Modulation of Adenosine 5'-Monophosphate Adsorption Onto Aqueous Resident Pyrite: Potential Mechanisms for Prebiotic Reactions

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Adenosine 5'-Monophosphate, Biomonomersadsorption Onto Minerals, Chemical Evolution, High Dipolar Moment Molecules, Iron-Sulfide Minerals, Pyrite

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The adsorption of adenosine 5'-monophosphate (5'-AMP) onto pyrite (FeS_2) and its modulation by acetate, an organic precursor of complex metabolic pathways, was studied in aqueous media that simulate primitive environments. 5'-AMP adsorption requires divalent cations, indicating that a cationic bridge mediates its attachment to negatively charged sites of the mineral surface. The isotherm of 5'-AMP adsorption exhibits a strong cooperative effect at low nucleotide concentrations in acetate-rich medium, whereas high levels of adsorption were only found at high nucleotide concentrations in a model of primitive seawater (acetate free). The modulating role of acetate is also evidenced in the presence of high dipolar moment molecules: dimethyl sulfoxide (Me_2SO) and dimethyl formamide (DMF) strongly inhibit 5'-AMP adsorption in acetate-rich media, whereas no effect of DMF was found in artificial seawater. The observation that exogenous divalent cations are not needed for acetate attachment onto FeS_2 reveals that organic acids can interact with the Fe^2+ atoms in the mineral surface. All considered, the results show that complex and flexible iron-sulfide/biomonomers interactions can be modulated by molecules that accumulate in the interface layer.

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