spectroscopy of Fully Reduced Flavins

Affiliations

Ultrafast Transient Mid IR to Visible Spectroscopy of Fully Reduced Flavins

Rui-Kun Zhao et al. Phys Chem Chem Phys. .

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 FADH(2). 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.

Similar articles

See all similar articles

Cited by 1 article

Publication types

Substances

LinkOut - more resources

Feedback