Abstract
The interaction between the Mn-cluster and its peripheral ligands in oxygen-evolving center is still unclear. Theoretical investigation on the coordination of histidine, H2O, and CI to Mn2O2 units in OEC is conducted. The following conclusions are obtained: (i) both histidine and H2O molecule, bound to the two Mn ions, respectively, are vertical to the Mn2O2 plane, and maintain a large distance; (ii) the two H2O molecules cannot bind to the same Mn2O2 unit. Based on Mn-cluster structure in OEC, we theoretically predict that two H2O molecules bind to the two Mn ions at the “C”-shaped open end in S0 state, while two His residues at the closed end. Cl ion can only terminally ligate at the open end. Individual valence for the four Mn ions in S0 state is assigned.
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Wild, A., Ball, R., Photosynthetic Unit and Photosystems, A Current View of the Photosynthetic Apparatus, Leiden: Backhugs Publishers, 1997, 127–153.
Debus, R. J., The manganese and calcium ions of photosynthetic oxygen evolution, Biochim. Biophys. Acta, 1992, 1102: 269.
Britt, R. D., Oxygen evolution, in Oxygenic Photosynthesis: The Light Reaction (eds. Ort, D. R., Yocum, C. F.), Dordrecht: Kluwer Academic Publishers, 1996, 137–164.
Rhee, K. H., Morris, E. P., Zheleva, D. et al., Two-dimensional structure of plant photosystem II at 8-Å resolution, Nature, 1997, 389: 522.
Yachandra, V. K., Sauer, K., Klein, M. P., Manganese cluster in photosynthesis: Where plants oxidize water to dioxygen, Chem. Rev, 1996, 96(7): 2927.
Schiller, H., Dittmer, J., Iuzzolino, L. et al., Structure and orientation of the oxygen-evolving manganese complex of green algae and higher plants investigated by X-ray absorption liner dichroism spectroscopy on oriented photosystem II membrane particles, Biochem., 1998, 37(20): 7340.
Chu, H. A., Nguyen, A. P., Debus, R. J., Amino acid residues that influence the binding of manganese or calcium to photosystem II—1. The lumenal interhelical domains of the D1 polypeptide, Biochem., 1995, 34(17): 5839.
Tang, X. S., Diner, B. A., Larsen, B. S. et al., Identification of histidine at the catalytic site of the photosynthetic oxygen-evolving complex, Proc. Natl. Acad. Sci. USA, 1994, 91: 704.
Magnuson, A., Andreasson, L. E., Different manganese binding sites in photosystem II probe by selective chemical modification of histidyl and carboxylic acid residues, Biochem., 1997, 36(11): 3254.
Ghirardi, M. L., Preston, C., Seibert, M., Use of a novel histidyl modifier to probe for residues on tris-treated photosystem II membrane fragments that may bind functional manganese, Biochem., 1998, 37(39): 13567.
Iuzzolino, L., Dittmer, J., Dorner, W. et al., X-ray absorption spectroscopy on layered photosystem II membrane particles suggests manganese-center oxidation of the oxygen-evolving complex for the S0-S1, S1-S2, S2-S3 transitions of the water oxidation cycle, Biochem., 1998, 37(49): 17112.
Hoganson, C. W., Babcock, G. T., A metallradical mechanism for the generation of oxygen from water in photosynthesis, Science, 1997, 277: 1953.
Renger, G., Mechanistic and structural aspects of photosynthetic water oxidation, Physiol. Plant., 1997, 100: 828.
Wincencjusz, H., Van Gorkom, H. J., Yocum, C. F., The photosynthetic oxygen evolving complex requires chloride for its redox state S2→S3 and S3→S0 transition but not for S0→S1 or S1→ S2 transition, Biochem., 1997, 36(12): 3663.
Proserpio, D. M., Rappe, A. K., Grorun, S. M., Theoretical modeling of the mechanism of dioxygen activation and evolution by tetranuclear manganese complexes, Inorg. Chim. Acta, 1993, 213: 319.
Siegbahn, P. E. M., Crabtree, R. H., Manganese oxyl radical intermediates and O-O bond formation in photosynthetic oxygen evolution and a proposed role for the calcium cofactor in photosystem II, J. Am. Chem. Soc, 1999, 121(1): 117.
Blankenship, R. E., Hartman, H., The origin and evolution of oxygenic photosynthesis, Trends in Biochem. Sciences, 1998, 23(3): 94.
Anangev, G. M., Dismukes, G. C., Calcium induces binding and formation of aspin-coupled dimanganese (II, II) center in the apo-water oxidation complex of photosystem II as precursor to the functional tetra Mn/Ca cluster, Biochem., 1997, 36(38): 11342.
Limburg, J., Vrettos, J. S., Liable-Sands, L. M. et al., A functional model for O-O bond formation by the O2-evolving complex in photosystem II, Science, 1999, 283: 1524.
Zhang, C. X., Fan, H. J., Li, L. B. et al., Theoretical study on primary reaction of photosynthetic bacteria, Science in China, Ser. C, 1999, 42(2): 155.
Messinger, J., Badger, M., Wydrzynski, T., Detection of one slowly exchanging substrate water molecule in the S3 state of photosystem II, Proc. Natl. Acad. Sci. USA, 1995, 92(8): 3209.
Hillier, W., Messinger, J., Wydrzynski, T., Kinetic determination of the fast exchanging substrate water molecule in the S3 state of photosystem II, Biochem., 1998, 37(48): 16908.
Boussac, A., Zimmermann, J. L., Rutherford, A. W. et al., Histidine oxidation in the oxygen-evolving photosystem-II enzyme, Nature, 1990, 347: 303.
Fernandez, C., Cinco, R., Robblee, J. et al., Calcium and chloride cofactors of O2 evolution-XAS evidence for a Mn/Ca/Cl heteronuclear cluster, in Photosynthesis: Mechanisms and Effects (ed. Garab, G.), Vol. 2, Dordrecht: Kluwer Academic Publishers, 1998, 1399–1402.
Roelofs, T. A., Liong, Q., Latimer, M. J. et al., Oxidation states of the manganese cluster during the flash-induced S-state cycle of the photosynthetic oxygen-evolving complex, Proc. Natl. Acad. Sci. USA, 1996, 93: 3335.
Åhrling, K. A., Peterson, S., Styring, S., An oscillating manganese electron paramagnetic resonance signal from the S0 state of the oxygen evolving complex in photosystem II, Biochem., 1997, 36(43): 13148.
Zhang, C. X., Pan, J., Li, L. B. et al., New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis, Chinese Science Bulletin, 1999, 44(22): 2209.
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Zhang, C., Pan, J., Li, L. et al. Theoretical investigation on peripheral ligands of oxygen-evolving center in photosystem II. Sci. China Ser. C.-Life Sci. 43, 337–346 (2000). https://doi.org/10.1007/BF02879297
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DOI: https://doi.org/10.1007/BF02879297