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The Catalytic Manganese Cluster: Protein Ligation

  • Chapter
Photosystem II

Part of the book series: Advances in Photosynthesis and Respiration ((AIPH,volume 22))

Summary

Water oxidation in Photosystem II (PS II) takes place under severe constraints. Because little surplus free energy is available, the midpoint potential of the (Mn)4 cluster must be tightly controlled to prevent it from increasing substantially as oxidizing equivalents are accumulated. In addition, the release of toxic, highly reactive intermediates of water oxidation must be minimized. To operate under these constraints, the reactivity of the (Mn)4-Ca2+-YZ complex is carefully controlled by its protein environment. This chapter describes the site-directed mutagenesis studies that have been undertaken to identify the amino acid residues that are responsible for this control. These residues include those that ligate the Mn and Ca2+ ions and those that influence the electron and proton transfer reactions of YZ and the (Mn)4-Ca2+ metal cluster. Most characterizations relied initially on non-invasive methods that were conducted in vivo. With improved methods for purifying PS II, characterizations increasingly involve newer developments in magnetic resonance, vibrational, and optical absorption spectroscopy. On the basis of the mutagenesis studies that are described in this chapter, possible ligands of the (Mn)4 cluster were proposed to include D1-Asp170, D1-His332, D1-Glu333, D1-His337 and D1-Asp342, plus the carboxyl-terminus of the D1 polypeptide at D1-Ala344. Possible ligands of the Ca2+ ion were proposed to include D1-Asp59, D1-Asp61 and D1-Asp342. In addition, D1-Glu189 was proposed to participate in a network of hydrogen bonds that facilitates electron transfer from the (Mn)4 cluster to YZ• during the higher S state transitions and D1-His190 was proposed to serve as the proton acceptor for YZ. The recent 3.2 Å and 3.5 Å X-ray crystallographic structural models of PS II support some of these proposals, but conflict with others, most notably the ligation of Ca2+ and the roles of D1-Glu189 and, in the 3.5 Å structural model, the role of the carboxyl-terminus of the D1 polypeptide. Two surprising aspects of the structural models are that one Mn ion is ligated by both D1-Asp170 and D1-Glu333 and another is ligated by both D1-Glu189 and D1-His332. The properties of the D1-Asp170 and D1-Glu333 mutants differ markedly, as do the properties of the D1-Glu189 and D1-His332 mutants. The main points of agreement and disagreement between the mutagenesis studies and the recent X-ray crystallographic structural models are discussed.

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Authors and Affiliations

  1. Department of Biochemistry, University of California-Riverside, Riverside, CA, 92521-0129, USA

    Richard J. Debus

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  1. Richard J. Debus
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  1. The Australian National University, Canberra, Australia

    Thomas J. Wydrzynski

  2. Okayama University, Okayama, Japan

    Kimiyuki Satoh

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Debus, R.J. (2005). The Catalytic Manganese Cluster: Protein Ligation. In: Wydrzynski, T.J., Satoh, K., Freeman, J.A. (eds) Photosystem II. Advances in Photosynthesis and Respiration, vol 22. Springer, Dordrecht. https://doi.org/10.1007/1-4020-4254-X_12

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