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High-Field/High-Frequency Electron Paramagnetic Resonance Involving Single- and Multiple-Transition Schemes

  • Chapter
Biophysical Techniques in Photosynthesis

Part of the book series: Advances in Photosynthesis and Respiration ((AIPH,volume 26))

During the last decade a tremendous growth in the combined efforts of biologists, chemists and physicists to understand the dominant factors determining the specifi city and directionality of transmembrane transfer processes in photosynthetic proteins has been observed. Among the large variety of experimental techniques used in these efforts, electron paramagnetic resonance (EPR) spectroscopy at high magnetic fi elds turned out to be particularly powerful. In conjunction with site-specifi c mutation strategies and advanced quantum-chemical computation methods for data interpretation in terms of protein structure and dynamics, new insights in biological processes have been have been obtained at the atomic and molecular levels. In this chapter, a few large paradigmatic biosystems from photosynthesis are surveyed as examples which have been explored lately by high-frequency/high-fi eld EPR techniques. Taking advantage of the improved spectral and temporal resolution of EPR at 95 GHz/3.4 T and 360 GHz/12.9 T, as compared to conventional X-band EPR (9.5 GHz/0.34 T), the proteins are characterized with respect to electronic properties, structure and dynamics. In this chapter, the following protein systems are primarily discussed: (1) In non-oxygenic photosynthesis, light-induced electrontransfer intermediates in wild-type and mutant reaction centers from photosynthetic bacteria as well as lightdriven proton-transfer intermediates of site-specifi cally nitroxide spin-labeled mutants of bacteriorhodopsin proteins, (2) in oxygenic photosynthesis, specifi c cofactors of the electron-transfer chains in Photosystem I and Photosystem II. The information obtained is complementary to that of protein crystallography, solid-state NMR, infrared and optical spectroscopy techniques. In addition, a few multifrequency EPR experiments on biomimetic donor-acceptor model systems are reviewed. As a unique strength, high-fi eld EPR can probe structure and dynamics of transient intermediates of proteins while staying in their working states on biologically relevant time scales. The chapter describes the underlying strategies for extending conventional EPR to high-field/high-frequency techniques, and highlights those aspects of structure-dynamics-function relations that are revealed from combining high-fi eld EPR with genetic engineering techniques to study site-specifi c mutants. The importance of DFT-based quantum-chemical interpretation of the experimental data (g, zero-fi eldsplitting and hyperfi ne tensors) is emphasized. The chapter concludes with a summary of specifi c advantages of high-field EPR and an outlook to major challenges this type of magnetic resonance spectroscopy faces in protein research.

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  1. Department of Physics, Free University Berlin, Arnimallee 14, 14195, Berlin, Germany

    Klaus Möbius

  2. Department of Chemical Physics, Weizmann Institute of Science, 76100, Rehovot, Israel

    Daniella Goldfarb

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Möbius, K., Goldfarb, D. (2008). High-Field/High-Frequency Electron Paramagnetic Resonance Involving Single- and Multiple-Transition Schemes. In: Aartsma, T.J., Matysik, J. (eds) Biophysical Techniques in Photosynthesis. Advances in Photosynthesis and Respiration, vol 26. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8250-4_14

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