Oxygen-evolving Center Of Photosystem Research Articles

Modeling magnetic interactions in high-valent trinuclear [Mn3(IV)O4]4+ complexes through highly compressed multi-configurational wave functions.

In this work we apply a quantum chemical framework, recently designed in our laboratories, to rationalize the low-energy electronic spectrum and the magnetic properties of an homo-valent trinuclear [Mn3(IV)O4]4+ model of the oxygen-evolving center in photosystem II. The method is based on chemically motivated molecular orbital unitary transformations, and the optimization of spin-adapted many-body wave functions, both for ground- and excited-states, in the transformed MO basis. In this basis, the configuration interaction Hamiltonian matrix of exchange-coupled multi-center clusters is extremely sparse and characterized by a unique block diagonal structure. This property leads to highly compressed wave functions (oligo- or single-reference) and crucially enables state-specific optimizations. This work is the first showing that compression and selective targeting of ground- and excited-states wave functions is possible for systems with three magnetic centers that are not exactly half-filled, and that potentially exhibit frustrated spin interactions. The reduced multi-reference character of the wave function greatly simplifies the interpretation of the ground- and excited-state electronic structures, and provides a route for the direct rationalization of magnetic interactions in these compounds, often considered a challenge in polynuclear transition-metal chemistry. In this study, strong electron correlation effects have explicitly been described by conventional and stochastic multiconfigurational methodologies, while dynamic correlation effects have been accounted for by multiconfigurational second order perturbation theory, CASPT2. Ab initio results for the [Mn3(IV)O4]4+ system have been mapped to a three-site Heisenberg model with two magnetic coupling constants. The magnetic coupling constants and the temperature dependence of the effective magnetic moment predicted by the ab initio calculations are in good agreement with the available experimental data, and confirm the antiferromagnetic interaction among the three magnetic centers, while providing a simple and rigorous description of the noncollinearity of the local spins, that characterize most of the low-energy states for this system.

Reactive Pendant Mn═O in a Synthetic Structural Model of a Proposed S4 State in the Photosynthetic Oxygen Evolving Complex.

The molecular mechanism of the Oxygen Evolving Center of photosystem II has been under debate for decades. One frequently cited proposal is the nucleophilic attack by water hydroxide on a pendant Mn═O moiety, though no chemical example of this reactivity at a manganese cubane cluster has been reported. We describe here the preparation, characterization, and a reactivity study of a synthetic manganese cubane cluster with a pendant manganese-oxo moiety. Reaction of this cluster with alkenes results in oxygen and hydrogen atom transfer reactions to form alcohol- and ketone-based oxygen-containing products. Nitrene transfer from core imides is negligible. The inorganic product is a cluster identical to the precursor, but with the pendant Mn═O moiety replaced by a hydrogen abstracted from the organic substrate, and is isolated in quantitative yield. 18O and 2H isotopic labeling studies confirm the transfer of atoms between the cluster and the organic substrate. The results suggest that the core cubane structure of this model compound remains intact, and that the pendant Mn═O moiety is preferentially reactive.

Biochemical and Spectroscopic Characterization of Highly Stable Photosystem II Supercomplexes from Arabidopsis

Photosystem II (PSII) is a large membrane supercomplex involved in the first step of oxygenic photosynthesis. It is organized as a dimer, with each monomer consisting of more than 20 subunits as well as several cofactors, including chlorophyll and carotenoid pigments, lipids, and ions. The isolation of stable and homogeneous PSII supercomplexes from plants has been a hindrance for their deep structural and functional characterization. In recent years, purification of complexes with different antenna sizes was achieved with mild detergent solubilization of photosynthetic membranes and fractionation on a sucrose gradient, but these preparations were only stable in the cold for a few hours. In this work, we present an improved protocol to obtain plant PSII supercomplexes that are stable for several hours/days at a wide range of temperatures and can be concentrated without degradation. Biochemical and spectroscopic properties of the purified PSII are presented, as well as a study of the complex solubility in the presence of salts. We also tested the impact of a large panel of detergents on PSII stability and found that very few are able to maintain the integrity of PSII. Such new PSII preparation opens the possibility of performing experiments that require room temperature conditions and/or high protein concentrations, and thus it will allow more detailed investigations into the structure and molecular mechanisms that underlie plant PSII function.

Structural Coupling of Extrinsic Proteins with the Oxygen-Evolving Center in Photosystem II.

Photosystem II (PSII), which catalyzes photosynthetic water oxidation, is composed of more than 20 subunits, including membrane-intrinsic and -extrinsic proteins. The PSII extrinsic proteins shield the catalytic Mn4CaO5 cluster from the outside bulk solution and enhance binding of inorganic cofactors, such as Ca2+ and Cl-, in the oxygen-evolving center (OEC) of PSII. Among PSII extrinsic proteins, PsbO is commonly found in all oxygenic organisms, while PsbP and PsbQ are specific to higher plants and green algae, and PsbU, PsbV, CyanoQ, and CyanoP exist in cyanobacteria. In addition, red algae and diatoms have unique PSII extrinsic proteins, such as PsbQ′ and Psb31, suggesting functional divergence during evolution. Recent studies with reconstitution experiments combined with Fourier transform infrared spectroscopy have revealed how the individual PSII extrinsic proteins affect the structure and function of the OEC in different organisms. In this review, we summarize our recent results and discuss changes that have occurred in the structural coupling of extrinsic proteins with the OEC during evolutionary history.

Artificial synthetic Mn(IV)Ca-oxido complexes mimic the oxygen-evolving complex in photosystem II.

A novel family of heteronuclear Mn(IV)Ca-oxido complexes containing Mn(IV)Ca-oxido cuboidal moieties and reactive water molecules on Ca(2+) have been synthesized and characterized to mimic the oxygen-evolving complex (OEC) of photosystem II (PSII) in nature.

Theoretical investigation on peripheral ligands of oxygen-evolving center in photosystem II

The interaction between the Mn-cluster and its peripheral ligands in oxygen-evolving center is still unclear. Theoretical investigation on the coordination of histidine, H(2)O, and CI to Mn2O2 units in OEC is conducted. The following conclusions are obtained: (i) both histidine and H(2)O molecule, bound to the two Mn ions, respectively, are vertical to the Mn2O2 plane, and maintain a large distance; (ii) the two H(2)O molecules cannot bind to the same Mn2O2 unit. Based on Mn-cluster structure in OEC, we theoretically predict that two H(2)O molecules bind to the two Mn ions at the "C"-shaped open end in S(0) 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 S(0) state is assigned.

The First Di‐μ3‐hydroxo‐Bridged Tetramanganese(II) Complex

Two molecules of water inserted between two dinuclear Mn species as μ3-hydroxo bridges are evident in the manganese–oxygen core of [{Mn(L)(OH)(thf)}2]·2THF (structure shown on the right). This discrete complex is thus an appealing functional model of the Mn4 core of the oxygen-evolving center in photosystem II at early S state. LH3 = 1,5-bis(3,5-dinitosalicylideneamino)pentan-3-ol; solid unmarked ellipsoids: N; open unmarked ellipsoids: O.