{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T11:37:12Z","timestamp":1790509032693,"version":"4.1.0"},"reference-count":90,"publisher":"Portland Press Ltd.","issue":"16","license":[{"start":{"date-parts":[[2019,7,25]],"date-time":"2019-07-25T00:00:00Z","timestamp":1564012800000},"content-version":"vor","delay-in-days":330,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["portlandpress.com"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2018,8,31]]},"abstract":"<jats:p>Until recently, prebiotic precursors to metabolic pathways were not known. In parallel, chemistry achieved the synthesis of amino acids and nucleotides only in reaction sequences that do not resemble metabolic pathways, and by using condition step changes, incompatible with enzyme evolution. As a consequence, it was frequently assumed that the topological organisation of the metabolic pathway has formed in a Darwinian process. The situation changed with the discovery of a non-enzymatic glycolysis and pentose phosphate pathway. The suite of metabolism-like reactions is promoted by a metal cation, (Fe(II)), abundant in Archean sediment, and requires no condition step changes. Knowledge about metabolism-like reaction topologies has accumulated since, and supports non-enzymatic origins of gluconeogenesis, the S-adenosylmethionine pathway, the Krebs cycle, as well as CO2 fixation. It now feels that it is only a question of time until essential parts of metabolism can be replicated non-enzymatically. Here, I review the \u2018accidents\u2019 that led to the discovery of the non-enzymatic glycolysis, and on the example of a chemical network based on hydrogen cyanide, I provide reasoning why metabolism-like non-enzymatic reaction topologies may have been missed for a long time. Finally, I discuss that, on the basis of non-enzymatic metabolism-like networks, one can elaborate stepwise scenarios for the origin of metabolic pathways, a situation that increasingly renders the origins of metabolism a tangible problem.<\/jats:p>","DOI":"10.1042\/bcj20160866","type":"journal-article","created":{"date-parts":[[2018,8,30]],"date-time":"2018-08-30T05:36:36Z","timestamp":1535607396000},"page":"2577-2592","update-policy":"https:\/\/doi.org\/10.1042\/crossmark_policy","source":"Crossref","is-referenced-by-count":112,"title":["An appeal to magic? The discovery of a non-enzymatic metabolism and its role in the origins of life"],"prefix":"10.1042","volume":"475","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9535-7413","authenticated-orcid":false,"given":"Markus","family":"Ralser","sequence":"first","affiliation":[{"name":"Department of Biochemistry and Cambridge Systems Biology Centre, University of Cambridge, 80 Tennis Court Rd, Cambridge CB2 1GA, U.K."},{"name":"Molecular Biology of Metabolism Laboratory, The Francis Crick Institute, 1 Midland Rd, London NW1 1AT, U.K."},{"name":"Department of Biochemistry, Charit\u00e8, Am Chariteplatz 1, 10117 Berlin, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"288","published-online":{"date-parts":[[2018,8,29]]},"reference":[{"key":"2021112216532329600_BCJ-2016-0866CC1","doi-asserted-by":"publisher","first-page":"2731","DOI":"10.1016\/j.febslet.2013.06.026","article-title":"Chemical and genomic evolution of enzyme-catalyzed reaction networks","volume":"587","author":"Kanehisa","year":"2013","journal-title":"FEBS Lett."},{"key":"2021112216532329600_BCJ-2016-0866CC2","doi-asserted-by":"publisher","first-page":"301","DOI":"10.1101\/gr.1926504","article-title":"Flux coupling analysis of genome-scale metabolic network reconstructions","volume":"14","author":"Burgard","year":"2004","journal-title":"Genome Res."},{"key":"2021112216532329600_BCJ-2016-0866CC3","doi-asserted-by":"publisher","first-page":"419","DOI":"10.1038\/nbt.2488","article-title":"A community-driven global reconstruction of human metabolism","volume":"31","author":"Thiele","year":"2013","journal-title":"Nat. Biotechnol."