Abstract

Hotly debated issues in the area of biological electron transfer (ET) involve questions of how long-range ET processes proceed along pathways that incorporate non-covalently linked cofactors interacting with their protein microenvironment. To contribute answers to such questions, time-resolved EPR (TREPR) experiments at various microwave frequency/magnetic field settings have been performed. In this overview, representative examples of this work from our laboratory are given which comprise transient intermediates of light-induced ET in (i) bacterial photosynthetic reaction centers and (ii) biomimetic model complexes. In these complexes the donor and acceptor components are tethered together either covalently via cyclohexenyl bridges or non-covalently via Watson-Crick base-pairing. The studies are aiming at broadening our knowledge of structure-dynamics-function relationships associated with ET processes. It is demonstrated that high-field TREPR opens new perspectives in elucidating complex photochemical ET reactions with different paramagnetic states and species involved.

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