Abstract
Current technical and methodical advances in electron paramagnetic resonance (EPR) spectroscopy have proven to be very beneficial for studies of stationary and short-lived paramagnetic states in proteins carrying organic cofactors. In particular, the large number of proteins with flavins as prosthetic groups can be examined splendidly by EPR in all its flavors. To understand how a flavin molecule can be fine-tuned for specific catalysis of different reactions, understanding of its electronic structure mediated by subtle protein-cofactor interactions is of utmost importance. The focus of this chapter is the description of recent research progress from our laboratory on EPR of photoactive flavoproteins. These catalyze a wide variety of important photobiological processes ranging from enzymatic DNA repair to plant phototropism and animal magnetoreception. Whereas increasing structural information on the principal architecture of photoactive flavoproteins is available to date, their primary photochemistry is still largely undetermined. Interestingly, although these proteins carry the same light-active flavin chromophore, their light-driven reactions differ significantly: Formations of photoexcited triplet states and short-lived radical pairs starting out from triplet or singlet-state precursors, as well as generation of stationary radicals have been reported recently. EPR spectroscopy is the method of choice to characterize such paramagnetic intermediates, and hence, to assist in unravelling the mechanisms of these inimitable proteins.
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Acknowledgements
We thank our colleagues, collaborators, and coworkers, who contributed substantially over the past 10 years to the work that is reviewed here: Adelbert Bacher (Technical University Munich), Alfred Batschauer (University of Marburg), Till Biskup (Oxford University), Robert Bittl (Free University Berlin), Richard Brosi (Free University Berlin), Lars-Oliver Essen (University of Marburg), Markus Fischer (University of Hamburg), Martin Fuchs (SLS, Paul-Scherrer-Institute Villigen), Elizabeth D. Getzoff (Scripps Research Institute, La Jolla), Peter Hegemann (Humboldt-University of Berlin), Kenichi Hitomi (Scripps Research Institute, La Jolla), Boris Illarionov (University of Hamburg), Sylwia Kacprzak (University of Freiburg), Chris Kay (University College London), Radoslaw Kowalczyk (University of Surrey, UK), Anthony R. Marino (University of Chicago), Tilo Mathes (Humbolt-University of Berlin), Klaus Möbius (Fee University Berlin), James R. Norris (University of Chicago), Asako Okafuji, Gerald Richter (Cardiff University), Alexander Schnegg (Free University Berlin), and Takeshi Todo (Osaka University). This work was supported by the Deutsche Forschungsgemeinschaft (DFG We 2376/3-1).
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Schleicher, E., Weber, S. (2011). Radicals in Flavoproteins. In: Drescher, M., Jeschke, G. (eds) EPR Spectroscopy. Topics in Current Chemistry, vol 321. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2011_301
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