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Search for intermediates of photosynthetic water oxidation

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Abstract

Photosystem II of cyanobacteria and plants incorporates the catalytic centre of water oxidation. Powered and clocked by quanta of light the centre accumulates four oxidising equivalents before oxygen is released. The first three oxidising equivalents are stored on the Mn4Ca-cluster, raising its formal oxidation state from S0 to S3 and the third on YZ, producing S3 YZox. From there on water oxidation proceeds in what appears as a single reaction step (S3 YZox(H2O)2O2 + 4H+ + S0. Intermediate oxidation products of bound water had not been detected, until our recent report on the stabilisation of such an intermediate by high oxygen pressure (NATURE 430, 2004, 480–483). Based on the oxygen titration (half-point 2.3 bar) the standard free-energy profile of a reaction sequence with a single intermediate was calculated. It revealed a rather small difference (−3 kJ mol−1) between the starting state [S3YZOX and the product state S0YZ + O2 + 4H+ . Here we describe the tests for side effects of exposing core particles to high oxygen pressure. We found the reduction of P680+ · in ns and the reduction/dismutation of quinones at the acceptor side of PSII both unaffected, and the inhibition of the oxygen evolving reaction by exposure to high O2-pressure was fully reversible by decompression to atmospheric conditions.

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Abbreviations

β-D- M:

n-dodecylβ-D-maltoside

Chl:

chlorophyll

D1, D2:

core subunits of Photosystem II

ET:

electron transfer

DCBQ:

2,5-dichloro-p-benzoquinone

FWHM:

full width at half maximum

MES:

2-(N-morpholino)-ethanesulfonic acid

OEC:

oxygen evolving complex

P680:

primary electron donor of PS II

PS II:

Photosystem II

QA, QB:

bound quinone acceptors in PS II

Si, (i = 0 - 4):

redox states of the catalytic centre

YZ:

redox-active tyrosine-161 of D1

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  1. Biophysik, Universität Osnabrück, 49069, Osnabrück, Germany

    Juergen Clausen & Wolfgang Junge

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  1. Juergen Clausen
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  2. Wolfgang Junge
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Correspondence to Wolfgang Junge.

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Clausen, J., Junge, W. Search for intermediates of photosynthetic water oxidation. Photosynth Res 84, 339–345 (2005). https://doi.org/10.1007/s11120-005-3480-1

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