High-field EPR Spectroscopy on Proteins and Their Model Systems Characterization of Transient Paramagnetic States

Preface. Acknowledgements. Chapter 1. Introduction: Why EPR at high magnetic fields?-- NMR versus EPR-- From basic EPR to pulsed multi-frequency spectroscopy at high magnetic fields, a chronological account. Chapter 2. Principles and illustrative examples of high-field/high-frequency EPR spectroscopy: Spin Hamiltonians and EPR experiments at high magnetic fields-- Organic radicals and low-spin transition metal ions (S=1/2)-- Triplet states and high-spin transition-metal ions (S>1/2)-- High-field EPR, ENDOR, TRIPLE, ESEEM, RIDME and PELDOR experiments-- Electron-nuclear hyperfine spectroscopy-- Liquid-solution steady-state ENDOR and TRIPLE-- Liquid phase ENDOR intensities and lineshapes-- TRIPLE resonance as an extension of ENDOR-- ENDOR in liquid crystals-- Porphyrinoid and chlorophyll ions-- Liquid-solution transient EPR and ENDOR in photochemistry-- CIDEP mechanisms in photochemical reactions-- Triplet mechanism (TM)-- Radical-pair mechanism (RPM)-- Spin-correlated radical pair mechanism (CCRP)-- CIDEP-enhanced ENDOR-- Transient intermediates in light-induced reactions-- Introduction-- Photochemical reactions in liquid solution, illustrative examples-- The compound 2,2-dimethoxy-1,2-diphenylethan-1-one-- The compound 2,4,6 trimethylbenzoyl-diphenyl-phosphine-oxide-- Solid-state pulse ENDOR and TRIPLE-- Systems without quadrupole interaction-- Systems with quadrupole interaction-- ESEEM hyperfine spectroscopy-- Electron-electron dipolar spectroscopy-- PELDOR-- RIDME. Chapter 3. Instrumentation: Introduction-- Time-resolved cw EPR techniques-- Pulsed EPR techniques-- Survey of high-field/high-frequency EPR spectrometers-- Historical overview of high-field/high-frequency EPR spectrometers-- Overview of laboratory-built and commercial spectrometers-- High-field multi-purpose spectrometers built at FU Berlin-- The 95-GHz spectrometer-- System description-- Probeheads-- Field-jump PELDOR-- Two-frequency PELDOR-- ENDOR-- The 360-GHz spectrometer-- Quasi-optical microwave propagation-- System description-- Pulsed orotron source-- Probeheads-- ENDOR. Chapter 4. Computational methods for data interpretation. Chapter 5. Applications of high-field EPR on selected proteins and their model systems: Introduction-- Non-oxygenic photosynthesis-- Multifrequency EPR on bacterial photosynthetic reaction centres (RCs)-- X-band EPR and ENDOR experiments-- 95-GHz EPR on primary donor cations P?+ in single-crystal RCs-- 360-GHz EPR on primary donor cations P?+ in mutant RCs-- Results of g-tensor computations of P?+-- 95-GHz EPR and ENDOR on the acceptors QA?- and QB?-- 95-GHz ESE-detected EPR on spin-correlated radical pairs P?+QA?-- 95-GHz RIDME and PELDOR on spin-correlated radical pairs P?+QA?-- Multifrequency EPR on primary donor triplet states in RCs-- Multifrequency EPR on bacteriorhodopsin (BR)-- Site-directed nitroxide spin labelling-- Hydrophobic barrier of the BR proton-transfer channel-- Modelling of solute-solvent interactions-- Conformational changes during the BR photocycle-- Distance and orientation measurements in spin-labelled proteins: Intoduction, High-field PELDOR and RIDME on nitroxide biradicals-- Oxygenic photosynthesis-- Multifrequency EPR on doublet states in Photosystem I (PS I)-- Multifrequency EPR on doublet states in Photosystem II (PS II)-- Multifrequency EPR on triplet states in antenna complexes, PS I, PS II-- Photoinduced electron transfer in biomimetic donor-acceptor model systems-- Introduction-- Covalently linked porphyrin-quinone dyad and triad model systems-- Base-paired porphyrin-quinone and -dinitrobenzene complexes-- DNA repair Photolyases-- Introduction-- High-field EPR and ENDOR experiments-- Colicin A bacterial toxin-- Introduction-- Models of transmembrane ion-channel formation-- 95-GHz EPR studies of membrane insertion. Chapter 6. Conclusions and perspectives. Chapter 7. References.