Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sources

Abstract P-N species e.g., amidophosphates readily phosphorylate organics, thereby overcoming the so-called ‘Phosphate Problem’. However, the formation of amidophosphates by plausible early Earth geochemical pathways is limited. We herein show that ammonolysis of the prebiotically plausible dimer of...

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Main Authors: Maheen Gull, Harold A. Cruz, Ramanarayanan Krishnamurthy, Matthew A. Pasek
Format: Article
Language:English
Published: Nature Portfolio 2025-06-01
Series:Communications Chemistry
Online Access:https://doi.org/10.1038/s42004-025-01577-0
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author Maheen Gull
Harold A. Cruz
Ramanarayanan Krishnamurthy
Matthew A. Pasek
author_facet Maheen Gull
Harold A. Cruz
Ramanarayanan Krishnamurthy
Matthew A. Pasek
author_sort Maheen Gull
collection DOAJ
description Abstract P-N species e.g., amidophosphates readily phosphorylate organics, thereby overcoming the so-called ‘Phosphate Problem’. However, the formation of amidophosphates by plausible early Earth geochemical pathways is limited. We herein show that ammonolysis of the prebiotically plausible dimer of phosphite, pyrophosphite, readily affords amidophosphite, the monomeric P-N derivative of phosphite. Amidophosphite then undergoes spontaneous oxidation to form monoamidophosphate (MAP) and diamidophosphate (DAP) at room temperature (yields of the inorganic P-N species up to 48%). Oxidation of amidophosphite is promoted by O2, H2O2, ClO⁻ and by UV light irradiation (365 nm). Both amidophosphite and MAP and the crude reaction mixture react with nucleosides to form nucleotides with both phosphate and H-phosphonate (yields up to 65%) at 80 °C in the presence of urea, showing that monoamidated phosphorus compounds also willingly promote prebiotic reactions. This observation expands the range of P-N phosphorylating agents that can play a role in the chemical evolution of prebiotic molecules on the early Earth.
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spelling doaj-art-e57196df6e4c407c981e7bc87feba7972025-08-20T04:01:52ZengNature PortfolioCommunications Chemistry2399-36692025-06-018111210.1038/s42004-025-01577-0Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sourcesMaheen Gull0Harold A. Cruz1Ramanarayanan Krishnamurthy2Matthew A. Pasek3School of Geosciences, University of South FloridaDepartment of Chemistry, The Scripps Research InstituteDepartment of Chemistry, The Scripps Research InstituteSchool of Geosciences, University of South FloridaAbstract P-N species e.g., amidophosphates readily phosphorylate organics, thereby overcoming the so-called ‘Phosphate Problem’. However, the formation of amidophosphates by plausible early Earth geochemical pathways is limited. We herein show that ammonolysis of the prebiotically plausible dimer of phosphite, pyrophosphite, readily affords amidophosphite, the monomeric P-N derivative of phosphite. Amidophosphite then undergoes spontaneous oxidation to form monoamidophosphate (MAP) and diamidophosphate (DAP) at room temperature (yields of the inorganic P-N species up to 48%). Oxidation of amidophosphite is promoted by O2, H2O2, ClO⁻ and by UV light irradiation (365 nm). Both amidophosphite and MAP and the crude reaction mixture react with nucleosides to form nucleotides with both phosphate and H-phosphonate (yields up to 65%) at 80 °C in the presence of urea, showing that monoamidated phosphorus compounds also willingly promote prebiotic reactions. This observation expands the range of P-N phosphorylating agents that can play a role in the chemical evolution of prebiotic molecules on the early Earth.https://doi.org/10.1038/s42004-025-01577-0
spellingShingle Maheen Gull
Harold A. Cruz
Ramanarayanan Krishnamurthy
Matthew A. Pasek
Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sources
Communications Chemistry
title Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sources
title_full Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sources
title_fullStr Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sources
title_full_unstemmed Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sources
title_short Phosphorylation of nucleosides by P-N bond species generated from prebiotic reduced phosphorus sources
title_sort phosphorylation of nucleosides by p n bond species generated from prebiotic reduced phosphorus sources
url https://doi.org/10.1038/s42004-025-01577-0
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AT ramanarayanankrishnamurthy phosphorylationofnucleosidesbypnbondspeciesgeneratedfromprebioticreducedphosphorussources
AT matthewapasek phosphorylationofnucleosidesbypnbondspeciesgeneratedfromprebioticreducedphosphorussources