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Ammonia binds to the manganese site of the O/sub 2/-evolving complex of photosystem II in the S/sub 2/ state

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00274a027· OSTI ID:5454976
In this paper, the authors have used low-temperature EPR spectroscopy to monitor the structure and magnetic properties of the Mn site in the presence of NH/sub 3/. They first address the effects on the S/sub 2/ state EPR signal caused by changing the pH from 6.0 to 7.5, since the previous studies were performed at pH 6.0. Next, they demonstrate that binding of NH/sub 3/ to the O/sub 2/-evolving complex causes large changes in the S/sub 2/ state multiline EPR signal trapped after illumination at 0/sup 0/C, indicating that NH/sub 3/ probably binds directly to the MN site in the S/sub 2/ state. However, NH/sub 3/ does not perturb that S/sub 2/ state EPR signal if the S/sub 2/ state is produced by illumination at 210 K, a temperature at which ligand exchange is inefficient. These results demonstrate that coordination of NH/sub 3/ to the Mn site occurs after formation of the S/sub 2/ state. The findings provide direct spectroscopic evidence that the Mn site of the O/sub 2/-evolving complex exchanges ligands, which suggests that the Mn site binds substrate H/sub 2/O molecules during the turnover of the O/sub 2/-evolving complex.
Research Organization:
Yale Univ., New Haven, CT
OSTI ID:
5454976
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:14; ISSN JACSA
Country of Publication:
United States
Language:
English

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