},{"key":"2021112216532329600_BCJ-2016-0866CC4","doi-asserted-by":"publisher","first-page":"16018","DOI":"10.1038\/ncomms16018","article-title":"The self-inhibitory nature of metabolic networks and its alleviation through compartmentalization","volume":"8","author":"Alam","year":"2017","journal-title":"Nat. Commun."},{"key":"2021112216532329600_BCJ-2016-0866CC5","doi-asserted-by":"publisher","first-page":"651","DOI":"10.1038\/35036627","article-title":"The large-scale organization of metabolic networks","volume":"407","author":"Jeong","year":"2000","journal-title":"Nature"},{"key":"2021112216532329600_BCJ-2016-0866CC6","doi-asserted-by":"publisher","first-page":"2635","DOI":"10.1002\/cbdv.201200281","article-title":"An open question on the origin of life: the first forms of metabolism","volume":"9","author":"Luisi","year":"2012","journal-title":"Chem. Biodivers."},{"key":"2021112216532329600_BCJ-2016-0866CC7","doi-asserted-by":"publisher","first-page":"729","DOI":"10.1002\/msb.20145351","article-title":"Prebiotic metabolic networks?","volume":"10","author":"Luisi","year":"2014","journal-title":"Mol. Syst. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC8","doi-asserted-by":"publisher","first-page":"27","DOI":"10.1007\/s00239-017-9822-8","article-title":"On the early evolution of catabolic pathways: a comparative genomics approach. I. The cases of glucose, ribose, and the nucleobases catabolic routes","volume":"86","author":"Rivas","year":"2018","journal-title":"J. Mol. Evol."},{"key":"2021112216532329600_BCJ-2016-0866CC9","doi-asserted-by":"publisher","first-page":"153","DOI":"10.1016\/j.copbio.2014.12.020","article-title":"The widespread role of non-enzymatic reactions in cellular metabolism","volume":"34","author":"Keller","year":"2015","journal-title":"Curr. Opin. Biotechnol."},{"key":"2021112216532329600_BCJ-2016-0866CC10","doi-asserted-by":"publisher","first-page":"285","DOI":"10.1016\/j.biocel.2008.08.022","article-title":"The origin and evolution of modern metabolism","volume":"41","author":"Caetano-Anolles","year":"2009","journal-title":"Int. J. Biochem. Cell Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC11","doi-asserted-by":"publisher","first-page":"99","DOI":"10.1080\/10409230490460765","article-title":"Prebiotic chemistry and the origin of the RNA world","volume":"39","author":"Orgel","year":"2004","journal-title":"Crit. Rev. Biochem. Mol. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC12","doi-asserted-by":"publisher","first-page":"941","DOI":"10.1016\/j.chembiol.2005.06.008","article-title":"A ribozyme for the aldol reaction","volume":"12","author":"Fusz","year":"2005","journal-title":"Chem. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC13","doi-asserted-by":"publisher","first-page":"466","DOI":"10.1016\/j.chembiol.2013.03.012","article-title":"The origin of RNA and \u2018my grandfather's axe\u2019","volume":"20","author":"Hud","year":"2013","journal-title":"Chem. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC14","doi-asserted-by":"publisher","first-page":"12503","DOI":"10.1073\/pnas.220406697","article-title":"Self-organizing biochemical cycles","volume":"97","author":"Orgel","year":"2000","journal-title":"Proc. Natl Acad. Sci. U.S.A."},{"key":"2021112216532329600_BCJ-2016-0866CC15","doi-asserted-by":"publisher","first-page":"104","DOI":"10.1002\/anie.201506585","article-title":"The origin of life \u2014 out of the blue","volume":"55","author":"Sutherland","year":"2016","journal-title":"Angew. Chem. Int. Ed."},{"key":"2021112216532329600_BCJ-2016-0866CC16","doi-asserted-by":"publisher","first-page":"e18","DOI":"10.1371\/journal.pbio.0060018","article-title":"The implausibility of metabolic cycles on the prebiotic Earth","volume":"6","author":"Orgel","year":"2008","journal-title":"PLoS Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC17","doi-asserted-by":"publisher","first-page":"367","DOI":"10.1016\/0022-2836(68)90392-6","article-title":"The origin of the genetic code","volume":"38","author":"Crick","year":"1968","journal-title":"J. Mol. