Energetics of abiogenic chemical systems.

After recalling the energy consumption necessary to produce the main categories of biochemicals from the equilibrium state of an hydrogenated atmosphere, the primary processes by which energy can be absorbed in a mixture of methane and ammonia in the presence of aqueous solutions are defined. From the very first excitations, unsaturated products are formed. In fact, this formation of atmospheric precursors is the primordial state of a photochemically induced redox dismutation. The evolution of solutions obtained from the dissolution of these atmospheric precursors in aqueous media is described from experimental data and analysed on energetic grounds. The relaxation of energy accumulated in such solutions involves non enzymic archetypes of the main categories of metabolic processes; in particular some unsaturated atmospheric precursors must be looked upon as primordial representatives of biochemical dehydrating agents. Absorption of light energy in the solutions obtained from the evolution of precursors happens near the visible range and should govern their further evolution. In fact, biochemicals which were previously detected as products of model experiments are not present in these solutions. They were probably obtained during analytical procedures from products of the evolution of atmospheric precursors which are unstable against decreases of pH. Cyclic autocatalytic effects must be involved in the further evolution of the models of the first aqueous solutions. Their possible role in the appearance of optical dissymmetry is emphasized on theoretical grounds.

The origin of adaptation and dyssymmetry in the evolution of autocatalytic systems.

The evolution of open systems that include several autocatalytic processes in parallel or in series is mathematically analyzed. For the case of two reactions in parallel, such systems progressively and finally select the reaction pathway which involves the better autocatalyst. The effect of parameters influencing the rate of this evolution is discussed. Where catalysts are strictly equivalent, e.g. enantiomers in a symmetrical surrounding, the evolution is amplified by fluctuations and retains finally only one reaction pathway, if the autocatalytic rates of reactions are more than proportional to the catalyst concentrations. When including two reactions in series, these open systems are also able to give oscillations.

Conditions of occurrence for primeval processes of transphosphorylations.

Model reactions of the phosphate group transfer through hydrolysis-condensation processes without enzymic catalysts are studied in dilute aqueous solutions. Tripolyphosphate and acetylphosphate are used as energy and phosphate donors to perform syntheses of pyrophosphate. Results are discussed in terms of the variation versus pH of the overall standard free enthalpy change.

Formation of prebiochemical compounds in models of the primitive earth's atmosphere. I: CH4 NH3 and CH4 N2 atmospheres.

In order to understand the formation of organic compounds in the primitive atmosphere, the first steps of evolution in models of the primitive atmosphere were investigated. Mixtures containing C-H-N elements were subjected to a low pressure silent electric discharge for several seconds, and the resulting effluents were analysed mainly by gas chromatography, infrared spectrometry and chemical analysis. The formation of hydrocarbon (i.e. ethylene, acetylene, methylacetylene) and of nitrogen containing compounds (i.e. hydrogen cyanide, cyanogen, saturated nitriles, acylonitrile, cyanoacetylene) is reported. The influence of the initial mixture composition on the amount of compounds formed was systematically studied. The nature of the nitrogen source (N2 or NH3) in the primitive atmosphere has a great influence on the amount and on the very nature of the synthesized products. It is shown that important precursors such as cyanogen and cyanoacetylene are formed only in very rich N2 mediums. These results show the important role played by the nature of the primitive atmosphere in the determination of the chemical evolution pathways.