Abstract
Flash-induced absorption changes in the Soret region arising from the [PD1PD2]+ state, the chlorophyll cation radical formed upon light excitation of Photosystem II (PSII), were measured in Mn-depleted PSII cores at pH 8.6. Under these conditions, TyrD is i) reduced before the first flash, and ii) oxidized before subsequent flashes. In wild-type PSII, when TyrD● is present, an additional signal in the [PD1PD2]+-minus-[PD1PD2] difference spectrum was observed when compared to the first flash when TyrD is not oxidized. The additional feature was “W-shaped” with troughs at 434 nm and 446 nm. This feature was absent when TyrD was reduced, but was present (i) when TyrD was physically absent (and replaced by phenylalanine) or (ii) when its H-bonding histidine (D2-His189) was physically absent (replaced by a Leucine). Thus, the simple difference spectrum without the double trough feature at 434 nm and 446 nm, seemed to require the native structural environment around the reduced TyrD and its H bonding partners to be present. We found no evidence of involvement of PD1, ChlD1, PheD1, PheD2, TyrZ, and the Cytb559 heme in the W-shaped difference spectrum. However, the use of a mutant of the PD2 axial His ligand, the D2-His197Ala, shows that the PD2 environment seems involved in the formation of “W-shaped” signal.
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Abbreviations
- Chl:
-
Chlorophyll
- ChlD1/ChlD2 :
-
Monomeric Chl on the D1 or D2 side, respectively
- Cyt:
-
Cytochrome
- DMSO:
-
Dimethyl sulfoxide
- EPR:
-
Electron Paramagnetic Resonance
- PD1 and PD2 :
-
Individual Chl on the D1 or D2 side, respectively, which constitute a pair of Chl with partially overlapping aromatic rings (P680)
- PheD1 and PheD2 :
-
Pheophytin on the D1 or D2 side, respectively
- PPBQ:
-
Phenyl p–benzoquinone
- PSII:
-
Photosystem II
- QA :
-
Primary quinone acceptor
- QB :
-
Secondary quinone acceptor
- TyrD :
-
The tyrosine 160 of D2 acting as a side-path electron donor of PSII
- TyrZ :
-
The tyrosine 161 of D1 acting as the electron donor to P680
- WT*3:
-
T. elongatus Mutant strain deleted of the psbA1 and psbA2 genes and with a His-tag on the carboxy terminus of CP43
- WT’:
-
T. elongatus Mutant strain deleted of the psbA1, psbA2 and psbD2 genes and with a His-tag on the carboxy terminus of CP43
- EDTA:
-
Ethylenediaminetetraacetic acid
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Acknowledgements
This work has been in part supported by (i) the French Infrastructure for Integrated Structural Biology (FRISBI) ANR-10-INBS-05, (ii) the Labex Dynamo (ANR-11-LABX-0011-01), (iii) the JSPS-KAKENHI Grant in Scientific Research on Innovative Areas JP17H064351 and a JSPS-KAKENHI Grant 21H02447 and (iv) the BBSRC grants BB/R001383/1, BB/V002015/1 and BB/R00921X. Adjélé Wilson is thanked for her advice on breaking Synechocystis cells using the French press.
Funding
Agence Nationale de la Recherche, ANR-10-INBS-05,ANR-11-LABX-0011-01, Japan Society for the Promotion of Science, JP17H064351, Biotechnology and Biological Sciences Research Council, BB/R001383/1.
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AB designed and performed experiments, wrote the main text, did the figures. MS designed and performed experiments and reviewed the manuscript. MN did some mutants. RN did a mutant. TN did a mutant. SV designed and performed experiments and reviewed the manuscript. AWR reviewed the manuscript. JS performed experiments and reviewed the manuscript.
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Boussac, A., Sugiura, M., Nakamura, M. et al. Absorption changes in Photosystem II in the Soret band region upon the formation of the chlorophyll cation radical [PD1PD2]+. Photosynth Res (2023). https://doi.org/10.1007/s11120-023-01049-3
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DOI: https://doi.org/10.1007/s11120-023-01049-3