Abstract
Our previous kinetic and thermodynamic studies upon the reactional system HCHO/HCN/ NH3 in aqueous solutions are completed. In the assumed prebiotic conditions of the primitive earth ([HCHO] and [HCN] near 1 g L−1, T = 25 °C, pH = 8, [NH3] very low), this system leads to 99.9% of α-hydroxyacetonitrile and 0.1% of α-aminoacetonitrile (precursor of the α-amino acid). The classical base-catalyzed hydration of nitriles, slow and not selective, can not modify significantly this proportion. On the contrary, we found two specific and efficient reactions of α-aminonitriles which shift the initial equilibrium in favor of the α-aminonitrile pathway. The first reaction catalyzed by formaldehyde generates α-aminoamides, precursors of α-aminoacids. The second reaction catalyzed by carbon dioxide affords hydantoins, precursors of N-carbamoyl-α-aminoacids. In the primitive hydrosphere, where the concentration in carbon dioxide was estimated to be higher than that of formaldehyde, the formation of hydantoins was consequently more efficient. The rates of hydrolysis of the α-aminoacetamide and of the hydantoin at pH 8 being very similar, the synthesis of the N-carbamoyl-α-amino acid seems then to be the fatal issue of the HCHO/HCN/NH3 system that nature used to perform its evolution. These N-protected α-amino acids offer new perspectives in prebiotic chemistry, in particular for the emergence of peptides on the prebiotic earth.
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Abelson, P. H.: 1966, Proc. Nat. Acad. Sci. USA 55, 1365.
Angelescu, E., Vasiliu, G. and Radvan, S.: 1940, Bull. Soc. Sci. Acad. Roum. 22, 411.
Angelescu, E., Vasiliu, G., Zavoianu, D. and Nan, F.: 1961, Studi. Cenetari de chimie Acad. R.P.R. 9, 459.
Bada, J. L. and Miller, S. L.: 1968, Science 159, 423.
Bar-Nun, A.and Shaviv, A.: 1975, Icarus 24, 197.
Béjaud, M., Mion, L. and Commeyras, A.: 1976, Bull. Soc. Chim. 1–2, 233.
Béjaud, M., Mion, L. and Commeyras, A.: 1976, Bull. Soc. Chim. 9–10, 1425.
Bergs, H.: 1929, Deutche Paten, No. 566.094.
Blagoeva, I. B., Pojarlieff, I. G. and Dimitrof, V. S.: 1978, J. Chem. Soc., Perkin Trans. 2, 887.
Brack, A. and Raulin, F.: 1991, L' évolution chimique et les origines de la vie, Masson, Paris (F).
Bücherer, H. T. and Fischbeck, W.: 1934, J. Prakt. Chem. 140, 69.
Bücherer, H. T. and Brand, W.: 1934, J. Prakt. Chem. 140, 129.
Bücherer, H. T. and Barsch, W.: 1934, J. Prakt. Chem. 140, 151.
Calvin, M.: 1969, Chemical Evolution, Oxford University Press, Oxford (GB).
Chameides, W. L. and Walker, J. C. G.: 1981, Origins Life Evol. Biosphere 11, 291–302.
Collet, H., Bied, C., Mion, L., Taillades, J. and Commeyras, A.: 1996, Tetrahedron Lett. 37, 9043.
Commeyras, A., Taillades, J., Mion, L., Pascal, R., Laspéras, M. and Rousset, A.: 1976, 1977, Brevet Européen, ANVAR (F), No. 7636520 and No. 30699.
Commeyras, A., Collet, H., Mion, L., Bénéfice, S., Calas, P., Choukroun, H. and Taillades, J.: 1994, Brevet Français, Paris (F), No. 94.12779, PCT/FR 95/01380
DiGiacchino, S., Paolinelli, A. and Re, L.: 1988, European Patent Application No. 88105584.2.
Eschenmoser, A.: 1994, Origins Life Evol. Biosph. 24, 389–423.
Fegley, B., Jr., Prinn, R. G., Hartman, H. and Watkins, G. H.: 1986, Nature 319, 305–308.
Ferris, J. P. and Hagan, W. J.: 1984, Tetrahedron 40, 1093–1120.
Ferris, J. P. and Chen, C. T.: 1975, Nature 258, 587.
Ferris, J. P., Williams, E. A., Nicodem, D. E., Hubbard, J. S. and Voecks, G. E.: 1974, Nature 249, 437.
Jammot, J., Pascal, R. and Commeyras, A.: 1989, Tetrahedron Lett. 30, 563.
Jammot, J.: 1988, Thèse de Doctorat, Université des sciences et techniques du Languedoc,Montpellier (F).
Jammot, J., Pascal, R. and Commeyras, A.: 1990, J. Chem. Soc., Perkin Trans. 2, 157–162.