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC18","doi-asserted-by":"publisher","first-page":"a002089","DOI":"10.1101\/cshperspect.a002089","article-title":"Historical development of origins research","volume":"2","author":"Lazcano","year":"2010","journal-title":"Cold Spring Harb. Perspect. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC19","doi-asserted-by":"publisher","first-page":"12","DOI":"10.1016\/j.tim.2015.10.003","article-title":"On the origin of heterotrophy","volume":"24","author":"Sch\u00f6nheit","year":"2016","journal-title":"Trends Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC20","doi-asserted-by":"publisher","first-page":"528","DOI":"10.1126\/science.117.3046.528","article-title":"A production of amino acids under possible primitive earth conditions","volume":"117","author":"Miller","year":"1953","journal-title":"Science"},{"key":"2021112216532329600_BCJ-2016-0866CC21","doi-asserted-by":"publisher","first-page":"159","DOI":"10.1007\/s11084-018-9555-8","article-title":"Acetyl phosphate as a primordial energy currency at the origin of life","volume":"48","author":"Whicher","year":"2018","journal-title":"Orig. Life Evol. Biosph."},{"key":"2021112216532329600_BCJ-2016-0866CC22","doi-asserted-by":"publisher","first-page":"153","DOI":"10.1073\/pnas.31.6.153","article-title":"On the evolution of biochemical syntheses","volume":"31","author":"Horowitz","year":"1945","journal-title":"Proc. Natl Acad. Sci. U.S.A."},{"key":"2021112216532329600_BCJ-2016-0866CC23","doi-asserted-by":"publisher","first-page":"985","DOI":"10.1042\/BST20140132","article-title":"The RNA world and the origin of metabolic enzymes","volume":"42","author":"Ralser","year":"2014","journal-title":"Biochem. Soc. Trans."},{"key":"2021112216532329600_BCJ-2016-0866CC24","doi-asserted-by":"publisher","first-page":"886","DOI":"10.1038\/nrmicro1023","article-title":"Genome-scale models of microbial cells: evaluating the consequences of constraints","volume":"2","author":"Price","year":"2004","journal-title":"Nat. Rev. Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC25","doi-asserted-by":"publisher","first-page":"16116","DOI":"10.1038\/nmicrobiol.2016.116","article-title":"The physiology and habitat of the last universal common ancestor","volume":"1","author":"Weiss","year":"2016","journal-title":"Nat. Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC26","doi-asserted-by":"publisher","first-page":"1155","DOI":"10.1038\/nbt1492","article-title":"A consensus yeast metabolic network reconstruction obtained from a community approach to systems biology","volume":"26","author":"Herrg\u00e5rd","year":"2008","journal-title":"Nat. Biotechnol."},{"key":"2021112216532329600_BCJ-2016-0866CC27","doi-asserted-by":"publisher","first-page":"1126","DOI":"10.1016\/j.cell.2017.02.001","article-title":"Remnants of an ancient metabolism without phosphate","volume":"168","author":"Goldford","year":"2017","journal-title":"Cell"},{"key":"2021112216532329600_BCJ-2016-0866CC28","doi-asserted-by":"publisher","first-page":"117","DOI":"10.1016\/j.coisb.2018.01.004","article-title":"Modern views of ancient metabolic networks","volume":"8","author":"Goldford","year":"2018","journal-title":"Curr. Opin. Syst. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC29","doi-asserted-by":"publisher","first-page":"16229","DOI":"10.1038\/nmicrobiol.2016.229","article-title":"Is LUCA a thermophilic progenote?","volume":"1","author":"Gogarten","year":"2016","journal-title":"Nat Microbiol"},{"key":"2021112216532329600_BCJ-2016-0866CC30","doi-asserted-by":"publisher","first-page":"940","DOI":"10.1038\/nature04640","article-title":"Production of the antimalarial drug precursor artemisinic acid in engineered yeast","volume":"440","author":"Ro","year":"2006","journal-title":"Nature"},{"key":"2021112216532329600_BCJ-2016-0866CC31","doi-asserted-by":"publisher","first-page":"89","DOI":"10.1128\/MMBR.00041-13","article-title":"Carbohydrate metabolism in Archaea: current insights into unusual enzymes and pathways and their regulation","volume":"78","author":"Br\u00e4sen","year":"2014","journal-title":"Microbiol. Mol. Biol. Rev."