Analysis of the electronic asymmetry of the primary electron donor of photosystem I of <i>Spirodela oligorrhiza</i> by photo-CIDNP solid-state NMR

The electron donor in photosystem I, the chlorophyll dimer P700, is studied by photo-CIDNP (photochemically induced dynamic nuclear polarization) MAS (magic-angle spinning) NMR on selectively 13C and uniformly 15N labeled PSI core preparations (PSI-100) obtained from the aquatic plant duckweed (Spirodela oligorrhiza). Light-induced signals originate from the isotope labelled nuclei of the cofactors involved in the spin-correlated radical pair forming upon light excitation. Signals are assigned to the two donor cofactors (Chl a and Chl a') and the two acceptor cofactors (both Chl a). Light induced signals originating from both donor and acceptor cofactors demonstrate that electron transfer occurs through both branches of cofactors in the pseudo-C2 symmetric Reaction Center (RC). The experimental results supported by quantum chemical calculations indicate that this functional symmetry occurs in PSI despite similarly sized chemical-shift differences between cofactors of PSI and the functionally asymmetric special-pair donor of the bacterial RC of Rhodobacter sphaeroides. This contributes to converging evidence that local differences in time-averaged electronic ground-state properties, over the donor are of little importance for functional symmetry breaking across photosynthetic RC species.