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Location of the High-Affinity Mn(2+) Site in Photosystem II Detected by PELDOR.

The location of the high-affinity Mn(2+) site in apo-photosystem (PS) II was investigated by pulsed EPR. The electron-electron magnetic dipole interaction of 1.7 MHz between the YD(•) radical and Mn(2+) ion was observed using the pulsed electron-electron double resonance (PELDOR) technique, and the Mn(2+) ion was bound to one apo-PS II in the absence and presence of Ca(2+). PELDOR signals were calculated using the previously determined spin distribution on the YD(•) radical and its known position in the crystal structure, assuming that the specific Mn(2+) site was located in the oxygen evolving complex. The results show that the high-affinity Mn(2+) site is located at the position denoted by Mn4(A) in the native crystal structure. The Mn(2+) is coordinated with axial ligands Asp170 and Glu333 in the D1 polypeptide.