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Out of the seven known pathways organisms use to fix CO2, the acetyl-CoA pathway is assumed to be the most ancient. Its enzymes bear primordial traits, including carbon\u2013metal bonds and an abundance of transition metal clusters. Ancient traits can also be reflected in structural folds adopted by the enzymes and the catalytic strategies they employ. Here I show that the most common catalytic strategies used to accelerate reactions in the acetyl-CoA pathway are cofactor-aided catalysis, electrostatic interactions and general acid\/base catalysis. Enzymes of the acetyl-CoA pathway are replete with Rossman folds, TIM barrel folds, and alpha-beta plaits. These topologies evolved before the divergence of bacteria and archaea, along with five other catalytic folds of the acetyl-CoA pathway. Rossmann folds and TIM barrels likely underwent rapid diversification early in the history of life. In contrast, over half of the folds in the pathway are weakly diversified folds that emerged only once in the history of life, at the origin of biological CO2 fixation. Ancient metabolic pathways point to enzymes with conserved structural cores, which uncover topologies and catalytic strategies employed at the onset of metabolism.<\/jats:p>","DOI":"10.1093\/femsec\/fiag041","type":"journal-article","created":{"date-parts":[[2026,4,22]],"date-time":"2026-04-22T11:51:00Z","timestamp":1776858660000},"source":"Crossref","is-referenced-by-count":3,"title":["Protein folds and catalytic strategies at the origin of biological CO2 fixation"],"prefix":"10.1093","volume":"102","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-2849-6304","authenticated-orcid":false,"given":"Natalia","family":"Mrnjavac","sequence":"first","affiliation":[{"name":"Institute of Molecular Evolution, Faculty of Mathematics and Natural Sciences, Heinrich Heine University D\u00fcsseldorf , 40225D\u00fcsseldorf,","place":["Germany"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"286","published-online":{"date-parts":[[2026,4,22]]},"reference":[{"key":"2026051510520006700_bib1","doi-asserted-by":"publisher","first-page":"493","DOI":"10.1038\/s41586-024-07487-w","article-title":"Accurate structure prediction of biomolecular interactions with AlphaFold 3","volume":"630","author":"Abramson","year":"2024","journal-title":"Nature"},{"key":"2026051510520006700_bib2","doi-asserted-by":"publisher","first-page":"870","DOI":"10.1016\/j.jmb.2006.01.015","article-title":"The structure of formylmethanofuran: tetrahydromethanopterin formyltransferase in complex with its coenzymes","volume":"357","author":"Acharya","year":"2006","journal-title":"J Mol Biol"},{"key":"2026051510520006700_bib3","doi-asserted-by":"publisher","first-page":"206","DOI":"10.1007\/s002030050562","article-title":"Function of H2-forming methylenetetrahydromethanopterin dehydrogenase from Methanobacterium thermoautotrophicum in coenzyme F420 reduction with H2","volume":"169","author":"Afting","year":"1998","journal-title":"Arch Microbiol"},{"key":"2026051510520006700_bib4","doi-asserted-by":"publisher","first-page":"e01963","DOI":"10.7554\/eLife.01963","article-title":"Atomic model of the F420-reducing [NiFe] hydrogenase by electron cryo-microscopy using a direct electron detector","volume":"3","author":"Allegretti","year":"2014","journal-title":"eLife"},{"key":"2026051510520006700_bib5","doi-asserted-by":"publisher","first-page":"e2207897119","DOI":"10.1073\/pnas.2207897119","article-title":"Creative destruction: new protein folds from old","volume":"119","author":"Alvarez-Carre\u00f1o","year":"2022","journal-title":"Proc Natl Acad Sci USA"},{"key":"2026051510520006700_bib6","doi-asserted-by":"publisher","first-page":"5134","DOI":"10.1093\/molbev\/msab240","article-title":"Fold evolution before LUCA: common ancestry of SH3 domains and OB domains","volume":"38","author":"Alvarez-Carre\u00f1o","year":"2021","journal-title":"Mol Biol Evol"},{"key":"2026051510520006700_bib7","doi-asserted-by":"publisher","first-page":"199","DOI":"10.1021\/acs.accounts.6b00321","article-title":"Entropy and enzyme catalysis","volume":"50","author":"\u00c5qvist","year":"2017","journal-title":"Acc Chem Res"},{"key":"2026051510520006700_bib8","doi-asserted-by":"publisher","first-page":"D335","DOI":"10.1093\/nar\/gkz990","article-title":"PDBe: improved findability of macromolecular structure data in the PDB","volume":"48","author":"Armstrong","year":"2020","journal-title":"Nucleic Acids Res"},{"key":"2026051510520006700_bib9","doi-asserted-by":"publisher","first-page":"e2315568121","DOI":"10.1073\/pnas.2315568121","article-title":"Structural and mechanistic basis of the central energy-converting methyltransferase complex of methanogenesis","volume":"121","author":"Aziz","year":"2024","journal-title":"Proc Natl Acad Sci USA"},{"key":"2026051510520006700_bib10","doi-asserted-by":"publisher","first-page":"477","DOI":"10.1073\/pnas.26.8.477","article-title":"Radioactive carbon as an indicator of carbon dioxide reduction: IV. 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