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

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.

[1]  R. Shapiro,et al.  The prebiotic role of adenine: A critical analysis , 1995, Origins of Life and Evolution of the Biosphere.

[2]  J. Ferris,et al.  Possible role of hydrogen cyanide in chemical evolution investigation of the proposed direct synthesis of peptides from hydrogen cyanide. , 1973, Journal of molecular biology.

[3]  S. Wasik,et al.  Aqueous solubilities and enthalpies of solution of adenine and guanine , 1984 .

[4]  L. Orgel,et al.  Studies in prebiotic synthesis. II. Synthesis of purine precursors and amino acids from aqueous hydrogen cyanide. , 1967, Journal of molecular biology.

[5]  A. Schwartz,et al.  Recent progress in the prebiotic chemistry of HCN , 2004, Origins of life.

[6]  L. Orgel,et al.  Conditions for Purine Synthesis: Did Prebiotic Synthesis Occur at Low Temperatures? , 1966, Science.

[7]  Alan W. Schwartz,et al.  Prebiotic adenine synthesis from HCN—Evidence for a newly discovered major pathway , 1983 .

[8]  L. Orgel,et al.  Synthesis of Adenine from HCN Tetramer and Ammonium Formate , 2002, Origins of life and evolution of the biosphere.

[9]  P. C. Joshi,et al.  HCN: A plausible source of purines, pyrimidines and amino acids on the primitive earth , 1978, Journal of Molecular Evolution.

[10]  J. Bada,et al.  Impact melting of frozen oceans on the early Earth: Implications for the origin of life , 1994, Proceedings of the National Academy of Sciences of the United States of America.

[11]  L. Orgel,et al.  Studies in prebiotic synthesis. IV. Conversion of 4-aminoimidazole-5-carbonitrile derivatives to purines. , 1968, Journal of molecular biology.

[12]  L. Orgel,et al.  An Unusual Photochemical Rearrangement in the Synthesis of Adenine from Hydrogen Cyanide1 , 1966 .

[13]  R. Wolfenden,et al.  Transition state stabilization by deaminases: Rates of nonenzymatic hydrolysis of adenosine and cytidine , 1987 .

[14]  J. Oró,et al.  Production of guanine from NH(4)CN polymerizations. , 1999, Journal of molecular evolution.

[15]  L. Orgel,et al.  Studies in prebiotic synthesis. VI. Synthesis of purine nucleosides. , 1968, Journal of molecular biology.

[16]  J. Oró,et al.  Synthesis of purines under possible primitive earth conditions. II. Purine intermediates from hydrogen cyanide. , 1962, Archives of biochemistry and biophysics.

[17]  C. Crestini,et al.  A possible prebiotic synthesis of purine, adenine, cytosine, and 4(3H)-pyrimidinone from formamide: implications for the origin of life. , 2001, Bioorganic & medicinal chemistry.

[18]  M. Levy,et al.  The stability of the RNA bases: implications for the origin of life. , 1998, Proceedings of the National Academy of Sciences of the United States of America.

[19]  J. Oró,et al.  Synthesis of purines under possible primitive earth conditions. I. Adenine from hydrogen cyanide. , 1961, Archives of biochemistry and biophysics.

[20]  Alan W. Schwartz,et al.  Acceleration of HCN oligomerization by formaldehyde and related compounds: Implications for prebiotic syntheses , 2005, Journal of Molecular Evolution.

[21]  J. Oró,et al.  Synthesis of adenine from ammonium cyanide , 1960 .

[22]  J L Bada,et al.  Prebiotic synthesis of adenine and amino acids under Europa-like conditions. , 2000, Icarus.

[23]  Alan W. Schwartz The Molecular Origins of Life: Origins of the RNA world , 1998 .