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An Investigation of Prebiotic Purine Synthesis from the Hydrolysis of HCN Polymers

  • Eduardo Borquez
  • H. James Cleaves
  • Antonio Lazcano
  • Stanley L. Miller
Article

Abstract

The polymerization of concentrated NH4CN solutions has been studied at various temperatures and ammonia concentrations. The products of the oligomerization of ammonium cyanide include adenine and guanine, as well as trace amounts of 2,6-diaminopurine. Our results indicate that the adenine yield is not strongly dependent on temperature. Guanine is produced in lower yield. The original studies by Oró and Kimball (1961) showed that the 6 N HCl hydrolysis of the NH4CN polymerization supernatant greatly increased the adenine yield. However, this hydrolysis also decomposes adenine and other purines. Therefore, we have measured the yields from an NH4CN polymerization as a function of hydrolysis time, and found that shorter hydrolytic periods give higher yields of adenine.We have also investigated the hydrolysis of the supernatant at pH 8, which is a more reasonable model of primitive oceanic conditions, and found that the adenine yield is comparable to that obtained with acid hydrolysis (approximately 0.1%). The yield of adenine does not decline at longer hydrolysis times because of the greater stability of adenine at pH 8. The insoluble black polymer formed from NH4CN has been analyzed by both acid and neutral hydrolysis. In both cases adenine yields of approximately 0.05% were obtained. This suggests that the polymer may have been as important a prebiotic source of purines as the usually analyzed supernatant.

