Abstract
Ferrihydrite is widespread in clays, soils, and living organisms and was found on Mars. This iron-mineral could be found on the prebiotic Earth, which also contained simple monomeric amino acids. For prebiotic chemistry, it is important to understand how amino acids have an effect on the process of iron oxide formations. There are three important results in this work: (a) preconcentration of cysteine and aspartic acid, (b) formation of cystine and probably the cysteine peptide occurred during ferrihydrite syntheses, and (c) amino acids have an effect on iron oxide synthesis. For samples containing aspartic acid and cysteine, their presence on the surface or mineral structure can be confirmed by FT-IR spectra. Surface charge analysis showed a relatively high decrease for samples synthesized with cysteine. Scanning electron microscopy did not show marked morphological differences among the samples, except for the seawater sample containing cysteine, which had a lamina-shaped morphology surrounded by circular iron particles, indicating the possible formation of a cysteine structure involving iron oxide particles. The thermogravimetric analysis of the samples indicates that the presence of salts and amino acids in the synthesis of ferrihydrite has an effect on the thermal behavior of the iron oxide/amino acids and modifying the water-loss temperature. The heating of the cysteine samples, synthesized in distilled water and artificial seawater, showed several peaks of degradation of cysteine. In addition, heating of the aspartic acid samples produced the polymerization of this amino acid and peaks of degradation of it. FTIR spectra and XRD patterns did not indicate the precipitation of methionine, 2-aminoisobutyric acid, lysine, or glycine with the iron oxide formations. However, the heating of the glycine, methionine and lysine samples, synthesized in artificial seawater, showed peaks that could be attributed to the degradation of them. Then this could be an indication that these amino acids precipitate with the minerals during the syntheses. Also, the dissolution of these amino acids in artificial seawater prevents the formation of ferrihydrite.
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YST acknowledges the undergraduate fellowship from CNPq. The authors thank the support of CNPq/Fundacao Araucaria (Programa de apoio a nucleos de excelencia-PRONEX, protocol 24732)
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CEAC and DAMZ conceptualization of the work. YST and CEAC performed the synthesis of iron oxide and SEM and TG analysis. RBS wrote original draft. ACSC performed X-ray experiments and analysis of the data. DAMZ and RBS review and editing the final version of the article. All authors agreed with the final version of the article.
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Tadayozzi, Y.S., Samulewski, R.B., Carneiro, C.E.A. et al. Ferrihydrite synthesis in the presence of amino acids and artificial seawater. Amino Acids 55, 607–618 (2023). https://doi.org/10.1007/s00726-023-03253-w
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DOI: https://doi.org/10.1007/s00726-023-03253-w