{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T22:22:17Z","timestamp":1790720537884,"version":"4.1.0"},"reference-count":47,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2023,3,31]],"date-time":"2023-03-31T00:00:00Z","timestamp":1680220800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"NASA Exobiology program","award":["80NSSC22K0509"],"award-info":[{"award-number":["80NSSC22K0509"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Life"],"abstract":"<jats:p>The in-fall of meteorites and interstellar dust particles during the Hadean\u2013Archean heavy bombardment may have provided the early Earth with various reduced oxidation state phosphorus compounds and minerals, including phosphite (HPO32\u2212)([Pi(III)]). The ion phosphite ([Pi(III)])has been postulated to be ubiquitous on the early Earth and consequently could have played a role in the emergence of organophosphorus compounds and other prebiotically relevant P species such as condensed P compounds, e.g., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III\u2013V)]). In the present study, we show that phosphite ([Pi(III)]) oxidizes under mild heating conditions (e.g., wet\u2013dry cycles and a prebiotic scenario mimicking a mildly hot-evaporating\/drying pool on the early Earth at 78\u201383 \u00b0C) in the presence of urea and other additives, resulting in changes to orthophosphate ([Pi(V)]) alongside the formation of reactive condensed P compounds (e.g., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III\u2013V)])) through a one-pot mechanism. Additionally, we also show that phosphite ([Pi(III)]) and the condensed P compounds readily react with organics (nucleosides and organic alcohol) to form organophosphorus compounds.<\/jats:p>","DOI":"10.3390\/life13040920","type":"journal-article","created":{"date-parts":[[2023,3,31]],"date-time":"2023-03-31T09:12:59Z","timestamp":1680253979000},"page":"920","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Prebiotic Chemistry of Phosphite: Mild Thermal Routes to Form Condensed-P Energy Currency Molecules Leading Up to the Formation of Organophosphorus Compounds"],"prefix":"10.3390","volume":"13","author":[{"given":"Maheen","family":"Gull","sequence":"first","affiliation":[{"name":"School of Geosciences, University of South Florida, Tampa, FL 33584, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tian","family":"Feng","sequence":"additional","affiliation":[{"name":"School of Geosciences, University of South Florida, Tampa, FL 33584, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Harold A.","family":"Cruz","sequence":"additional","affiliation":[{"name":"Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5238-610X","authenticated-orcid":false,"given":"Ramanarayanan","family":"Krishnamurthy","sequence":"additional","affiliation":[{"name":"Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1280-9555","authenticated-orcid":false,"given":"Matthew A.","family":"Pasek","sequence":"additional","affiliation":[{"name":"School of Geosciences, University of South Florida, Tampa, FL 33584, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,3,31]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"853","DOI":"10.1073\/pnas.0708205105","article-title":"Rethinking early Earth phosphorus geochemistry","volume":"105","author":"Pasek","year":"2008","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1743","DOI":"10.1098\/rstb.2006.1901","article-title":"Phosphorus in prebiotic chemistry","volume":"361","author":"Schwartz","year":"2006","journal-title":"Philos. Trans. R. Soc. Lond. B Biol. Sci."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"4-1","DOI":"10.1029\/2001JE001529","article-title":"Cataclysmic bombardment throughout the inner solar system 3.9\u20134.0 Ga","volume":"107","author":"Kring","year":"2002","journal-title":"J. Geophys. Res. Planets"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1847","DOI":"10.1126\/science.1113544","article-title":"The origin of planetary impactors in the inner solar system","volume":"309","author":"Strom","year":"2005","journal-title":"Science"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"459","DOI":"10.1023\/A:1006523226472","article-title":"Primary sources of phosphorus and phosphates in chemical evolution","volume":"27","year":"1997","journal-title":"Orig. Life Evol. Biosph."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1007\/s11084-007-9110-5","article-title":"Extraterrestrial flux of potentially prebiotic C, N, and P to the early Earth","volume":"38","author":"Pasek","year":"2008","journal-title":"Orig. Life Evol. Biosph."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"515","DOI":"10.1089\/ast.2005.5.515","article-title":"Aqueous corrosion of phosphide minerals from iron meteorites: A highly reactive source of prebiotic phosphorus on the surface of the early Earth","volume":"5","author":"Pasek","year":"2005","journal-title":"Astrobiology"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1721","DOI":"10.1016\/j.gca.2006.12.018","article-title":"A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life","volume":"71","author":"Pasek","year":"2007","journal-title":"Geochim. Cosmochim. Acta"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"344","DOI":"10.1038\/s41561-020-0556-7","article-title":"Supply of phosphate to early Earth by photogeochemistry after meteoritic weathering","volume":"13","author":"Ritson","year":"2020","journal-title":"Nat. Geosci."