Photosynthetica 2009, 47(4):567-574 | DOI: 10.1007/s11099-009-0082-8

The reduced S-1 and S-2 oxidation states of the O2-evolving complex of photosystem II: An EPR microwave power saturation study

D. Koulougliotis1,*
1 Institute of Materials Science, NCSR "Democritos", Aghia Paraskevi Attikis, Athens, Greece

Progressive microwave power saturation (P1/2) measurements have been performed on the tyrosine D radical (YD *) of photosystem II (PSII) in order to examine its relaxation enhancement by the oxygen-evolving complex (OEC) poised to the reduced S-1 and S-2 oxidation states by NO treatment. Analysis of the power saturation curves showed that the S-1 oxidation state of the OEC does not enhance the relaxation of YD *: it therefore possesses a diamagnetic ground state. In contrast, the Mn(II)-Mn(III) multiline electron paramagnetic resonance (EPR) signal characteristic of the S-2 oxidation state of the OEC was shown to provide a relaxation enhancement pathway for YD *, however less efficient relative to the one provided by the S2-state multiline EPR signal. We also examined the YD * relaxation enhancement characteristics of the EPR-silent oxidation state produced after brief (1-5 min) dark incubation at 0°C of a PSII sample poised to the EPRactive S-2 state. This EPR-silent oxidation state denoted as "0°C incubation" state was shown to possess remarkably similar P1/2 values with the EPR-active S-2 state in the overall examined temperature range (6-20 K). In addition, these values remained unchanged after successive cycles of the OEC between the EPR-active S-2 state and the "0°C incubation" state. The data presented in this work point to the conclusion that the "0°C incubation" state is indeed an S-2 oxidation state with half-integer spin.

Additional key words: oxygen-evolving complex; photosystem II; power saturation; reduced S-states

Received: May 22, 2009; Accepted: November 11, 2009; Published: December 1, 2009  Show citation

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Koulougliotis, D. (2009). The reduced S-1 and S-2 oxidation states of the O2-evolving complex of photosystem II: An EPR microwave power saturation study. Photosynthetica, 47(4), 567-574. doi: 10.1007/s11099-009-0082-8
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