Ammonia Binding in the Second Coordination Sphere of the Oxygen-Evolving Complex of Photosystem II

作者：Vinyard David J; Askerka Mikhail; Debus Richard J; Batista Victor S; Brudvig Gary W

来源：Biochemistry, 2016, 55(31): 4432-4436.

DOI：10.1021/acs.biochem.6b00543

Ammonia binds to two sites in the oxygen evolving complex (OEC) of Photosystem II (PSII). The first is as a terminal ligand to Mn in the S-2 state, and the second is at a site outside the OEC that is competitive with chloride. Binding of ammonia in this latter secondary site results in the S-2 state S = 5/2 spin isomer being favored over the S = 1/2 spin isomer. Using electron paramagnetic resonance spectroscopy, we find that ammonia binds to the secondary site in wild-type Synechocystis sp. PCC 6803 PSII, but not in D2-K317A mutated PSII that does not bind chloride. By combining these results with quantum mechanics/molecular mechanics-calculations, we propose that ammonia binds in the secondary site in competition with D1-D61 as a hydrogen bond acceptor to the OEC terminal Water ligand, W1. Implications for the mechanism of ammonia binding via its primary site directly to Mn4 in the OEC are discussed.

• 出版日期2016-8-9