Kasting, J. F.: 1990, Origins Life Evol. Biosphere 20, 199–231.
Kasting, J. F. and Ackerman, T. P.: 1986, Science 234(4782), 1383–1385.
Koberstein, E.: 1973, Ind. Eng. Chem. Process. Des. Dev. 12, 444.
Lellouch, E., Romani, P. N. and Rosenqvist, J.: 1994, Icarus 108(1), 112–136.
Lemmon, R. M.: 1970, Chem. Rev. 70, 95.
Mansani, R.: 1995, Phys. Org. Chem. 8, 721–730.
Miller, S. L.: 1955, J. Am. Chem. Soc. 77, 2351.
Miller, S. L.: 1957, Biochem. Biophys. Acta 23, 480.
Miller, S. L. and Van Trump, J. E.: 1981, in Wolman and Yecheskel (eds.), Origin. Life, Proc. ISSOL Meet. 3 rd, D. Reidel Publ. Co., Dordrecht, The Netherlands, pp. 135–141.
Moser, R. E., Clagget, A. R. and Matthews, C. N.: 1968, Tetrahedron Letters 13, 1599.
Moser, R. E., Clagget, A. R. and Matthews, C. N.: 1968, Tetrahedron Letters 13, 1605.
Moutou, G., Taillades, J., Bénéfice-Malouet, S., Commeyras, A., Messina, G. and Mansani, R.: 1995, J. Phys. Org. Chem. 8, 721–730.
Owen, T., Cess, R. D. and Ramanathan, V.: 1979, Nature 277, 640–642.
Palm, C. and Calvin, M.: 1962, J. Am. Chem. Soc. 84, 2115.
Pascal, R., Taillades, J. and Commeyras, A.: 1978, Bull. Soc. Chim. 3–4, 177–184.
Pascal, R., Taillades, J. and Commeyras, A.: 1978, Tetrahedron 34, 2275–2281.
Pascal, R., Taillades, J. and Commeyras, A.: 1980, Tetrahedron 36, 2999–3006.
Pinto, J. P., Randall Gladstone, G. and Yuk Ling Yung: 1980, Science 210, 183–184.
Ponnamperuma, C. and Woeller, F. H.: 1967, Currents Modern Biol. 1, 156.
Raulin, F.: 1992, J. British Interplanetary Soc. 45, 257–271.
Riley, J. P. and Skirrow (eds.): 1961, Chemical Oceanography, Vol. 1, Academic Press, London.
Rousset, A., Laspéras, M., Taillades, J. and Commeyras, A.: 1984, Bull. Soc. Chim. 5–6, 209.
Rousset, A., Laspéras, M., Taillades, J. and Commeyras, A.: 1980, Tetrahedron 36, 2649.
Sanchez, R. A., Ferris, J. P. and Orgel, L. E.: 1966, Science 154, 784.
Sanchez, R. A., Ferris, J. P. and Orgel, L. E.: 1967, J. Mol. Biol. 30, 223.
Schavoand, A. and Winkler, C.: 1959, Can. J. Chem. 37, 655.
Schlesinger, G. and Miller, S. L.: 1973, J. Am. Chem. Soc. 95, 3729.
Strecker, A.: 1850, Ann. 75, 28.
Summers, D. P. and Chang, S.: 1993, Nature 365, 630–633.
Taillades, J., Brugidou, J., Pascal, R., Sola, R., Mion, L. and Commeyras, A.: 1986, L' Actualite chimique, 13–20.
Toublanc, D., Parisot, J. P., Brillet, J., Gautier, D., Raulin, F. and Mckay, C. P.: 1995, Icarus 113(1), 2–26.
Van Trump, J. E.: 1975, PhD Thesis, University of California, San Diego, USA.
Ware, I.: 1950, Chem. Rev. 46, 403–469.
Wilhelm, E., Battino, R. and Wilcock, R. D.: 1977, Chem. Rev. 77, 219–262.
Winnewisser, G. and Herbst, E.: 1987, Top. Curr. Chem. 139, 19–172.
Wood, J. A. and Chang, S.: 1985, The Cosmic History of the Biogenic Elements and Compounds. NASA SP476, Washington DC, USA.
Yamagata, Y. and Mohri, T.: 1982, Origins of Life 12, 41.
Yuaso, S. and Ishigami, M.: 1975, Origins of Life 6, 75.
Yung, Y. L. and Mac Elroy, M.B.: 1979, Science 203, 1002–1004.
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Taillades, J., Beuzelin, I., Garrel, L. et al. N-Carbamoyl-α-Amino Acids Rather than Free α-Amino Acids Formation in the Primitive Hydrosphere: A Novel Proposal for the Emergence of Prebiotic Peptides. Orig Life Evol Biosph 28, 61–77 (1998). https://doi.org/10.1023/A:1006566810636
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DOI: https://doi.org/10.1023/A:1006566810636