{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,6]],"date-time":"2026-09-06T10:43:00Z","timestamp":1788691380770,"version":"build-2803163510"},"reference-count":45,"publisher":"MDPI AG","issue":"6","license":[{"start":{"date-parts":[[2023,5,31]],"date-time":"2023-05-31T00:00:00Z","timestamp":1685491200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"NSF and the NASA Astrobiology Program, under the NSF Center for Chemical Evolution","award":["CHE-1504217"],"award-info":[{"award-number":["CHE-1504217"]}]},{"name":"NSF and the NASA Astrobiology Program, under the NSF Center for Chemical Evolution","award":["436 80NM0018F0612"],"award-info":[{"award-number":["436 80NM0018F0612"]}]},{"name":"NASA Habitable Worlds program","award":["CHE-1504217"],"award-info":[{"award-number":["CHE-1504217"]}]},{"name":"NASA Habitable Worlds program","award":["436 80NM0018F0612"],"award-info":[{"award-number":["436 80NM0018F0612"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Life"],"abstract":"<jats:p>The formose reaction is a plausible prebiotic chemistry, famed for its production of sugars. In this work, we demonstrate that the Cannizzaro process is the dominant process in the formose reaction under many different conditions, thus necessitating a catalyst for the formose reaction under various environmental circumstances. The investigated formose reactions produce primarily organic acids associated with metabolism, a protometabolic system, and yield very little sugar left over. This is due to many of the acids forming from the degradation and Cannizaro reactions of many of the sugars produced during the formose reaction. We also show the heterogeneous Lewis-acid-based catalysis of the formose reaction by mineral systems associated with serpentinization. The minerals that showed catalytic activity include olivine, serpentinite, and calcium, and magnesium minerals including dolomite, calcite, and our Ca\/Mg-chemical gardens. In addition, computational studies were performed for the first step of the formose reaction to investigate the reaction of formaldehyde, to either form methanol and formic acid under a Cannizzaro reaction or to react to form glycolaldehyde. Here, we postulate that serpentinization is therefore the startup process necessary to kick off a simple proto metabolic system\u2014the formose protometabolic system.<\/jats:p>","DOI":"10.3390\/life13061297","type":"journal-article","created":{"date-parts":[[2023,6,1]],"date-time":"2023-06-01T01:40:56Z","timestamp":1685583656000},"page":"1297","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Serpentinization-Associated Mineral Catalysis of the Protometabolic Formose System"],"prefix":"10.3390","volume":"13","author":[{"given":"Arthur","family":"Omran","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of North Florida, Jacksonville, FL 32224, USA"},{"name":"Department of Geosciences, University of South Florida, Tampa, FL 33620, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Asbell","family":"Gonzalez","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of North Florida, Jacksonville, FL 32224, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1238-190X","authenticated-orcid":false,"given":"Cesar","family":"Menor-Salvan","sequence":"additional","affiliation":[{"name":"Departmento de Biologia de Sistemas, Universidad de Alcala, 28805 Alcala de Henares, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michael","family":"Gaylor","sequence":"additional","affiliation":[{"name":"Analytical Sciences, Small Molecules Technologies, Bayer U.S., Saint Louis, MO 63167, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Physics and Atmospheric Sciences, Jackson State University, Jackson, MS 39217, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5290-6136","authenticated-orcid":false,"given":"Jerzy","family":"Leszczynski","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Physics and Atmospheric Sciences, Jackson State University, Jackson, MS 39217, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2635-0143","authenticated-orcid":false,"given":"Tian","family":"Feng","sequence":"additional","affiliation":[{"name":"Department of Geosciences, University of South Florida, Tampa, FL 33620, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,5,31]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Yadav, M., and Yadav, H.S. (2021). Biochemistry: Fundamentals and Bioenergetics, Bentham Science Publishers.","DOI":"10.2174\/97816810884711210101"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"20200423","DOI":"10.1098\/rsta.2020.0423","article-title":"Protometabolism as out-of-equilibrium chemistry","volume":"380","author":"Nader","year":"2022","journal-title":"Philos. Trans. R. Soc. A"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3047","DOI":"10.1039\/D1CS01178B","article-title":"Systems chemistry of peptide-assemblies for biochemical transformations","volume":"51","author":"Chatterjee","year":"2022","journal-title":"Chem. Soc. