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K.H. Lemke

Publications and source records attributed to K.H. Lemke.

2 recordsLinked to original sources

Peptide synthesis in early earth hydrothermal systems

We report here results from experiments and thermodynamic calculations that demonstrate a rapid, temperature-enhanced synthesis of oligopeptides from the condensation of aqueous glycine. Experiments were conducted in custom-made hydrothermal reactors, and organic compounds were characterized with ultraviolet-visible procedures. A comparison of peptide yields at 260??C with those obtained at more moderate temperatures (160??C) gives evidence of a significant (13 kJ ?? mol -1 ) exergonic shift. In contrast to previous hydrothermal studies, we demonstrate that peptide synthesis is favored in hydrothermal fluids and that rates of peptide hydrolysis are controlled by the stability of the parent amino acid, with a critical dependence on reactor surface composition. From our study, we predict that rapid recycling of product peptides from cool into near-supercritical fluids in mid-ocean ridge hydrothermal systems will enhance peptide chain elongation. It is anticipated that the abundant hydrothermal systems on early Earth could have provided a substantial source of biomolecules required for the origin of life. Astrobiology 9, 141-146. ?? 2009 Mary Ann Liebert, Inc. 2009.

Astrobiology

An hydrothermal experimental study of the cobalt-cobalt oxide redox buffer

Equilibrium aqueous hydrogen concentration and corresponding energies of reaction, ??Grxno(T, P), for the reaction Co(s) + H2O(l) = CoO(s) + H2(aq) have been determined at temperatures between 256 and 355 ??C and at 400 bar. Steady-state concentrations of hydrogen were approached in experiments under conditions of both H2 excess and deficiency containing the solids Co, CoO and liquid water. All experiments were carried out in flexible gold and titanium reactors with the capability of on-line fluid sampling. Measured equilibrium molal concentrations of H2(aq) at 256, 274, 300, 324 and 355 ??C are 0.81(?? 0.01) ?? 10- 3 1.11(?? 0.01) ?? 10- 3, 1.92(?? 0.01) ?? 10- 3, 3.71(?? 0.06) ?? 10- 3, 7.54(?? 0.12) ?? 10- 3, respectively, and corresponding values of ??Grxno(T, P) in units kJ ?? mol- 1 are 31.4(?? 0.1), 31.0(?? 0.1), 29.8(?? 0.1), 27.7(?? 0.5) and 25.5(?? 0.9), respectively. Using published heat capacity data for Co(s) and CoO(s) and - 79.6 J ?? mol- 1 ?? K- 1 for the entropy of formation of CoO we calculated for this study a value for ??GCoO,Tr,Pro = - 214.5(?? 0.9) kJ ?? mol- 1 and ??HCoO,Tr,Pro = - 238.3(?? 0.9) kJ ?? mol- 1 at 25 ??C and 1 bar. The value of ??HCoO,Tr,Pro determined in this study compares well with the reported calorimetric value of - 238.9(?? 1.2) kJ ?? mol- 1 [Boyle, B.J., King, E.G., Conway, K.C., 1954. Heats of formation of nickel and cobalt oxides (NiO and CoO) by combustion calorimetry. Journal of the American Chemical Society, 76, 3835-3837]. ?? 2008 Elsevier B.V. All rights reserved.

Chemical Geology