},{"key":"2021112216532329600_BCJ-2016-0866CC32","doi-asserted-by":"publisher","first-page":"231","DOI":"10.1042\/bj20021472","article-title":"The unique features of glycolytic pathways in Archaea","volume":"375","author":"Verhees","year":"2003","journal-title":"Biochem. J."},{"key":"2021112216532329600_BCJ-2016-0866CC33","doi-asserted-by":"publisher","first-page":"563","DOI":"10.1126\/science.aao2410","article-title":"Reversibility of citrate synthase allows autotrophic growth of a thermophilic bacterium","volume":"359","author":"Mall","year":"2018","journal-title":"Science"},{"key":"2021112216532329600_BCJ-2016-0866CC34","doi-asserted-by":"publisher","first-page":"559","DOI":"10.1126\/science.aao3407","article-title":"A primordial and reversible TCA cycle in a facultatively chemolithoautotrophic thermophile","volume":"359","author":"Nunoura","year":"2018","journal-title":"Science"},{"key":"2021112216532329600_BCJ-2016-0866CC35","doi-asserted-by":"publisher","first-page":"301","DOI":"10.1038\/nchem.2202","article-title":"Common origins of RNA, protein and lipid precursors in a cyanosulfidic protometabolism","volume":"7","author":"Patel","year":"2015","journal-title":"Nat. Chem."},{"key":"2021112216532329600_BCJ-2016-0866CC36","doi-asserted-by":"publisher","first-page":"1470","DOI":"10.1073\/pnas.0912628107","article-title":"Lack of evolvability in self-sustaining autocatalytic networks constraints metabolism-first scenarios for the origin of life","volume":"107","author":"Vasas","year":"2010","journal-title":"Proc. Natl Acad. Sci. U.S.A."},{"key":"2021112216532329600_BCJ-2016-0866CC37","doi-asserted-by":"publisher","first-page":"895","DOI":"10.1038\/nchem.1467","article-title":"Prebiotic synthesis of simple sugars by photoredox systems chemistry","volume":"4","author":"Ritson","year":"2013","journal-title":"Nat. Chem."},{"key":"2021112216532329600_BCJ-2016-0866CC38","doi-asserted-by":"publisher","first-page":"239","DOI":"10.1038\/nature08013","article-title":"Synthesis of activated pyrimidine ribonucleotides in prebiotically plausible conditions","volume":"459","author":"Powner","year":"2009","journal-title":"Nature"},{"key":"2021112216532329600_BCJ-2016-0866CC39","doi-asserted-by":"publisher","first-page":"52","DOI":"10.12688\/wellcomeopenres.12103.2","article-title":"1H-NMR as implemented in several origin of life studies artificially implies the absence of metabolism-like non-enzymatic reactions by being signal-suppressed","volume":"2","author":"Keller","year":"2018","journal-title":"Wellcome Open Res."},{"key":"2021112216532329600_BCJ-2016-0866CC40","doi-asserted-by":"publisher","first-page":"1088","DOI":"10.1126\/science.1105692","article-title":"Iron isotope constraints on the Archean and Paleoproterozoic ocean redox state","volume":"307","author":"Rouxel","year":"2005","journal-title":"Science"},{"key":"2021112216532329600_BCJ-2016-0866CC41","doi-asserted-by":"publisher","first-page":"308","DOI":"10.1016\/S0020-1693(03)00442-0","article-title":"The bioinorganic chemistry of the ancient ocean: the co-evolution of cyanobacterial metal requirements and biogeochemical cycles at the Archean\u2013Proterozoic boundary?","volume":"356","author":"Saito","year":"2003","journal-title":"Inorg. Chim. Acta"},{"key":"2021112216532329600_BCJ-2016-0866CC42","doi-asserted-by":"publisher","first-page":"295","DOI":"10.1111\/gbi.12036","article-title":"Authigenic iron oxide proxies for marine zinc over geological time and implications for eukaryotic metallome evolution","volume":"11","author":"Robbins","year":"2013","journal-title":"Geobiology"},{"key":"2021112216532329600_BCJ-2016-0866CC43","doi-asserted-by":"publisher","first-page":"e1501235","DOI":"10.1126\/sciadv.1501235","article-title":"Conditional iron and pH-dependent activity of a non-enzymatic glycolysis and pentose phosphate pathway","volume":"2","author":"Keller","year":"2016","journal-title":"Sci. Adv."