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Omran, A. (2020). Plausibility of the Formose Reaction in Alkaline Hydrothermal Vent Environments. Space Life Sci., 1\u201313.","DOI":"10.1007\/s11084-020-09599-5"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1016\/S0040-4039(01)99487-0","article-title":"On the mechanism of the formose reaction","volume":"1","author":"Breslow","year":"1959","journal-title":"Tetrahedron Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"3720","DOI":"10.1021\/ja410886c","article-title":"Deuterium Studies Reveal a New Mechanism for the Formose Reaction Involving Hydride Shifts","volume":"136","author":"Appayee","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_7","first-page":"295","article-title":"Bildung einer zuckerartigen Substanz durch Synthese","volume":"120","author":"Butlerow","year":"1861","journal-title":"Eur. J. Org. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"196","DOI":"10.1126\/science.1092464","article-title":"Borate Minerals Stabilize Ribose","volume":"303","author":"Ricardo","year":"2004","journal-title":"Science"},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Omran, A., Menor-Salvan, C., Springsteen, G., and Pasek, M. (2020). The Messy Alkaline Formose Reaction and Its Link to Metabolism. Life, 10.","DOI":"10.3390\/life10080125"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"111","DOI":"10.1016\/j.precamres.2008.04.002","article-title":"The prebiotic geochemistry of formaldehyde","volume":"164","author":"Cleaves","year":"2008","journal-title":"Precambrian Res."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"383","DOI":"10.1007\/BF02101643","article-title":"Prebiotic synthesis in atmospheres containing CH4, CO, and CO2","volume":"19","author":"Schlesinger","year":"1983","journal-title":"J. Mol. Evol."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1007\/BF02627950","article-title":"The potential for prebiotic synthesis in hydrothermal systems","volume":"24","author":"Ferris","year":"1994","journal-title":"Orig. Life Evol. Biosph."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"125","DOI":"10.1038\/355125a0","article-title":"Endogenous production, exogenous delivery and impact-shock synthesis of organic molecules: An inventory for the origins of life","volume":"355","author":"Chyba","year":"1992","journal-title":"Nature"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"129","DOI":"10.1038\/343129a0","article-title":"Impact delivery and erosion of planetary oceans in the early inner Solar System","volume":"343","author":"Chyba","year":"1990","journal-title":"Nature"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"184","DOI":"10.1016\/j.epsl.2008.10.012","article-title":"Serpentinization of the martian crust during Noachian","volume":"277","author":"Quesnel","year":"2009","journal-title":"Earth Planet. Sci. Lett."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"L10203","DOI":"10.1029\/2005GL022691","article-title":"Have olivine, will gas: Serpentinization and the abiogenic production of methane on Mars","volume":"32","author":"Oze","year":"2005","journal-title":"Geophys. Res. Lett."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"364","DOI":"10.1089\/ast.2006.6.364","article-title":"Serpentinization and Its Implications for Life on the Early Earth and Mars","volume":"6","author":"Schulte","year":"2006","journal-title":"Astrobiology"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"587","DOI":"10.1089\/ast.2014.1188","article-title":"Serpentinization and the formation of H2 and CH4 on celestial bodies (planets, moons, comets)","volume":"15","author":"Holm","year":"2015","journal-title":"Astrobiology"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"3625","DOI":"10.1016\/j.gca.2006.04.016","article-title":"Formation and evolution of carbonate chimneys at the Lost City Hydrothermal Field","volume":"70","author":"Ludwig","year":"2006","journal-title":"Geochim. Cosmochim. Acta"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1428","DOI":"10.1126\/science.1102556","article-title":"A Serpentinite-Hosted Ecosystem: The Lost City Hydrothermal Field","volume":"307","author":"Kelley","year":"2005","journal-title":"Science"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"375","DOI":"10.1002\/2015GC005869","article-title":"Geologic evolution of the Lost City Hydrothermal Field","volume":"17","author":"Denny","year":"2016","journal-title":"Geochem. Geophys. Geosyst."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"8652","DOI":"10.1021\/acs.chemrev.5b00014","article-title":"From Chemical Gardens to Chemobrionics","volume":"115","author":"Barge","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"4393","DOI":"10.1002\/ange.201107754","article-title":"Formation and Evolution of Chemical Gradients and Potential Differences Across Self-Assembling Inorganic Membranes","volume":"124","author":"Glaab","year":"2012","journal-title":"Angew. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2806","DOI":"10.1021\/acs.biochem.6b00255","article-title":"A Global Scale Scenario for Prebiotic Chemistry: Silica-Based Self-Assembled Mineral Structures and Formamide","volume":"55","author":"Saladino","year":"2016","journal-title":"Biochemistry"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"95","DOI":"10.1007\/s10498-011-9150-3","article-title":"Calcium Carbonate Nucleation in an Alkaline Lake Surface Water, Pyramid Lake, Nevada, USA","volume":"18","author":"Reddy","year":"2012","journal-title":"Aquat. Geochem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"197","DOI":"10.1111\/j.1574-6941.1994.tb00066.x","article-title":"Precipatation of calcium carbonate by Vibrio spp. from an inland saltern","volume":"13","author":"Rivadeneyra","year":"1994","journal-title":"FEMS Microbiol. Ecol."