Redirecting electron transfer in photosystem II from water to redox-active metal complexes |
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Authors: | Ulas Gözde Brudvig Gary W |
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Institution: | Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, United States. |
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Abstract: | A negatively charged region on the surface of photosystem II (PSII) near Q(A) has been identified as a docking site for cationic exogenous electron acceptors. Oxygen evolution activity, which is inhibited in the presence of the herbicide 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), is recovered by adding Co(III) complexes. Thus, a new electron-transfer pathway is created with Co(III) as the new terminal electron acceptor from Q(A)(-). This binding site is saturated at ~2.5 mM Co(III)], which is consistent with the existence of low-affinity interactions with a solvent-exposed surface. This is the first example of a higher plant PSII in which the electron-transfer pathway has been redirected from the normal membrane-associated quinone electron acceptors to water-soluble electron acceptors. The proposed Co(III) binding site may enable efficient collection of electrons generated from photochemical water oxidation by PSII immobilized on an electrode surface. |
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