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"329","DOI":"10.1016\/j.gsf.2016.06.008","article-title":"Schreibersite on the early Earth: Scenarios for prebiotic phosphorylation","volume":"8","author":"Pasek","year":"2017","journal-title":"Geosci. Front."},{"key":"ref_11","unstructured":"Melosh, H.J. (1989). Impact Cratering: A Geologic Process, Oxford University Press. [1st ed.]."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"329","DOI":"10.1146\/annurev.earth.32.101802.120458","article-title":"Spherule layers\u2014Records of ancient impacts","volume":"32","author":"Simonson","year":"2004","journal-title":"Annu. Rev. Earth Planet Sci."},{"key":"ref_13","first-page":"253","article-title":"Rust and schreibersite in Apollo 16 highland rocks-Manifestations of volatile-element mobility","volume":"Volume 12","author":"Hunter","year":"1982","journal-title":"Proceedings of the 12th Lunar and Planetary Science Conference"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"847","DOI":"10.1134\/S0016702906090011","article-title":"Experimental data on the thermal reduction of phosphorus and iron and their significance for the interpretation of the impact reworking of lunar materials","volume":"44","author":"Yakovlev","year":"2006","journal-title":"Geochem. Int."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4109","DOI":"10.1016\/0016-7037(92)90023-C","article-title":"Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite","volume":"56","author":"Cooper","year":"1992","journal-title":"Geochim. Cosmochim. Acta"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"10089","DOI":"10.1073\/pnas.1303904110","article-title":"Evidence for reactive reduced phosphorus species in the early Archean Ocean","volume":"110","author":"Pasek","year":"2013","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"553","DOI":"10.1038\/ngeo580","article-title":"Lightning-induced reduction of phosphorus oxidation state","volume":"2","author":"Pasek","year":"2009","journal-title":"Nat. Geosci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"7671","DOI":"10.1021\/es901469t","article-title":"Detection of geothermal phosphite using high-performance liquid chromatography","volume":"43","author":"Pech","year":"2009","journal-title":"Environ. Sci. Technol."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"15468","DOI":"10.1073\/pnas.1408134111","article-title":"Redox chemistry in the phosphorus biogeochemical cycle","volume":"111","author":"Pasek","year":"2014","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"149","DOI":"10.1016\/j.chemgeo.2017.11.008","article-title":"Phosphorylation on the early earth","volume":"475","author":"Pasek","year":"2017","journal-title":"Chem. Geol."},{"key":"ref_21","first-page":"479","article-title":"Phosphorus as a factor in the origin of life","volume":"43","author":"Gulick","year":"1955","journal-title":"Am. Sci."},{"key":"ref_22","doi-asserted-by":"crossref","unstructured":"Egel, R., Lankenau, D.-H., and Mulkidjanian, A.Y. (2011). Origins of Life: The Primal Self-Organization, Springer. [1st ed.].","DOI":"10.1007\/978-3-642-21625-1"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"193","DOI":"10.3390\/challe5020193","article-title":"Prebiotic Phosphorylation Reactions on the Early Earth","volume":"5","author":"Gull","year":"2014","journal-title":"Challenges"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"17198","DOI":"10.1038\/srep17198","article-title":"Nucleoside phosphorylation by the mineral schreibersite","volume":"5","author":"Gull","year":"2015","journal-title":"Sci. Rep."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"20160","DOI":"10.1039\/C6CP00836D","article-title":"The evolution of the surface of the mineral schreibersite in prebiotic chemistry","volume":"18","author":"Qasim","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Gull, M., Feng, T., and Pasek, M.A. (2022). Results of an Eight-Year Extraction of Phosphorus Minerals within the Seymchan Meteorite. Life, 12.","DOI":"10.3390\/life12101591"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"386","DOI":"10.3390\/life3030386","article-title":"Phosphate activation via reduced oxidation state phosphorus (P). Mild routes to condensed-P energy currency molecules","volume":"3","author":"Kee","year":"2013","journal-title":"Life"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"503","DOI":"10.1006\/jtbi.1996.0385","article-title":"Entropy and charge in molecular evolution\u2014The case of phosphate","volume":"187","author":"Arrhenius","year":"1997","journal-title":"J. Theor. Biol."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"251","DOI":"10.1007\/BF01654094","article-title":"The effect of Mg2+ and Ca2+ on urea-catalyzed phosphorylation reactions","volume":"2","author":"Handschuh","year":"1973","journal-title":"J. Mol. Evol."