Oxidoreductases and metal cofactors in the functioning of Earth

This is a Preprint and has not been peer reviewed. The published version of this Preprint is available: https://doi.org/10.1042/EBC20230012. This is version 2 of this Preprint.

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Bruno Hay Mele, Maria Monticelli, Serena Leone, Deborah Bastoni, Bernardo Barosa, Martina Cascone, Flavia Migliaccio, Francesco Montemagno, Annarita Ricciardelli, Luca Tonietti, Alessandra Rotundi, Angelina Cordone, Donato Giovannelli


Life sustains itself using energy generated by thermodynamic disequilibria, commonly existing as redox disequilibria. Metals are significant players in controlling redox reactions, as they are essential components of the engine that life uses to tap into the thermodynamic disequilibria necessary for metabolism. The number of proteins that evolved to catalyze redox reactions is extraordinary, as is the diversification level of metal cofactors and catalytic domain structures involved. Notwithstanding the importance of the topic, the relationship between metals and the redox reactions they are involved in has been poorly explored. This work reviews the structure and function of different prokaryotic organometallic-protein complexes, highlighting their pivotal role in controlling biogeochemistry. We focus on a specific subset of metal-containing oxidoreductases (EC1 or EC7.1), which are directly involved in biogeochemical cycles, i.e., at least one substrate or product is a small inorganic molecule that is or can be exchanged with the environment. Based on these inclusion criteria, we select and report 59 metalloenzymes, describing the organometallic structure of their active sites, the redox reactions in which they are involved, and their biogeochemical roles.




Biochemistry, Biophysics, and Structural Biology, Biogeochemistry, Biology, Microbiology


Redox reactions, metalloproteins, organometallic compounds, ligands, metabolism, biogeochemistry, metalloproteins, organometallic compounds, ligands, metabolism, biogeochemistry


Published: 2023-05-15 02:37

Last Updated: 2023-05-16 15:25

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CC BY Attribution 4.0 International

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Conflict of interest statement:
The authors declare that there are no competing interests associated with the manuscript.

Data Availability (Reason not available):
The underlying data is available under the Zenodo repository doi: 10.5281/zenodo.7934782