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"519","DOI":"10.1111\/j.1745-6584.1987.tb02881.x","article-title":"Hydrogeology of an Alkaline Fly Ash Landfill in Eastern Iowa","volume":"25","author":"Spencer","year":"1987","journal-title":"Groundwater"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"4307","DOI":"10.1021\/cr030680z","article-title":"Lewis Acids: From Conventional Homogeneous to Green Homogeneous and Heterogeneous Catalysis","volume":"103","author":"Corma","year":"2003","journal-title":"Chem. Rev."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"4243","DOI":"10.1021\/jacs.5b01352","article-title":"Metal\u2013Organic Framework Based upon the Synergy of a Br\u00f8nsted Acid Framework and Lewis Acid Centers as a Highly Efficient Heterogeneous Catalyst for Fixed-Bed Reactions","volume":"137","author":"Li","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"4268","DOI":"10.1021\/acscatal.2c00229","article-title":"Structure\u2013Activity Relationships in Lewis Acid\u2013Base Heterogeneous Catalysis","volume":"12","author":"Abdelgaid","year":"2022","journal-title":"ACS Catal."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1175","DOI":"10.1039\/c0gc00923g","article-title":"Selective conversion of trioses to lactates over Lewis acid heterogeneous catalysts","volume":"13","author":"Li","year":"2011","journal-title":"Green Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"3133","DOI":"10.1039\/C9GC00770A","article-title":"Woody species: A new bio-based material for dual Ca\/Mg catalysis with remarkable Lewis acidity properties","volume":"21","author":"Deyris","year":"2019","journal-title":"Green Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.cplett.2010.11.060","article-title":"Applications and validations of the Minnesota density functionals","volume":"502","author":"Zhao","year":"2011","journal-title":"Chem. Phys. Lett."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 Suite of Density Functional for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functional and Systematic Testing of Four M06-Class Functional and 12 Other Functional","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"157","DOI":"10.1021\/ar700111a","article-title":"Density Functionals with Broad Applicability in Chemistry","volume":"41","author":"Zhao","year":"2008","journal-title":"Acc. Chem. Res."},{"key":"ref_36","unstructured":"Hehre, W.J., Radom, L., Schleyer, P.R., and Pople, J.A. (1986). Ab Initio Molecular Orbital Theory, Wiley."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1016\/0009-2614(96)00349-1","article-title":"Ab initio study of solvated molecules: A new implementation of the polarizable continuum model","volume":"255","author":"Cossi","year":"1996","journal-title":"Chem. Phys. Lett."},{"key":"ref_38","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2009). Gaussian 09, Gaussian, Inc.. Revision A.1."},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Armbruster, T., and Danisi, R.M. (2015). Highlights in Mineralogical Crystallography, Walter de Gruyter.","DOI":"10.1515\/9783110417104"},{"key":"ref_40","first-page":"4515","article-title":"Bial\u2019s Test, a Fast and Affordable way to Detect Formaldehyde","volume":"27","author":"Omran","year":"2020","journal-title":"Biomed. Res. J."},{"key":"ref_41","doi-asserted-by":"crossref","unstructured":"Omran, A., and Pasek, M. (2020). A Constructive Way to Think about Different Hydrothermal Environments for the Origins of Life. Life, 10.","DOI":"10.3390\/life10040036"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"140","DOI":"10.1038\/s42004-020-00387-w","article-title":"Mineral-mediated carbohydrate synthesis by mechanical forces in a primordial geochemical setting","volume":"3","author":"Haas","year":"2020","journal-title":"Commun. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"9457","DOI":"10.1021\/ja201769f","article-title":"Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles","volume":"133","author":"Kim","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"1787","DOI":"10.1039\/c1nj20191c","article-title":"Hydrothermal formose reaction","volume":"35","author":"Kopetzki","year":"2011","journal-title":"New J. Chem."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"8659","DOI":"10.1021\/acs.jpca.7b08002","article-title":"Metal-Ion- and Hydrogen-Bond-Mediated Interstellar Prebiotic Chemistry: The First Step in the Formose Reaction","volume":"121","author":"Thripati","year":"2017","journal-title":"J. Phys. Chem. A"}],"container-title":["Life"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2075-1729\/13\/6\/1297\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:46:08Z","timestamp":1760125568000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2075-1729\/13\/6\/1297"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,5,31]]},"references-count":45,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2023,6]]}},"alternative-id":["life13061297"],"URL":"https:\/\/doi.org\/10.3390\/life13061297","relation":{},"ISSN":["2075-1729"],"issn-type":[{"value":"2075-1729","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,5,31]]}}}