Keywords

2,6-diaminopurine adenine guanine NH4CN polymerization 

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References

  1. Bada, J. L., Bigham, C. and Miller, S. L.: 1994, Impact Melting of Frozen Oceans on the Early Earth: Implications for the Origin of Life’, Proc. Natl. Acad. Sci. USA 91, 1248–1250.PubMedGoogle Scholar
  2. Devoe, H. and Wasik, S. P.: 1984, Aqueous Solubilities and Enthalpies of Solution of Adenine and Guanine, J. Sol. Chem. 13, 51–60.CrossRefGoogle Scholar
  3. Ferris, J. P. and Orgel, L. E.: 1966, An Unusual Photochemical Rearrangement in the Synthesis of Adenine from Hydrogen Cyanide, J. Am. Chem. Soc. 88, 1074.CrossRefGoogle Scholar
  4. Ferris, J. P., Donner, D. B. and Lobo, A. P.: 1973, Possible Role of Hydrogen Cyanide in Chemical Evolution. Investigation on the Proposed Direct Synthesis of Peptides from Hydrogen Cyanide, J. Mol. Biol. 74, 499–508.CrossRefPubMedGoogle Scholar
  5. Ferris, J. P., Joshi, P. C., Edelson, E. H. and Lawless, J. G.: 1978, HCN: A Plausible Source of Purines, Pyrimidines, and Amino Acids on the Primitive Earth, J. Mol. Evol. 11, 293–311.CrossRefPubMedGoogle Scholar
  6. Frick, L., MacNeela, J. P. and Wolfenden, R.: 1987, Transition State Stabilization by Deaminases: Rates of Nonezymatic Hydrolysis of Adenosine and Cytidine, Bioorganic Chem. 15, 100–108.CrossRefGoogle Scholar
  7. Hill, A. and Orgel, L. E.: 2002, Synthesis of Adenine from HCN Tetramer and Ammonium Formate, Orig. Life Evol. Biosph. 32, 99–102.CrossRefPubMedGoogle Scholar
  8. Levy, M. and Miller, S. L.: 1998, The Stability of RNA Bases: Implications for the Origin of Life, Proc. Natl. Acad. Sci. USA 95, 7933–7938.CrossRefPubMedGoogle Scholar
  9. Levy, M., Miller, S. L. and Oró, J.: 1999, Production of Guanine from NH4CN Polymerizations, J. Mol. Evol. 49, 165–168.PubMedGoogle Scholar
  10. Levy, M., Miller, S. L., Brinton, K., Bada, J. L.: 2000, Prebiotic Synthesis of Adenine and Amino Acids under Europa-like Conditions, Icarus 145, 609–613.CrossRefPubMedGoogle Scholar
  11. Oró, J.: 1960, Synthesis of Adenine from Ammonium Cyanide, Biochem. Biophys. Res. Comm. 2, 407–412.CrossRefGoogle Scholar
  12. Oró, J. and Kimball, A. P.: 1961, Synthesis of Purines under Primitive Earth Conditions. I. Adenine from Hydrogen Cyanide, Arch. Biochem. Biophys. 94, 217–227.CrossRefPubMedGoogle Scholar
  13. Oró, J. and Kimball, A. P. 1962, Synthesis of Purines under Primitive Earth Conditions. II. Purine Intermediates from Hydrogen Cyanide, Arch. Biochem. Biophys. 96, 293–313.CrossRefPubMedGoogle Scholar
  14. Saladino, R., Crestini, C., Costanzo, G., Negri, R. and Di Mauro, E.: 2001, A Possible Prebiotic Synthesis of Purines: Adenine, Cytosine and 4(3H)-pyrimidinone from Formamide: Implications for the Origin of Life, Bioorganic Med. Chem. 9, 1249–1253.CrossRefGoogle Scholar
  15. Sanchez, R. A., Ferris, J. P. and Orgel, L. E.: 1966 Conditions for Purine Synthesis: Did Prebiotic Synthesis Occur at Low Temperatures? Science 153, 72–73.PubMedGoogle Scholar
  16. Sanchez, R. A., Ferris, J. P. and Orgel, L. E.: 1967, Studies in Prebiotic Synthesis. II. Synthesis of Purine Precursors and Amino Acids from Aqueous Hydrogen Cyanide, J.Mol. Biol. 30, 223–253.PubMedGoogle Scholar
  17. Sanchez, R.A., Ferris, J. P. and Orgel, L. E.: 1968, Studies in Prebiotic Synthesis. IV. The Convertion of 4-aminoimidazole-5-carbonitrile Derivatives to Purines, J. Mol. Biol. 38, 121–128.CrossRefPubMedGoogle Scholar
  18. Schwartz, A. W.: 1998, ‘Origins of the RNA World’, in A. Brack (ed.), The Molecular Origins of Life: Assembling Pieces of the Puzzle, Cambridge University Press, New York, pp. 237–254.Google Scholar
  19. Schwartz, A. W. and Goverde, M.: 1982, Acceleration of HCN Oligomerization by Formaldehyde and Related Compounds: Implications for Prebiotic Synthesis, J. Mol. Evol. 18, 351–353.CrossRefPubMedGoogle Scholar
  20. Schwartz, A.W., Voet, A. B. and Van Der Veen,M.: 1984, Recent Progress in the Prebiotic Chemistry of HCN, Orig. Life 14, 91–98.CrossRefPubMedGoogle Scholar
  21. Shapiro, R.: 1995, The Prebiotic Role of Adenine: A Critical Analysis, Orig. Life Evol. Biosph. 25, 238–239.CrossRefGoogle Scholar
  22. Voet, A. B. and Schwartz, A. W.: 1983, Prebiotic Adenine Synthesis from HCN: Evidence for a Newly Discovered Major Pathway, Bioorganic Chem. 12, 8–17.CrossRefGoogle Scholar

Copyright information

© Springer Science + Business Media, Inc. 2005

Authors and Affiliations

  • Eduardo Borquez
    • 1
    • 3
  • H. James Cleaves
    • 1
  • Antonio Lazcano
    • 2
  • Stanley L. Miller
    • 1
  1. 1.Department of Chemistry and BiochemistryUniversity of CaliforniaSan Diego, La JollaU.S.A.
  2. 2.Facultad de CienciasUNAM, Cd. UniversitariaMexicoMexico
  3. 3.BostonU.S.A.

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