Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic Mo<sup>V</sup>O(μ-S)Cu<sup>I</sup> complexes

Gourlay, Craig; Nielsen, David J.; Evans, David J.; White, Jonathan M.; Young, Charles G.

doi:10.1039/c7sc04239f

Cited by 20 publications

(16 citation statements)

References 64 publications

(102 reference statements)

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“…The relevance of MoCu-CODH as an inspiring system for future biomimetic and bioengineering applications is currently growing. This is due not only to the relevance of the reactions it catalyzes, but also to its resistance to atmospheric O 2 exposure—a rare feature in the case of enzymes expressing carbon monoxide dehydrogenase and hydrogenase activities (Choi et al, 2017; Gourlay et al, 2018; Groysman et al, 2018). Notably, the recent establishment of a functional heterologous expression system for the MoCu-CODH enzyme (Kaufmann et al, 2018) together with developments in the computational chemistry field will hopefully boost the positive feedback among biochemical, biomimetic and quantum chemical studies, opening new perspectives for a deeper understanding of this interesting metalloenzyme.…”

Section: Discussionmentioning

confidence: 99%

The Challenging in silico Description of Carbon Monoxide Oxidation as Catalyzed by Molybdenum-Copper CO Dehydrogenase

et al. 2019

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Carbon monoxide (CO) is a highly toxic gas to many living organisms. However, some microorganisms are able to use this molecule as the sole source of carbon and energy. Soil bacteria such as the aerobic Oligotropha carboxidovorans are responsible for the annual removal of about 2x108 tons of CO from the atmosphere. Detoxification through oxidation of CO to CO2 is enabled by the MoCu-dependent CO-dehydrogenase enzyme (MoCu-CODH) which—differently from other enzyme classes with similar function—retains its catalytic activity in the presence of atmospheric O2. In the last few years, targeted advancements have been described in the field of bioengineering and biomimetics, which is functional for future technological exploitation of the catalytic properties of MoCu-CODH and for the reproduction of its reactivity in synthetic complexes. Notably, a growing interest for the quantum chemical investigation of this enzyme has recently also emerged. This mini-review compiles the current knowledge of the MoCu-CODH catalytic cycle, with a specific focus on the outcomes of theoretical studies on this enzyme class. Rather controversial aspects from different theoretical studies will be highlighted, thus illustrating the challenges posed by this system as far as the application of density functional theory and hybrid quantum-classical methods are concerned.

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Section: Discussionmentioning

confidence: 99%

The Challenging in silico Description of Carbon Monoxide Oxidation as Catalyzed by Molybdenum-Copper CO Dehydrogenase

et al. 2019

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“…Acidobacteria and Chloroflexi expressed all four subunits of CODH, while Actinobacteria, Desulfobacterota, and Latescibacterota did not express the coxG subunit. The coxG gene was also absent from the form 1 (bona fide CO dehydrogenase) Mo-CODH from the chemoautotroph Alkalilimnicola ehrlichei MLHE-1 [67], suggesting that the presence of this gene is not crucial for CO oxidation [92,93]. Interestingly, while the auxiliary subunits of CODH, affiliated to poribacterial MAGs, were expressed, the large CO-oxidizing subunit was absent in the representatives of this phylum.…”

Section: Gene Expression Of Carbon Fixation and Energy Production Pathways: Case Study Of P Ficiformismentioning

confidence: 98%

Rethinking symbiotic metabolism: trophic strategies in the microbiomes of different sponge species

Burgsdorf

Sizikov

Squatrito

et al. 2021

Preprint

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In this study we describe the major lithoheterotrophic and autotrophic processes in 21 microbial sponge-associated phyla using novel and existing genomic and transcriptomic datasets. We show that a single gene family, molybdenum-binding subunit of dehydrogenase (coxL), likely evolved to benefit both lithoheterotrophic and organoheterotrophic symbionts, through adaptation to different inorganic and organic substrates. We show the main microbial carbon fixation pathways in sponges are restricted to specialized symbiotic lineages within five phyla. We also propose that sponge symbionts, in particular Acidobacteria, are capable of assimilating carbon through anaplerotic processes. However, the presence of symbionts genomically capable of autotrophy does not inform on their actual contribution to light and dark carbon fixation. Using radioisotope assays we identified variability in the relative contributions of chemosynthesis to total carbon fixation in different sponge species. Furthermore, the symbiosis of sponges with two closely related Cyanobacteria results in outcomes that are not predictable by analysis of -omics data alone: Candidatus Synechococcus spongiarum contributes to the holobiont carbon budget by transfer of photosynthates, while Candidatus Synechococcus feldmannii does not. Our results highlight the importance of combining sequencing data with physiology to gain a broader understanding of carbon metabolism within holobionts characterized by highly diverse microbiomes.

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“…33 This metal cofactor has led to the synthesis of a number of biomimetic Mo-Cu complexes, but none of them had been reported to show catalytic activity for CO 2 reduction. [34][35][36][37][38] In this work, we have performed in-depth investigations of the CO 2 electroreduction catalytic activity of one of these complexes, 38 [(bdt)Mo VI (O)S 2 Cu I CN] 2À , 1, (bdt ¼ benzenedithiolate), in which Mo and Cu ions are connected by two m 2 -sulde ligands and the MPT ligand is mimicked by the bdt ligand chelating the Mo ion. While mimicking the structure of CODH2 active site, complex 1 reproduces the function of FDH, catalyzing CO 2 reduction with a high selectivity for formate production.…”

Section: Introductionmentioning

confidence: 99%

A bioinspired molybdenum–copper molecular catalyst for CO₂ electroreduction

et al. 2020

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Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic Mo^VO(μ-S)Cu^I complexes

Abstract: Complexes exhibiting the MoVO(μ-S)CuI cores, EPR properties, electronic structures and biomimetic reactions of aerobic Mo/Cu-containing carbon monoxide dehydrogenases are reported.

Cited by 20 publications

References 64 publications

The Challenging in silico Description of Carbon Monoxide Oxidation as Catalyzed by Molybdenum-Copper CO Dehydrogenase

The Challenging in silico Description of Carbon Monoxide Oxidation as Catalyzed by Molybdenum-Copper CO Dehydrogenase

Rethinking symbiotic metabolism: trophic strategies in the microbiomes of different sponge species

A bioinspired molybdenum–copper molecular catalyst for CO₂ electroreduction

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Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic MoVO(μ-S)CuI complexes

Abstract: Complexes exhibiting the MoVO(μ-S)CuI cores, EPR properties, electronic structures and biomimetic reactions of aerobic Mo/Cu-containing carbon monoxide dehydrogenases are reported.

Cited by 20 publications

References 64 publications

The Challenging in silico Description of Carbon Monoxide Oxidation as Catalyzed by Molybdenum-Copper CO Dehydrogenase

The Challenging in silico Description of Carbon Monoxide Oxidation as Catalyzed by Molybdenum-Copper CO Dehydrogenase

Rethinking symbiotic metabolism: trophic strategies in the microbiomes of different sponge species

A bioinspired molybdenum–copper molecular catalyst for CO2 electroreduction

Contact Info

Product

Resources

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Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic Mo^VO(μ-S)Cu^I complexes

A bioinspired molybdenum–copper molecular catalyst for CO₂ electroreduction