},{"key":"2021112216532329600_BCJ-2016-0866CC44","doi-asserted-by":"publisher","first-page":"927","DOI":"10.1111\/brv.12140","article-title":"The return of metabolism: biochemistry and physiology of the pentose phosphate pathway","volume":"90","author":"Stincone","year":"2015","journal-title":"Biol. Rev. Camb. Philos. Soc."},{"key":"2021112216532329600_BCJ-2016-0866CC45","doi-asserted-by":"publisher","first-page":"47","DOI":"10.1111\/j.1574-6941.1996.tb00332.x","article-title":"A systematic survey for thermophilic fermentative bacteria and archaea in high temperature petroleum reservoirs","volume":"21","author":"Grassia","year":"1996","journal-title":"FEMS Microbiol. Ecol."},{"key":"2021112216532329600_BCJ-2016-0866CC46","doi-asserted-by":"publisher","first-page":"461","DOI":"10.1139\/m69-081","article-title":"Thermostability of glycolytic enzymes from thermophilic clostridia","volume":"15","author":"Howell","year":"1969","journal-title":"Can. J. Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC47","doi-asserted-by":"publisher","first-page":"725","DOI":"10.1002\/msb.20145228","article-title":"Non-enzymatic glycolysis and pentose phosphate pathway-like reactions in a plausible Archean ocean","volume":"10","author":"Keller","year":"2014","journal-title":"Mol. Syst. Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC48","doi-asserted-by":"publisher","first-page":"7403","DOI":"10.1073\/pnas.1702274114","article-title":"Nonenzymatic gluconeogenesis-like formation of fructose 1,6-bisphosphate in ice","volume":"114","author":"Messner","year":"2017","journal-title":"Proc. Natl Acad. Sci. U.S.A."},{"key":"2021112216532329600_BCJ-2016-0866CC49","doi-asserted-by":"crossref","first-page":"1914","DOI":"10.1007\/978-1-4419-9863-7_1268","volume-title":"Encyclopedia of Systems Biology","author":"Wienkoop","year":"2013"},{"key":"2021112216532329600_BCJ-2016-0866CC50","doi-asserted-by":"publisher","first-page":"735","DOI":"10.1007\/s10545-007-0590-2","article-title":"Detection of transaldolase deficiency by quantification of novel seven-carbon chain carbohydrate biomarkers in urine","volume":"30","author":"Wamelink","year":"2007","journal-title":"J. Inherit. Metab. Dis."},{"key":"2021112216532329600_BCJ-2016-0866CC51","doi-asserted-by":"publisher","DOI":"10.1038\/nprot.2009.140","article-title":"Quantification of Saccharomyces cerevisiae pentose-phosphate pathway intermediates by LC-MS\/MS","author":"Wamelink","year":"2009","journal-title":"Nat. Protoc. Exch."},{"key":"2021112216532329600_BCJ-2016-0866CC52","doi-asserted-by":"publisher","first-page":"443","DOI":"10.1016\/j.gca.2014.03.004","article-title":"Iron isotopes in an Archean ocean analogue","volume":"133","author":"Busigny","year":"2014","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2021112216532329600_BCJ-2016-0866CC53","doi-asserted-by":"publisher","first-page":"205","DOI":"10.1016\/0301-9268(85)90031-2","article-title":"Iron and sulfur in the pre-biologic ocean","volume":"28","author":"Walker","year":"1985","journal-title":"Precambrian Res."},{"key":"2021112216532329600_BCJ-2016-0866CC54","doi-asserted-by":"publisher","first-page":"e1001926","DOI":"10.1371\/journal.pbio.1001926","article-title":"A bioenergetic basis for membrane divergence in archaea and bacteria","volume":"12","author":"Sojo","year":"2014","journal-title":"PLoS Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC55","doi-asserted-by":"publisher","first-page":"269","DOI":"10.1007\/s002030050780","article-title":"Microbial genomes and \u2018missing\u2019 enzymes: redefining biochemical pathways","volume":"172","author":"Cordwell","year":"1999","journal-title":"Arch. Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC56","doi-asserted-by":"publisher","first-page":"424","DOI":"10.1007\/PL00006565","article-title":"On the origin of metabolic pathways","volume":"49","author":"Lazcano","year":"1999","journal-title":"J. Mol. Evol."},{"key":"2021112216532329600_BCJ-2016-0866CC57","doi-asserted-by":"publisher","first-page":"719","DOI":"10.3390\/md9050719","article-title":"The biological deep sea hydrothermal vent as a model to study carbon dioxide capturing enzymes","volume":"9","author":"Minic","year":"2011","journal-title":"Mar. Drugs"},{"key":"2021112216532329600_BCJ-2016-0866CC58","doi-asserted-by":"publisher","first-page":"88","DOI":"10.1016\/j.asr.2003.05.006","article-title":"Prebiotic organic synthesis under hydrothermal conditions: an overview","volume":"33","author":"Simoneit","year":"2004","journal-title":"Adv. Space Res."},{"key":"2021112216532329600_BCJ-2016-0866CC59","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.surg.2014.07.014","article-title":"Autophagy: self-preservation through cannibalism of proteins and organelles","volume":"157","author":"Vlada","year":"2015","journal-title":"Surgery"},{"key":"2021112216532329600_BCJ-2016-0866CC60","doi-asserted-by":"publisher","first-page":"402","DOI":"10.1016\/j.tibs.2018.03.008","article-title":"Hypothesis on the synchronistic evolution of autotrophy and heterotrophy","volume":"43","author":"Gutekunst","year":"2018","journal-title":"Trends Biochem. Sci."},{"key":"2021112216532329600_BCJ-2016-0866CC61","doi-asserted-by":"publisher","first-page":"77","DOI":"10.1016\/j.mib.2017.12.010","article-title":"Native metals, electron bifurcation, and CO2 reduction in early biochemical evolution","volume":"43","author":"Sousa","year":"2018","journal-title":"Curr. Opin. Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC62","doi-asserted-by":"publisher","first-page":"343","DOI":"10.1002\/anie.201609615","article-title":"Spontaneous emergence of S-adenosylmethionine and the evolution of methylation","volume":"56","author":"Laurino","year":"2017","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"2021112216532329600_BCJ-2016-0866CC63","doi-asserted-by":"publisher","first-page":"793","DOI":"10.1016\/S0092-8674(00)81263-5","article-title":"The origin and early evolution of life: prebiotic chemistry, the pre-RNA world, and time","volume":"85","author":"Lazcano","year":"1996","journal-title":"Cell"},{"key":"2021112216532329600_BCJ-2016-0866CC64","doi-asserted-by":"publisher","first-page":"1135","DOI":"10.1130\/0091-7613(1996)024&lt;1135:EIPGPF&gt;2.3.CO;2","article-title":"Evidence in pre-2.2 Ga paleosols for the early evolution of atmospheric oxygen and terrestrial biota","volume":"24","author":"Ohmoto","year":"1996","journal-title":"Geology"},{"key":"2021112216532329600_BCJ-2016-0866CC65","doi-asserted-by":"publisher","first-page":"81","DOI":"10.1111\/j.1462-2920.2006.01118.x","article-title":"Autotrophic CO2 fixation via the reductive tricarboxylic acid cycle in different lineages within the phylum Aquificae: evidence for two ways of citrate cleavage","volume":"9","author":"H\u00fcgler","year":"2007","journal-title":"Environ. Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC66","doi-asserted-by":"publisher","first-page":"47","DOI":"10.1007\/BF00032643","article-title":"A reverse KREBS cycle in photosynthesis: consensus at last","volume":"24","author":"Buchanan","year":"1990","journal-title":"Photosynth. Res."},{"key":"2021112216532329600_BCJ-2016-0866CC67","doi-asserted-by":"publisher","first-page":"7704","DOI":"10.1073\/pnas.110153997","article-title":"The origin of intermediary metabolism","volume":"97","author":"Morowitz","year":"2000","journal-title":"Proc. Natl Acad. Sci. U.S.A."