Ml. Gilchrist et al., PROXIMITY OF THE MANGANESE CLUSTER OF PHOTOSYSTEM-II TO THE REDOX-ACTIVE TYROSINE Y-Z, Proceedings of the National Academy of Sciences of the United Statesof America, 92(21), 1995, pp. 9545-9549
Electron spin echo electron-nuclear double resonance (ESE-ENDOR) exper
iments performed on a broad radical electron paramagnetic resonance (E
PR) signal observed in photosystem II particles depleted of Ca2+ indic
ate that this signal arises from the redox-active tyrosine Y-Z. The ty
rosine EPR signal width is increased relative to that observed in a ma
nganese-depleted preparation due to a magnetic interaction between the
photosystem II manganese cluster and the tyrosine radical. The mangan
ese cluster is located asymmetrically with respect to the symmetry-rel
ated tyrosines Y-Z and Y-D. The distance between the Y-Z tyrosine and
the manganese cluster is estimated to be approximately 4.5 Angstrom. D
ue to this close proximity of the Mn cluster and the redox-active tyro
sine Y-Z, we propose that this tyrosine abstracts protons from substra
te water bound to the Mn cluster.