18O isotope effect in the photosynthetic water splitting process

Abstract

In mass spectroscopic experiments of oxygen evolution in Photosystem II at 50% enrichment of H 2 18O, one expects equal signals of 18O 2 and 16O 2 unless one of the isotopes is favored by the oxygen evolving complex (OEC). We have observed a deviation from this expectation, being a clear indication of an isotope effect. We have measured the effect to be 1.14–1.30, which is higher than the theoretically predicted value of 1.014–1.06. This together with the strong temperature variation of the measured effect with a discontinuity at 11 °C observed for wild-type tobacco and at 9 °C for a yellow-green tobacco mutant suggest that an additional mechanism is responsible for the observed high isotope effect. The entry of a finite size of water clusters to the cleavage site of the OEC can explain the observation.