Interactions between glycine derivatives and mineral surfaces: Implications for the origins of life on planetary surfaces

Biology

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[0400] Biogeosciences, [5215] Planetary Sciences: Astrobiology / Origin Of Life

Scientific paper

Various mechanisms could have delivered amino acids to the prebiotic Earth (Miller and Orgel 1974). The polymerization of amino acids may have been important for the origin of life, as peptides may have been components for the first self-replicating systems (Kauffman 1971; Yao et al 1998). Though amino acid concentrations in the primitive oceans were likely too dilute for significant oligomerization to occur (Cleaves et al 2009), mineral surface adsorption may have concentrated these biomolecules (Bernal 1951; Lambert 2008). Few studies have examined the catalytic effects of mineral surfaces on aqueous peptide oligomerization or degradation. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied the reverse reaction of polymer degradation to measure potential mineral catalysis. Glycine (G) derivatives glycylglycine (GG), diketopiperazine (DKP), and glycylglycylglycine (GGG) were reacted with different minerals (calcite, hematite, montmorillonite, rutile, amorphous silica, and pyrite) in the presence of 0.05 M pH 8.1 KHCO3 buffer and 0.1 M NaCl as background electrolyte. Experiments were performed by reacting the aqueous amino acid derivative-mineral mixtures in a thermostatted oven (modified to accommodate a mechanical rotator) at 25°, 50° or 70°C. Samples were removed after 30, 60, 90, and 140 hours. Samples were then analyzed using high performance liquid chromatography to quantify the products. Besides mineral catalysis, it was determined that degradation of GGG proceeds principally via a GGG → DKP + G mechanism, rather than via GGG → GG + G. Below 70°C kinetics were generally too sluggish to detect catalytic activity over reasonable laboratory time-scales at this pH. At 70°C, pyrite was the only mineral with detectible catalytic effects on the degradation of GGG. GGG degraded ~ 1.5 - 4 x faster in the presence of pyrite than in control reactions, depending on the ratio of solution to mineral surface area. Catalysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. These and other results will be presented and discussed. References Bernal, J. D. (1951) The Physical Basis of Life (Routledge, London). Cleaves, H.J., Aubrey, A.D., Bada, J.L. (2009) An evaluation of the critical parameters for abiotic peptide synthesis in submarine hydrothermal systems. Origins of Life Evol Biosph. 39:109-26. Kauffman, S.A. (1971) Cellular homeostasis, epigenesis and replication in randomly aggregated macromolecular systems. Cybernetics and Systems: An International Journal 1: 71 - 96. Lambert, J. (2008) Adsorption and polymerization of amino acids on mineral surfaces: A review. Origins of Life Evol. Biosph. 38: 211-42. Miller, S.L. and Orgel, L.E. (1974) The Origins of Life on the Earth, Prentice Hall (Englewood Cliffs, NJ) Yao, Y., Ghosh, I., Zutshi, R., Chmielewski, J. (1998) Selective amplification by auto- and cross-catalysis in a replicating peptide system. Nature 396, 447 - 450.

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