Article

Phosphorylation, oligomerization and self-assembly in water under potential prebiotic conditions

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Abstract

Prebiotic phosphorylation of (pre)biological substrates under aqueous conditions is a critical step in the origins of life. Previous investigations have had limited success and/or require unique environments that are incompatible with subsequent generation of the corresponding oligomers or higher-order structures. Here, we demonstrate that diamidophosphate (DAP)—a plausible prebiotic agent produced from trimetaphosphate—efficiently (amido)phosphorylates a wide variety of (pre)biological building blocks (nucleosides/tides, amino acids and lipid precursors) under aqueous (solution/paste) conditions, without the need for a condensing agent. Significantly, higher-order structures (oligonucleotides, peptides and liposomes) are formed under the same phosphorylation reaction conditions. This plausible prebiotic phosphorylation process under similar reaction conditions could enable the systems chemistry of the three classes of (pre)biologically relevant molecules and their oligomers, in a single-pot aqueous environment.

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Acknowledgements

The work was supported by a grant from the Simons Foundation to R.K. (327124) and NASA (NNX14AP59G). This is manuscript #29523 from The Scripps Research Institute. The authors thank M. Wood, T. Fassel and W.B. Kiosses of the Core Microscope Facility of TSRI, M. Janssen for initial TEM measurements, J. Kelly's laboratory for DLS measurements, L. Leman for help with analysis of peptides and the S.F. Dowdy laboratory for MALDI-TOF analysis. The authors also thank R. Ghadiri, D. Deamer, S. Mansy, P. Banerjee, J. Szostak, G. Joyce and our lab members for discussions.

Author information

Author notes

    • Clémentine Gibard
    • , Subhendu Bhowmik
    •  & Megha Karki

    These authors contributed equally to this work.

Affiliations

  1. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA

    • Clémentine Gibard
    • , Subhendu Bhowmik
    • , Megha Karki
    • , Eun-Kyong Kim
    •  & Ramanarayanan Krishnamurthy

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Contributions

R.K. conceived the project. R.K., C.G., S.B., M.K. and E.-K.K. designed the experiments. C.G. and S.B. performed the nucleoside/nucleotide/oligonucleotide phosphorylation experiments. M.K., S.B. and C.G. performed the amino acid phosphorylation experiments. M.K. performed the liposome studies. E.-K.K. and S.B. made the initial observations of DAP-mediated phosphorylation. R.K. wrote the paper with input from C.G., S.B., M.K. and E.-K.K. All authors discussed the results and commented on the manuscript. C.G., S.B. and M.K. contributed equally to this work.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Ramanarayanan Krishnamurthy.

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