Abstract
The origin of the extraordinary high redox potential of P680, the primary electron donor of Photosystem II, is still unknown. Photochemically induced dynamic nuclear polarisation (photo-CIDNP) 13C magic-angle spinning (MAS) NMR is a powerful method to study primary electron donors. In order to reveal the electronic structure of P680, we compare new photo-CIDNP MAS NMR data of Photosystem II to those of Photosystem I. The comparison reveals that the electronic structure of the P680 radical cation is a Chl a cofactor with strong matrix interaction, while the radical cation of P700, the primary electon donor of Photosystem I, appears to be a Chl a cofactor which is essentially undisturbed. Possible forms of cofactor–matrix interactions are discussed.
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Abbreviations
- Chl:
-
chlorophyll
- CSA:
-
chemical shift anisotropy
- DD:
-
differential decay
- ENDOR:
-
electron nuclear double resonance
- EPR:
-
electron paramagnetic resonance
- FTIR:
-
Fourier transform infrared
- hf:
-
hyperfine
- HOMO:
-
highest occupied molecular orbital
- LUMO:
-
lowest unoccupied molecular orbital
- MAS:
-
magic angle spinning
- photo-CIDNP:
-
photochemically induced dynamic nuclear polarisation
- PS I, II:
-
Photosystems I, II
- TSM:
-
three-spin mixing
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Diller, A., Alia, Roy, E. et al. Photo-CIDNP solid-state NMR on Photosystems I and II:what makes P680 special?. Photosynth Res 84, 303–308 (2005). https://doi.org/10.1007/s11120-005-0411-0
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DOI: https://doi.org/10.1007/s11120-005-0411-0