Artificial Mn4-oxido complexes mimic the oxygen-evolving center in photosynthesis

Chang, Wenjun; Chen, Chang-Hui; Dong, Hongbiao; Zhang, Chunxi

doi:10.1016/j.scib.2017.04.005

Cited by 11 publications

(5 citation statements)

References 22 publications

(24 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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“…It is a great challenge and a long-standing issue for chemists to synthesize the OEC in the laboratory ( Zhang, 2015 ; Li et al, 2020b ). During the last two decades, numerous multi-manganese complexes have been synthesized ( Wieghardt, 1989 ; Limburg et al, 1999 ; Mukhopadhyay et al, 2004 ; Mullins and Pecoraro, 2008 ; Dismukes et al, 2009 ; Gerey et al, 2016 ; Chang et al, 2017 ). Significant advances for the mimicking of the OEC have emerged since 2011 ( Tsui et al, 2013a ; Chen et al, 2017 ; Paul et al, 2017 ).…”

Section: Mimicking the Oecmentioning

confidence: 99%

“…All atomic coordinates used for BVS calculation were taken from the first monomer of PS II in the crystal structure data with PDB-IDs: 4UB6 (Suga et al, 2015), 6DHE (Kern et al, 2018), 6DHF (Kern et al, 2018), 6DHO (Kern et al, 2018), 6JLK (Suga et al, 2019), and 6JLL (Suga et al, 2019(Suga et al, ), respectively. et al, 2016Chang et al, 2017). Significant advances for the mimicking of the OEC have emerged since 2011 (Tsui et al, 2013a;Chen et al, 2017;Paul et al, 2017).…”

Section: Mimicking the Oecmentioning

confidence: 99%

Mimicking the Oxygen-Evolving Center in Photosynthesis

Chen

Yao

et al. 2022

Front. Plant Sci.

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The oxygen-evolving center (OEC) in photosystem II (PSII) of oxygenic photosynthetic organisms is a unique heterometallic-oxide Mn4CaO5-cluster that catalyzes water splitting into electrons, protons, and molecular oxygen through a five-state cycle (Sn, n = 0 ~ 4). It serves as the blueprint for the developing of the man-made water-splitting catalysts to generate solar fuel in artificial photosynthesis. Understanding the structure–function relationship of this natural catalyst is a great challenge and a long-standing issue, which is severely restricted by the lack of a precise chemical model for this heterometallic-oxide cluster. However, it is a great challenge for chemists to precisely mimic the OEC in a laboratory. Recently, significant advances have been achieved and a series of artificial Mn4XO4-clusters (X = Ca/Y/Gd) have been reported, which closely mimic both the geometric structure and the electronic structure, as well as the redox property of the OEC. These new advances provide a structurally well-defined molecular platform to study the structure–function relationship of the OEC and shed new light on the design of efficient catalysts for the water-splitting reaction in artificial photosynthesis.

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“…Experiments have revealed that the removal or substitution of Ca will affect the oxidation activity of OEC and the generation of oxygen. − So far, Ca can only be functionally replaced by Sr with lower activity . Many studies have been performed to investigate the unique functions of Ca 2+ , and the mechanisms have been proposed so far include: (i) maintaining the arrangement of the hydrogen bond network; − (ii) promoting the transfer of protons and electrons; ,, (iii) stabilizing the high oxidation state and efficient oxidation of manganese; − (iv) maintaining the overall structure; , (v) the activation of water in the process of oxo–oxyl coupling; and (vi) indirectly modulates the redox potential of D1-Tyr161 (Y Z ) …”

Section: Introductionmentioning

confidence: 99%

The Role of Redox-Inactive Metals in Modulating the Redox Potential of the Mn₄CaO₄ Model Complex

Gao

Fan

2022

Inorg. Chem.

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Photosynthetic oxygen-evolving center (OEC), the "engine of life", is a unique Mn 4 CaO 5 cluster catalyzing the water oxidation. The role of redox-inactive component Ca 2+ , which can only be functionally replaced by Sr 2+ in a biological environment, has been under debate for a long time. Recently, its modulating effect on the redox potential of native OEC and artificial structural OEC model complex has received great attention, and linear relationship between the potential and the Lewis acidity of the redox-inactive metal has been proposed for the MMn 3 O 4 model complex. In this work, the modulating effect has been studied in detail using the Mn 4 CaO 4 model complex, which is the closest structural model to OEC to date and has a similar redox potential at the S 1 −S 2 transition. We found the redox-inactive metal only has a weak modulating effect on the potential, which is comparable in strength to that of the ligand environments. Meanwhile, the net charge of the complex, which could be changed along with the redox-inactive metal, has a high impact on the potential and can be unified by protonation, deprotonation, or ligand modification. Although the modulating effect of the redox-inactive metal is not very strong, the linear relationship between the potential and the Lewis acidity is still valid for Mn 4 MO 4 complexes. Our results of strong modulating effects for net charge and weak modulating effects for redox-inactive metal fit with the previous experimental observations on Mn 4 MO 4 (M = Ca 2+ , Y 3+ , and Gd 3+ ) model complexes, and suggest that Ca 2+ can be structurally and electrochemically replaced with other metal cations, together with proper ligand modifications.

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Artificial Mn4-oxido complexes mimic the oxygen-evolving center in photosynthesis

Cited by 11 publications

References 22 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

Mimicking the Oxygen-Evolving Center in Photosynthesis

The Role of Redox-Inactive Metals in Modulating the Redox Potential of the Mn₄CaO₄ Model Complex

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Artificial Mn4-oxido complexes mimic the oxygen-evolving center in photosynthesis

Cited by 11 publications

References 22 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

Mimicking the Oxygen-Evolving Center in Photosynthesis

The Role of Redox-Inactive Metals in Modulating the Redox Potential of the Mn4CaO4 Model Complex

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The Role of Redox-Inactive Metals in Modulating the Redox Potential of the Mn₄CaO₄ Model Complex