The biochemical activation of amino acids by adenosine triphosphate (ATP) drives the synthesis of proteins that are essential for all life. On the early Earth, before the emergence of cellular life, the chemical condensation of amino acids to form prebiotic peptides or proteins may have been activated by inorganic polyphosphates, such as tri metaphosphate (TP). Plausible volcanic and other potential sources of TP are known, and TP readily activates amino acids for peptide synthesis. But de novo peptide synthesis also depends on pH, temperature, and processes of solvent drying, which together define a varied range of potential activating conditions. Although we cannot replay the tape of life on Earth, we can examine how activator, temperature, acidity and other conditions may have collectively shaped its prebiotic evolution. Here, reactions of two simple amino acids, glycine and alanine, were tested, with or without TP, over a wide range of temperature (0–100 °C) and acidity (pH 1–12), while open to the atmosphere. After 24 h, products were analyzed by HPLC and mass spectrometry. In the absence of TP, glycine and alanine readily formed peptides under harsh near-boiling temperatures, extremes of pH, and within dry solid residues. In the presence of TP, however, peptides arose over a much wider range of conditions, including ambient temperature, neutral pH, and in water. These results show how polyphosphates such as TP may have enabled the transition of peptide synthesis from harsh to mild early Earth environments, setting the stage for the emergence of more complex prebiotic chemistries.
Trimetaphosphate Prebiotic Alanine Glycine de novo peptides Drying-induced condensation
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D. Baum, A. Donnelly, K. Schloss, and K. Vetsigian provided helpful discussions and feedback. This work was funded in part by the Vilas Distinguished Achievement Professorship (L.L. and J.Y.), the Office of the Vice Chancellor for Research and Graduate Education (L.L. and J.Y.), the Wisconsin Institute for Discovery (J.Y.), the Janis Apinis Professorship (L.L.) at the School of Pharmacy, all at the University of Wisconsin-Madison; a Robert Draper Technology Innovation Fund grant (L.L.), shared instrument grant (L.L.), and Accelerator Fund grant (J.Y.) from the Wisconsin Alumni Research Foundation (WARF); and grants R01DK071801 (L.L.), R01AI091646 (J.Y.), U19AI0104317 (J.Y.), and a shared instrument grant NCRR S10RR029531 (L.L.) for the Orbitrap instruments, from the U.S. National Institutes of Health.
I.S. and J.Y. conceived the project and wrote the manuscript, Y.F. and L.L. contributed to the writing. Y.F. performed the MS/MS analyses. I.S. carried out the experiments, collected the data, and performed the analysis. All authors discussed the results and contributed to the manuscript.
Compliance with Ethical Standards
Author Disclosure Statement
The authors declare no competing financial interests exist.
Materials & Correspondence
The data that support the findings of this study are available from J.Y. upon reasonable request.
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