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1111\/j.1472-4669.2012.00323.x","article-title":"The significance of Mg in prebiotic geochemistry","volume":"10","author":"Holm","year":"2012","journal-title":"Geobiology"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"483","DOI":"10.1007\/s11084-011-9235-4","article-title":"Links between hydrothermal environments, pyrophosphate, Na+, and early evolution","volume":"41","author":"Holm","year":"2011","journal-title":"Orig. Life Evol. Biosph."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"553","DOI":"10.1038\/s41561-019-0371-1","article-title":"Ammonium availability in the Late Archaean nitrogen cycle","volume":"12","author":"Yang","year":"2019","journal-title":"Nat. Geosci."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"60","DOI":"10.1007\/s00239-022-10086-w","article-title":"Organophosphorus Compound Formation through the Oxidation of Reduced Oxidation State Phosphorus Compounds on the Hadean Earth","volume":"91","author":"Gull","year":"2022","journal-title":"J. Mol. Evol."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"883","DOI":"10.1073\/pnas.1916109117","article-title":"A carbonate-rich lake solution to the phosphate problem of the origin of life","volume":"117","author":"Toner","year":"2020","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"539","DOI":"10.1579\/0044-7447-33.8.539","article-title":"A perspective on the role of minerals in prebiotic synthesis","volume":"33","author":"Schoonen","year":"2004","journal-title":"AMBIO A J. Hum. Environ."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"984","DOI":"10.1126\/science.1182669","article-title":"The silicate-mediated formose reaction: Bottom-up synthesis of sugar silicates","volume":"327","author":"Lambert","year":"2010","journal-title":"Science"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"231","DOI":"10.1007\/BF01654004","article-title":"Further studies of urea-catalyzed phosphorylation reactions","volume":"2","author":"Orgel","year":"1973","journal-title":"J. Mol. Evol."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"490","DOI":"10.1126\/science.171.3970.490","article-title":"Urea-inorganic phosphate mixtures as prebiotic phosphorylating agents","volume":"171","author":"Lohrmann","year":"1971","journal-title":"Science"},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Gull, M., Omran, A., Feng, T., and Pasek, M.A. (2020). Silicate-, magnesium ion-, and urea-induced prebiotic phosphorylation of uridine via pyrophosphate; revisiting the hot drying water pool scenario. Life, 10.","DOI":"10.3390\/life10080122"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"109","DOI":"10.1007\/s00239-013-9605-9","article-title":"Prebiotic phosphate ester syntheses in a deep eutectic solvent","volume":"78","author":"Gull","year":"2014","journal-title":"J. Mol. Evol."},{"key":"ref_41","doi-asserted-by":"crossref","unstructured":"Gull, M., and Pasek, M.A. (2021). Catalytic Prebiotic Formation of Glycerol Phosphate Esters and an Estimation of Their Steady State Abundance under Plausible Early Earth Conditions. Catalysts, 11.","DOI":"10.3390\/catal11111384"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"633","DOI":"10.1007\/BF00325563","article-title":"pH-dependence of 31 P-NMR spectroscopic parameters of monofluorophosphate, phosphate, hypophosphate, phosphonate, phosphinate and their dimers and trimers","volume":"348","author":"Yoza","year":"1994","journal-title":"Fresenius J. Anal. Chem."},{"key":"ref_43","unstructured":"Pasek, M.A. (2018). Phosphorus NMR of Natural Samples, Free Radical Consulting. [1st ed.]."},{"key":"ref_44","doi-asserted-by":"crossref","unstructured":"Gull, M., and Pasek, M.A. (2021). The role of glycerol and its derivatives in the biochemistry of living organisms, and their prebiotic origin and significance in the evolution of life. Catalysts, 11.","DOI":"10.3390\/catal11010086"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"368","DOI":"10.4139\/sfj.57.368","article-title":"Effect of pH on conversion of hypophosphite and phosphite to phosphate by wet oxidation","volume":"57","author":"Fujita","year":"2006","journal-title":"J. Surf. Finish. Soc. Jpn."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1038\/s42004-022-00761-w","article-title":"Phosphorylation in liquid sulfur dioxide under prebiotically plausible conditions","volume":"5","author":"Sydow","year":"2022","journal-title":"Commun. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"5122","DOI":"10.1021\/acsomega.7b00970","article-title":"Sulfurization of H-phosphonate diesters by elemental sulfur under aqueous conditions","volume":"2","year":"2017","journal-title":"ACS Omega"}],"container-title":["Life"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2075-1729\/13\/4\/920\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:07:27Z","timestamp":1760123247000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2075-1729\/13\/4\/920"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,3,31]]},"references-count":47,"journal-issue":{"issue":"4","published-online":{"date-parts":[[2023,4]]}},"alternative-id":["life13040920"],"URL":"https:\/\/doi.org\/10.3390\/life13040920","relation":{},"ISSN":["2075-1729"],"issn-type":[{"value":"2075-1729","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,3,31]]}}}