Iron-only Fe-nitrogenase underscores common catalytic principles in biological nitrogen fixation

Trncik, Christian; Detemple, Franka; Einsle, Oliver

doi:10.1038/s41929-023-00952-1

Cited by 26 publications

(36 citation statements)

References 79 publications

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“…Three states are lowest in energy and almost degenerate (within 3−4 kJ/mol): BS-2358, 3468, and 2478 (the numbers denote the Fe ions with β spin; atom numbering shown in Figure 1a). These correspond to the three BS7 in the Noodleman nomenclature for the MoFe cluster, 13 with the extra Fe8 ion having a surplus 13 with the order BS7 < BS10 ≈ BS8 < BS9 ≈ BS4 < BS6 ≈ BS5 < BS3 < BS1, with an ambiguity only for the BS2 state, which is similar to BS3 for TPSSh but similar to BS5 with r 2 SCAN. This order is rather different from what was observed for the E 0 state of Mo-nitrogenase: BS7 < BS6 < BS2 < BS8 < BS4 ≈ BS10 < BS9 < BS5 < BS3 < BS1.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The crystal structure is a mixture of the resting state (E 0 ) and a turnover state in which the S2B ion is replaced by a light atom, modeled by O in the PDB file. 13 The two states have almost equal occupancy (0.5/0.5 in subunit A and 0.4/0.6 in subunit D). Gln-176 also shows two conformations.…”

Section: ■ Methodsmentioning

confidence: 99%

“…In this study, we have used this new version of quantum refinement to study the protonation state of the homocitrate ligand in the crystal structure of Fe-nitrogenase (8BOQ). 13 Coordinates, occupancies, Bfactors, and structure factors were obtained from this structure. We used the minimal QM model in Figure 1a for the QM calculations with the TPSS-D4/def2-SV(P) method 30,31,57 in the singlet state and BS state 2358 (obtained with the Flipspin approach in ORCA).…”

Section: ■ Methodsmentioning

confidence: 99%

“…All calculations were based on the recent crystal structure of Fe-only nitrogenase from Azotobacter vinelandii (PDB code 8BOQ), with a resolution of 1.55 Å. 13 The calculations encompassed the entire α 2 β 2 γ 2 heterohexamer as the subunits are intertwined. Likewise, two Mg 2+ ions were retained because they are deeply buried in the protein, stabilizing the subunit interface.…”

Section: ■ Methodsmentioning

confidence: 99%

“…Crystal structures of Mo-nitrogenase have been known since 1992 , and of V-nitrogenase since 2017 . However, the first crystal structure of Fe-only nitrogenase was published this year, and a cryogenic electron microscopy structure has also been presented . The studies have shown that all nitrogenases involve two proteins: the Fe protein and the Mo/V/FeFe protein.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Protonation of Homocitrate and the E₁ State of Fe-Nitrogenase Studied by QM/MM Calculations

Jiang,

Lundgren,

Ryde

2023

Inorg. Chem.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Methodsmentioning

confidence: 99%

Section: ■ Methodsmentioning

confidence: 99%

Section: ■ Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Protonation of Homocitrate and the E₁ State of Fe-Nitrogenase Studied by QM/MM Calculations

Jiang,

Lundgren,

Ryde

2023

Inorg. Chem.

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Highly Efficient Nitrogen‐Fixing Microbial Hydrogel Device for Sustainable Solar Hydrogen Production

Lee,

Yoon,

Park

et al. 2023

Advanced Materials

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Conversion of sunlight and organic carbon substrates to sustainable energy sources through microbial metabolism has great potential for the renewable energy industry. Despite recent progress in microbial photosynthesis, the development of microbial platforms that warrant efficient and scalable fuel production remains in its infancy. Efficient transfer and retrieval of gaseous reactants and products to and from microbes are particular hurdles. Here, inspired by water lily leaves floating on water, we present a microbial device designed to operate at the air‐water interface and facilitate concomitant supply of gaseous reactants, smooth capture of gaseous products, and efficient sunlight delivery. The floatable device carrying Rhodopseudomonas parapalustris, of which nitrogen fixation activity is firstly determined through this study, exhibits a hydrogen production rate of 104 mmol/h∙m2, which is 53 times higher than that of a conventional device placed at a depth of 2 cm in the medium. Furthermore, a scaled‐up device with an area of 144 cm2 generates hydrogen at a high rate of 1.52 L/h∙m2. Efficient nitrogen fixation and hydrogen generation, low fabrication cost, and mechanical durability corroborate the potential of the floatable microbial device toward practical and sustainable solar energy conversion.This article is protected by copyright. All rights reserved

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Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron‐based Metal‐Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis

Wang,

Fan,

Guo

et al. 2024

Angewandte Chemie

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Engineering advantageous defects to construct well‐defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH3 synthesis from N2 and H2O due to the chemical inertness of N2 molecule. Here, we report defective Fe‐based metal‐organic framework (MOF) photocatalysts via a non‐thermal plasma‐assisted synthesis strategy, where their NH3 production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH− and H2O). Specially, the optimized MIL‐100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.7‐ and 7.7‐fold activity enhancement comparable to the pristine catalyst under visible light irradiation. As revealed by experimental and theoretical calculation results, the dual defects in the catalyst induce the formation of abundant and highly accessible coordinatively unsaturated Fe active sites and synergistically optimize their geometric and electronic structures, which favors the injection of more d‐orbital electrons in Fe sites into the N2 π* antibonding orbital to achieve N2 activation and the formation of a key intermediate *NNH in the reaction. This work provides a guidance on the rational design and accurate construction of porous catalysts with precise defective structures for high‐performance activation of catalytic molecules.

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Iron-only Fe-nitrogenase underscores common catalytic principles in biological nitrogen fixation

Cited by 26 publications

References 79 publications

Protonation of Homocitrate and the E₁ State of Fe-Nitrogenase Studied by QM/MM Calculations

Protonation of Homocitrate and the E₁ State of Fe-Nitrogenase Studied by QM/MM Calculations

Highly Efficient Nitrogen‐Fixing Microbial Hydrogel Device for Sustainable Solar Hydrogen Production

Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron‐based Metal‐Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis

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Iron-only Fe-nitrogenase underscores common catalytic principles in biological nitrogen fixation

Cited by 26 publications

References 79 publications

Protonation of Homocitrate and the E1 State of Fe-Nitrogenase Studied by QM/MM Calculations

Protonation of Homocitrate and the E1 State of Fe-Nitrogenase Studied by QM/MM Calculations

Highly Efficient Nitrogen‐Fixing Microbial Hydrogel Device for Sustainable Solar Hydrogen Production

Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron‐based Metal‐Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis

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Protonation of Homocitrate and the E₁ State of Fe-Nitrogenase Studied by QM/MM Calculations

Protonation of Homocitrate and the E₁ State of Fe-Nitrogenase Studied by QM/MM Calculations