Structural models of the biological oxygen-evolving complex: achievements, insights, and challenges for biomimicry

Paul, S.; Neese, Frank; Pantazis, Dimitrios A.

doi:10.1039/c7gc00425g

Cited by 81 publications

(68 citation statements)

References 217 publications

(320 reference statements)

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“…A large number of artificial Mn complexes have been reported in the literature [82,92,95,[97][98][99][100][101][102][103][104]. Among them, tetra-manganese complexes containing Mn 4 O 4 -cubane [101,[105][106][107][108] are attractive.…”

Section: Challenge For the Synthesis Of The Oec In The Laboratorymentioning

confidence: 99%

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Yao

Chen

et al. 2020

Catalysts

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The oxygen-evolving center (OEC) in photosystem II (PSII) of plants, algae and cyanobacteria is a unique natural catalyst that splits water into electrons, protons and dioxygen. The crystallographic studies of PSII have revealed that the OEC is an asymmetric Mn4CaO5-cluster. The understanding of the structure-function relationship of this natural Mn4CaO5-cluster is impeded mainly due to the complexity of the protein environment and lack of a rational chemical model as a reference. Although it has been a great challenge for chemists to synthesize the OEC in the laboratory, significant advances have been achieved recently. Different artificial complexes have been reported, especially a series of artificial Mn4CaO4-clusters that closely mimic both the geometric and electronic structures of the OEC in PSII, which provides a structurally well-defined chemical model to investigate the structure-function relationship of the natural Mn4CaO5-cluster. The deep investigations on this artificial Mn4CaO4-cluster could provide new insights into the mechanism of the water-splitting reaction in natural photosynthesis and may help the development of efficient catalysts for the water-splitting reaction in artificial photosynthesis.

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Section: Challenge For the Synthesis Of The Oec In The Laboratorymentioning

confidence: 99%

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Yao

Chen

et al. 2020

Catalysts

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“…The surrounding ligands of the Mn 4 CaO 4 cluster are provided by eight (CH 3 ) 3 CCO 2 − anions and three neutral ligands (two pivalic acid and one pyridine molecules), similar to the peripheral ligands of the OEC (Figure B). Therefore, this new model complex was considered to closely mimic the natural OEC in respects of not only the core structure, but also the peripheral ligands ,. The oxidation states of the four Mn ions (III, III, IV, IV) in the model complex are the same as that of the S 1 state OEC …”

Section: Closer Mimicking Of the Oecmentioning

confidence: 99%

Natural and Artificial Mn₄Ca Cluster for the Water Splitting Reaction

Chen

Zhao

et al. 2017

ChemSusChem

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The oxygen‐evolving center (OEC) in photosystem II (PSII) is a unique biological catalyst that splits water into electrons, protons, and O2 by using solar energy. Recent crystallographic studies have revealed that the structure of the OEC is an asymmetric Mn4Ca cluster, which provides a blueprint to develop man‐made water‐splitting catalysts for artificial photosynthesis. Although it is a great challenge to mimic the whole structure and function of the OEC in the laboratory, significant advances have recently been achieved. In this Minireview, recent progress on mimicking the natural OEC is discussed. New strategies are suggested to construct more stable and efficient new generation of catalytic materials for the water splitting reaction based on the artificial Mn4Ca cluster in the future.

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“…The OEC is oxidized by successive light-induced electron transfers along a sequence of storage states S i (i = 0-4 denotes the number of stored oxidizing equivalents) with S 4 being a transient state that evolves dioxygen resetting the cluster to S 0 ( Figure 1d). Among the many open questions regarding aspects of the structure and function of PSII, the definition of the geometric/electronic structure and mechanistic principles of the OEC remain in primary focus [3][4][5][6][7][8][9][10][11][12], not least because of the potential relevance of this unique biological catalyst for the development of bioinspired artificial photosynthetic systems [13][14][15][16][17][18][19][20][21][22][23][24][25][26].…”

Section: Introductionmentioning

confidence: 99%

The S3 State of the Oxygen-Evolving Complex: Overview of Spectroscopy and XFEL Crystallography with a Critical Evaluation of Early-Onset Models for O–O Bond Formation

Pantazis

2019

Inorganics

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The catalytic cycle of the oxygen-evolving complex (OEC) of photosystem II (PSII) comprises five intermediate states Si (i = 0–4), from the most reduced S0 state to the most oxidized S4, which spontaneously evolves dioxygen. The precise geometric and electronic structure of the Si states, and hence the mechanism of O–O bond formation in the OEC, remain under investigation, particularly for the final steps of the catalytic cycle. Recent advances in protein crystallography based on X-ray free-electron lasers (XFELs) have produced new structural models for the S3 state, which indicate that two of the oxygen atoms of the inorganic Mn4CaO6 core of the OEC are in very close proximity. This has been interpreted as possible evidence for “early-onset” O–O bond formation in the S3 state, as opposed to the more widely accepted view that the O–O bond is formed in the final state of the cycle, S4. Peroxo or superoxo formation in S3 has received partial support from computational studies. Here, a brief overview is provided of spectroscopic information, recent crystallographic results, and computational models for the S3 state. Emphasis is placed on computational S3 models that involve O–O formation, which are discussed with respect to their agreement with structural information, experimental evidence from various spectroscopic studies, and substrate exchange kinetics. Despite seemingly better agreement with some of the available crystallographic interpretations for the S3 state, models that implicate early-onset O–O bond formation are hard to reconcile with the complete line of experimental evidence, especially with X-ray absorption, X-ray emission, and magnetic resonance spectroscopic observations. Specifically with respect to quantum chemical studies, the inconclusive energetics for the possible isoforms of S3 is an acute problem that is probably beyond the capabilities of standard density functional theory.

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Structural models of the biological oxygen-evolving complex: achievements, insights, and challenges for biomimicry

Abstract: Recent developments on structural mimics for the oxygen-evolving complex of photosystem II are reviewed and discussed.

Cited by 81 publications

References 217 publications

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Natural and Artificial Mn₄Ca Cluster for the Water Splitting Reaction

The S3 State of the Oxygen-Evolving Complex: Overview of Spectroscopy and XFEL Crystallography with a Critical Evaluation of Early-Onset Models for O–O Bond Formation

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Structural models of the biological oxygen-evolving complex: achievements, insights, and challenges for biomimicry

Abstract: Recent developments on structural mimics for the oxygen-evolving complex of photosystem II are reviewed and discussed.

Cited by 81 publications

References 217 publications

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Mimicking the Catalytic Center for the Water-Splitting Reaction in Photosystem II

Natural and Artificial Mn4Ca Cluster for the Water Splitting Reaction

The S3 State of the Oxygen-Evolving Complex: Overview of Spectroscopy and XFEL Crystallography with a Critical Evaluation of Early-Onset Models for O–O Bond Formation

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Natural and Artificial Mn₄Ca Cluster for the Water Splitting Reaction