bi6b00543_si_002.pdb (204.21 kB)
Ammonia Binding in the Second Coordination Sphere of the Oxygen-Evolving Complex of Photosystem II
dataset
posted on 2016-07-19, 00:00 authored by David
J. Vinyard, Mikhail Askerka, Richard J. Debus, Victor S. Batista, Gary W. BrudvigAmmonia 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 S2 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 S2 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.