Interaction between adenine and Cu2+ and Fe3+-montmorillonites: a prebiotic chemistry experiment

Abstract

The modification of minerals with metals can promote changes in their surface and, consequently, in their physicochemical properties. Minerals could have played an important role in the origin of life as they can protect molecules against degradation by radiation and hydrolysis, pre-concentrate molecules from dilute solutions and catalyse the formation of polymers. Thus, the current work studied the modification of montmorillonite with Cu2+ and Fe3+ ions. These modified montmorillonites were used to study the interaction with adenine dissolved in distilled water and artificial seawater 4.0 Gy (Gy = billion years ago). The most important result of this work is that the adsorption of adenine onto modified montmorillonites is a complex interaction among adenine, salts in seawater and Cu2+/Fe3+-montmorillonite (Cu2+/Fe3+-Mont) . The adsorption of Cu2+ and Fe3+ onto montmorillonite decreased its surface area and pore volume. The Sips isotherm model showed the best fit of the data and n values indicate that the adenine adsorption process was homogeneous. The highest adenine adsorption was obtained in artificial seawater 4.0 Gy onto Fe3+-Mont at 60°C and the lowest in distilled water or artificial seawater 4.0 Gy onto montmorillonite [montmorillonite washed with distilled water (Mont-STD)] at 60°C. Adenine adsorption onto Mont-STD/montmorillonite modified with 500 ml of 0.1 mol l−1 of CuCl2 and Fe3+-Mont was an exothermic process and an endothermic process, respectively. For all adsorptions ΔG was negative. The adsorption of adenine onto Fe3+-Mont was ruled out by entropy and the other samples by enthalpy and entropy, being a major contribution for Gibbs free energy from enthalpy. The Fourier transform-infrared data indicate that the interaction of adenine with minerals may occur through the NH2 functional group.