Any proposed model of Earth's primitive environments requires a combination of geochemical variables. Many experiments are prepared in aqueous solutions and in the presence of minerals. However, most sorption experiments are performed in distilled water, and just a few in seawater analogues, mostly inconsistent with a representative primitive ocean model. Therefore, it is necessary to perform experiments that consider the composition and concentration of dissolved salts in the early ocean to understand how these variables could have affected the absorption of organic molecules into minerals. In this work, the adsorption of adenine, adenosine, and 5'AMP onto Namontmorillonite was studied using a primitive ocean analog (4.0 Ga) from experimental and computational approaches. The order of sorption of the molecules was: 5'AMP > adenine > adenosine. Infrared spectra showed that the interaction between these molecules and montmorillonite occurs through the NH group. In addition, electrostatic interaction between negatively charged montmorillonite and positively charge N1 of these molecules could occur. Results indicate that dissolved salts affect the sorption in all cases; the size and structure of each organic molecule influence the amount sorbed. Specifically, the X-ray diffraction patterns show that dissolved salts occupy the interlayer space in Na-montmorillonite and compete with organic molecules for available sites. The adsorption capacity is clearly affected by dissolved salts in thermodynamic terms as deduced by isotherm models. Indeed, molecular dynamic models suggest that salts are absorbed in the interlamellar space and can interact with oxygen atoms exposed in the edges of clay or in its surface, reducing the sorption of the organic molecules. This research shows that the sorption process could be affected by high concentration of salts, since ions and organic molecules may compete for available sites on inorganic surfaces. Salt concentration in primitive oceans may have strongly affected the sorption, and hence the concentration processes of organic molecules on minerals.

Cysteine-protected metal nanoparticles (NPs) have shown interesting physicochemical properties of potential utility in biomedical applications and in the understanding of protein folding. Herein, cysteine interaction with gold, silver, and copper NPs is characterized by Raman spectroscopy and density functional theory calculations to elucidate the molecular conformation and adsorption sites for each metal. The experimental analysis of Raman spectra upon adsorption with respect to free cysteine indicates that while the C−S bond and carboxyl group are similarly affected by adsorption on the three metal NPs, the amino group is sterically influenced by the electronegativity of each metal, causing a greater modification in the case of gold NPs. A theoretical approach that takes into consideration intermolecular interactions using two cysteine molecules is proposed using a S−metal−S interface motif anchored to the metal surface. These interactions generate the stabilization of an organo−metallic complex that combines gauche (P H ) and anti (P C ) rotameric conformers of cysteine on the surface of all three metals. Similarities between the calculated Raman spectra and experimental data confirm the thiol and carboxyl as adsorption groups for gold, silver, and copper NPs and suggest the formation of monomeric "staple motifs" that have been found in the protecting monolayer of atomic-precise thiolatecapped metal nanoclusters.

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Abstract:Urea is an organic molecule present in most living organisms. Historically, it was the first organic molecule synthesized in the laboratory. In prebiotic chemistry, urea readily forms in different laboratory simulations using different energy sources. Furthermore, the role of solid surfaces, particularly minerals, might have been crucial to increase the complexity of the organic matter which may have led to the subsequent emergence of life on Earth.In this work, the radiolysis of urea in presence of a clay is studied to determine to what extent the mineral surfaces influence the decomposition of organics. The results indicate that urea is relatively stable to ionizing radiation in aqueous solutions and up to 20 kGy no decomposition is observed. Moreover, the presence of sodium montmorillonite, by a mechanism until now unknown, affects the radiolytic behavior and urea remains in the heterogeneous solution without a change in concentration even at very high doses (140 kGy). These results indicate that solids could have protected some organics, like urea, from degradation enabling them to remain in the environment on the primitive Earth.

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