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A physicochemical orthophosphate cycle via a kinetically stable thermodynamically activated intermediate enables mild prebiotic phosphorylations.

ABSTRACT: The incorporation of orthophosphate from scarce geochemical sources into the organic compounds essential for life under mild conditions is a fundamental challenge for prebiotic chemistry. Here we report a prebiotic system capable of overcoming this challenge by taking inspiration from extant life's recycling of orthophosphate via its conversion into kinetically stable thermodynamically activated (KSTA) nucleotide triphosphates (e.g. ATP). We separate the activation of orthophosphate from its transfer to organic compounds by, crucially, first accumulating a KSTA phosphoramidate. We use cyanate to activate orthophosphate in aqueous solution under mild conditions and then react it with imidazole to accumulate the KSTA imidazole phosphate. In a paste, imidazole phosphate phosphorylates all the essential building blocks of life. Integration of this chemistry into a wet/dry cycle enables the continuous recycling of orthophosphate and the accretion of phosphorylated compounds. This system functions even at low reagent concentrations due to solutes concentrating during evaporation. Our system demonstrates a general strategy for how to maximise the usage of scarce resources based upon cycles which accumulate and then release activated intermediates.

SUBMITTER: Maguire OR

PROVIDER: S-EPMC8448844 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Reorganization from Kinetically Stable Aggregation States to Thermodynamically Stable Nanotubes of BINOL-Derived Amphiphiles in Water.

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| S-EPMC3183798 | biostudies-other

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Highly Selective Separation Intermediate-Size Anionic Pollutants from Smaller and Larger Analogs via Thermodynamically and Kinetically Cooperative-Controlled Crystallization.

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| S-EPMC7967070 | biostudies-literature

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| S-EPMC2329685 | biostudies-literature

Prediction of new thermodynamically stable aluminum oxides.

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Project description:The formation of a new, dihydrate crystalline form of 5-methyluridine (m(5)U) was selectively induced by a protein additive, antifreeze protein (AFP) in a highly efficient manner (in 10(-6) molar scale, whereas known kinetic additives need 0.1 molar scale). The hemihydrate form (form I, the only previously known crystalline form of m(5)U) and the dihydrate form of m(5)U (form II) obtained herein were characterized using X-ray crystallography and differential scanning calorimetry (DSC). Compared to form I, remarkably, form II is thermodynamically and kinetically less preferred. The presence of AFP can selectively inhibit the appearance of form I and hence allows the growth of form II, the pure form of which cannot grow directly from m(5) U supersaturated solutions under the same conditions. An explanation supported by both experimental and theoretical results is provided for the AFP-induced selection process. Implications on AFP-induced ice shape changes are also discussed. Control of crystallization from supersaturated solutions is of great interest in both fundamental research and practical applications in fields like chemistry, pharmacology and materials science. These findings suggest that crystallization processes with AFPs could be valuable for selective growth of hydrates and polymorphs of important pharmaceutical compounds.

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Transmembrane helices containing a charged arginine are thermodynamically stable.

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