},{"key":"2021112216532329600_BCJ-2016-0866CC68","doi-asserted-by":"publisher","first-page":"13168","DOI":"10.1073\/pnas.0404922101","article-title":"Universality in intermediary metabolism","volume":"101","author":"Smith","year":"2004","journal-title":"Proc. Natl Acad. Sci. U.S.A."},{"key":"2021112216532329600_BCJ-2016-0866CC69","doi-asserted-by":"publisher","first-page":"200","DOI":"10.1073\/pnas.87.1.200","article-title":"Evolution of the first metabolic cycles","volume":"87","author":"W\u00e4chtersh\u00e4user","year":"1990","journal-title":"Proc. Natl Acad. Sci. U.S.A."},{"key":"2021112216532329600_BCJ-2016-0866CC70","doi-asserted-by":"publisher","first-page":"16032","DOI":"10.1021\/ja066103k","article-title":"Driving parts of Krebs cycle in reverse through mineral photochemistry","volume":"128","author":"Zhang","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"2021112216532329600_BCJ-2016-0866CC71","doi-asserted-by":"publisher","first-page":"1716","DOI":"10.1038\/s41559-017-0311-7","article-title":"Metals promote sequences of the reverse Krebs cycle","volume":"1","author":"Muchowska","year":"2017","journal-title":"Nat. Ecol. Evol."},{"key":"2021112216532329600_BCJ-2016-0866CC72","doi-asserted-by":"publisher","first-page":"1019","DOI":"10.1038\/s41559-018-0542-2","article-title":"Native iron reduces CO2 to intermediates and end-products of the acetyl-CoA pathway","volume":"2","author":"Varma","year":"2018","journal-title":"Nat. Ecol. Evol."},{"key":"2021112216532329600_BCJ-2016-0866CC73","first-page":"148","article-title":"The role of citric acid in intermediate metabolism in animal tissues","volume":"4","author":"Krebs","year":"1937","journal-title":"Enzymologia"},{"key":"2021112216532329600_BCJ-2016-0866CC74","doi-asserted-by":"publisher","first-page":"83","DOI":"10.1038\/s41559-017-0083","article-title":"Sulfate radicals enable a non-enzymatic Krebs cycle precursor","volume":"1","author":"Keller","year":"2017","journal-title":"Nat. Ecol. Evol."},{"key":"2021112216532329600_BCJ-2016-0866CC75","doi-asserted-by":"publisher","first-page":"91","DOI":"10.1038\/s41467-017-02591-0","article-title":"Linked cycles of oxidative decarboxylation of glyoxylate as protometabolic analogs of the citric acid cycle","volume":"9","author":"Springsteen","year":"2018","journal-title":"Nat. Commun."},{"key":"2021112216532329600_BCJ-2016-0866CC76","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.molcel.2007.03.016","article-title":"Hydrogen peroxide sensing and signaling","volume":"26","author":"Veal","year":"2007","journal-title":"Mol. Cell"},{"key":"2021112216532329600_BCJ-2016-0866CC77","doi-asserted-by":"publisher","first-page":"e1001446","DOI":"10.1371\/journal.pbio.1001446","article-title":"Reconstruction of ancestral metabolic enzymes reveals molecular mechanisms underlying evolutionary innovation through gene duplication","volume":"10","author":"Voordeckers","year":"2012","journal-title":"PLoS Biol."},{"key":"2021112216532329600_BCJ-2016-0866CC78","doi-asserted-by":"publisher","first-page":"312","DOI":"10.1104\/pp.106.077073","article-title":"Reactive species and antioxidants. Redox biology is a fundamental theme of aerobic life","volume":"141","author":"Halliwell","year":"2006","journal-title":"Plant Physiol."},{"key":"2021112216532329600_BCJ-2016-0866CC79","volume-title":"Beginnings of Cellular Life: Metabolism Recapitulates Biogenesis","author":"Morowitz","year":"1992"},{"key":"2021112216532329600_BCJ-2016-0866CC80","doi-asserted-by":"publisher","first-page":"495","DOI":"10.1038\/nchem.1650","article-title":"Competition between model protocells driven by an encapsulated catalyst","volume":"5","author":"Adamala","year":"2013","journal-title":"Nat. Chem."},{"key":"2021112216532329600_BCJ-2016-0866CC81","doi-asserted-by":"publisher","first-page":"65","DOI":"10.1016\/0891-5849(89)90102-0","article-title":"Oxygen radical chemistry of polyunsaturated fatty acids","volume":"7","author":"Gardner","year":"1989","journal-title":"Free Radic. Biol. Med."},{"key":"2021112216532329600_BCJ-2016-0866CC82","doi-asserted-by":"publisher","first-page":"456","DOI":"10.1016\/0003-9861(92)90016-P","article-title":"Oxidation of polyunsaturated fatty acids and lipids through thiyl and sulfonyl radicals: reaction kinetics, and influence of oxygen and structure of thiyl radicals","volume":"292","author":"Sch\u00f6neich","year":"1992","journal-title":"Arch. Biochem. Biophys."},{"key":"2021112216532329600_BCJ-2016-0866CC83","doi-asserted-by":"publisher","first-page":"281","DOI":"10.1016\/S0966-842X(99)01539-5","article-title":"Variation and evolution of the citric-acid cycle: a genomic perspective","volume":"7","author":"Huynen","year":"1999","journal-title":"Trends Microbiol."},{"key":"2021112216532329600_BCJ-2016-0866CC84","doi-asserted-by":"publisher","first-page":"293","DOI":"10.1007\/BF02338838","article-title":"The puzzle of the Krebs citric acid cycle: assembling the pieces of chemically feasible reactions, and opportunism in the design of metabolic pathways during evolution","volume":"43","author":"Mel\u00e9ndez-Hevia","year":"1996","journal-title":"J. Mol. Evol."},{"key":"2021112216532329600_BCJ-2016-0866CC85","doi-asserted-by":"publisher","first-page":"219","DOI":"10.1111\/j.1365-3040.1990.tb01306.x","article-title":"The relationship between the Rubisco reaction mechanism and models of photosynthesis","volume":"13","author":"Collatz","year":"1990","journal-title":"Plant Cell Environ."},{"key":"2021112216532329600_BCJ-2016-0866CC86","doi-asserted-by":"publisher","first-page":"549","DOI":"10.1021\/cr970010r","article-title":"Mechanism of Rubisco: the carbamate as general base","volume":"98","author":"Cleland","year":"1998","journal-title":"Chem. Rev."},{"key":"2021112216532329600_BCJ-2016-0866CC87","doi-asserted-by":"publisher","first-page":"124","DOI":"10.1016\/j.febslet.2004.06.064","article-title":"Oxygen-dependent H2O2 production by Rubisco","volume":"571","author":"Kim","year":"2004","journal-title":"FEBS Lett."},{"key":"2021112216532329600_BCJ-2016-0866CC88","doi-asserted-by":"publisher","DOI":"10.12688\/wellcomeopenres.12103.1","article-title":"Primordial Krebs-cycle-like non-enzymatic reactions detected by mass spectrometry and nuclear magnetic resonance","volume":"2","author":"Keller","year":"2017","journal-title":"Wellcome Open Res."},{"key":"2021112216532329600_BCJ-2016-0866CC89","doi-asserted-by":"publisher","first-page":"1151","DOI":"10.1126\/science.1093057","article-title":"Prebiotic amino acids as asymmetric catalysts","volume":"303","author":"Pizzarello","year":"2004","journal-title":"Science"},{"key":"2021112216532329600_BCJ-2016-0866CC90","doi-asserted-by":"publisher","first-page":"8914","DOI":"10.1021\/ja047930t","article-title":"The direct amino acid-catalyzed asymmetric incorporation of molecular oxygen to organic compounds","volume":"126","author":"C\u00f3rdova","year":"2004","journal-title":"J. Am. Chem. Soc."}],"container-title":["Biochemical Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/portlandpress.com\/biochemj\/article-pdf\/475\/16\/2577\/693325\/bcj-2016-0866c.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/portlandpress.com\/biochemj\/article-pdf\/475\/16\/2577\/693325\/bcj-2016-0866c.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2021,11,22]],"date-time":"2021-11-22T18:37:56Z","timestamp":1637606276000},"score":1,"resource":{"primary":{"URL":"https:\/\/portlandpress.com\/biochemj\/article\/475\/16\/2577\/49772\/An-appeal-to-magic-The-discovery-of-a-non"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,8,29]]},"references-count":90,"journal-issue":{"issue":"16","published-print":{"date-parts":[[2018,8,31]]}},"URL":"https:\/\/doi.org\/10.1042\/bcj20160866","relation":{},"ISSN":["0264-6021","1470-8728"],"issn-type":[{"value":"0264-6021","type":"print"},{"value":"1470-8728","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,8,29]]}}}