Did Salts in Seawater Play an Important Role in the Adsorption of Molecules on Minerals in the Prebiotic Earth? The Case of the Adsorption of Thiocyanate onto Forsterite-91.

Thiocyanate may have played as important a role as cyanide in the synthesis of several molecules. However, its concentration in the seas of the prebiotic Earth could have been very low. Thiocyanate was dissolved in two different seawaters: a) a composition that comes close to the seawater of the prebiotic Earth (seawater-B, Ca2+ and Cl-) and b) a seawater (seawater-A, Mg2+ and SO42-) that could be related to the seas of Mars and other moons in the solar system. In addition, forsterite-91 was a very common mineral on the prebiotic Earth and Mars. Two important results are reported in this work: 1) thiocyanate adsorbed onto forsterite-91 and 2) the amount of thiocyanate adsorbed, adsorption thermodynamic, and adsorption kinetic depend on the composition of the artificial seawater. For all experiments, the adsorption was thermodynamically favorable (ΔG < 0). The adsorption data fitted well in the Freundlich and Langmuir-Freundlich models. When dissolving thiocyanate in seawater 4.0-A-Gy and seawater 4.0-B-Gy, the adsorption of thiocyanate onto forsterite-91 was ruled by enthalpy and entropy, respectively. As shown by n values, the thiocyanate/foraterite-91 system is heterogeneous. For all kinetic data, the pseudo-first-order model presented the best fit. The constant rate for thiocyanate dissolved in seawater 4.0-A-Gy was twice that compared to thiocyanate dissolved in seawater 4.0-B-Gy or ultrapure-water. The interaction between thiocyanate and Fe2+ of forsterite-91 was with the nitrogen atom of thiocyanate. In the presence of thiocyanate, sulfate interacts with forsterite-91 as an inner-sphere surface complex, and without thiocyanate as an outer-sphere surface complex.

Ferrihydrite synthesis in the presence of amino acids and artificial seawater.

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.

Direct Synthesis of HKUST-1 onto Cotton Fabrics and Properties.

Metal-organic frameworks are crystalline nanostructures formed by a metal interspersed by an organic binder. These metal-organic materials are examples of nanomaterials applied to textile material in search of new functionalized textiles. Cotton is a cellulosic fiber of great commercial importance, and has good absorption capacity and breathability; however, due to these characteristics, it is susceptible to the development of microorganisms on its surface. This work aims to analyze how the direct synthesis of HKUST-1 in cotton fabric modifies the chemical and physical properties. The material obtained was characterized by scanning electron microscopy to obtain its morphology, by spectrophotometry CIE L*a*b* to verify the color change, by a biological test to verify its resistance to microorganisms and, finally, by a unidirectional traction test to verify the change in its mechanical resistance. Thereby, it was possible to observe the formation of MOFs with the morphology of nanorods, and also, with regard to HKUST-1 in the cotton fabric, when applied, an elimination percentage higher than 99% was observed for both bacteria, E. coli and S. aureus. The presence of MOF was detected even after washing, however, the loss of 75% in the mechanical resistance of the material makes its potential for textile finishing unworkable.

Lipase immobilization on biodegradable film with sericin.

An ecofriendly and low-cost film composed by cassava starch, polyvinyl alcohol, and sericin blend (CS-PVA-SS) was synthesized, characterized, and applied as a novel support for Botryosphaeria ribis EC-01 lipase immobilization by enzyme-film-enzyme adsorption. Film revealed thickness between 230 and 309 µm and higher flexibility and malleability in comparison with film without SS. Based on p-nitrophenyl palmitate hydrolysis reaction, the activity retention of immobilized lipase was 987%. For optimal conditions, the yield in ethyl oleate was 95% for immobilized enzyme. Maximum yield was obtained at 49°C, molar ratio oleic acid:ethanol of 1:3, 1.25 g lipase film or 50 U (1.03 ± 0.03 mg protein) and 30 h. Even after seven cycles of use, immobilized lipase showed 52% reduction in ester yield. Biodegradable and biorenewable film is a promising material as a support to immobilize lipases and application in biocatalysis.

Reply to Nayak, P.K. Comment on "Samulewski et al. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34".

We have considered the criticisms raised by Pranaba K. Nayak [...].

Study of Ferrocyanide Adsorption onto Different Minerals as Prebiotic Chemistry Assays.

Considered one of the most promising building blocks of life on primitive Earth, cyanide and its complexes are likely to have played an important role in the emergence of life on the planet. Investigation into cyanide on Earth has primarily considered high concentrations, but the cyanide concentration in the oceans of prebiotic Earth was exceptionally low. Thus, Bernal's hypothesis has allowed investigators to work around this problem. We observed, however, that cyanide does not adsorb onto several minerals; therefore, ferrocyanide could be used as a cyanide source when adsorbed onto mineral surfaces to promote the synthesis of molecules of biological significance. When adsorbed onto bentonite, a mineral that has Fe3+ atoms in its interlayers, the formation of Prussian blue analog complexes occurs through endothermic reaction and with increased entropy. The adsorption of ferrocyanide onto kaolinite indicates an exothermic and outer-sphere interaction, which results in degeneracy breakdown for C ≡ N stretch energy into two new bands of FTIR-ATR spectrum. Magnetite, which has iron atoms in its structure, and ferrocyanide interactions have been observed by outer-sphere coordination as well as the formation of Prussian blue analogs, as confirmed by the appearance of a new doublet in the Mössbauer spectra and a broadband close to 750 nm at UV-visible spectroscopy. Magnetite and kaolinite experiments presented relevant results only when performed in seawater, which suggests the importance of seawater composition for prebiotic experiments. These obtained results prove that ferrocyanide interacts with minerals differently according to structure and composition and show that this complex, like the Prussian blue analogs, may have played a crucial role as a source of cyanide on primitive Earth.

Surface Modification of Polyester Fabrics by Ozone and Its Effect on Coloration Using Disperse Dyes.

Polyester fibers (PES) are the most consumed textile fibers due to their low water absorption; non-ionic character and high crystallinity. However, due to their chemical structure, the chemical interactions between polyester, finishing products, and dyes are quite challenging. We report on the use of ozone to modify the surface of polyester fibers with the goal of improving the interaction of the modified surface with finishing compounds and dyes. We used C.I. Disperse Yellow 211 to dye ozone-treated polyester fabrics and evaluated the effects of ozone treatment using FTIR-ATR, Raman spectroscopy, SEM imaging, rubbing tests, and capillarity measurements. We evaluated the dyeing performance via color analysis, and determined the dyeing kinetics. Experimental results indicate that the modification of polyester fabrics with ozone is a feasible pre-treatment that improves dyeing efficiency allowing better solidity of color and a decrease in the amount of dye required.

Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions.

Magnetite is an iron oxide mineral component of primitive Earth. It is naturally synthesized in different ways, such as magma cooling as well as olivine decomposition under hydrothermal conditions. It is probable magnetite played a significant role in biogenesis. The seawater used in the current work contained high Mg2+, Ca2+ and SO42- concentrations, unlike the seawater of today that has high Na+ and Cl- concentrations. It is likely that this seawater better resembled the ion composition of the seas of the Earth from 4 billion years ago. Cyanide and thiocyanate were common molecules in prebiotic Earth, and especially in primitive oceans, where they could act on the magnetite mechanism synthesis via Fe2+ interaction. In this research, magnetite samples that were synthesized under prebiotic conditions in the presence of cyanide or thiocyanate, (both with and without artificial seawater), showed that, besides magnetite, goethite and ferrihydrite can be produced through different Fe2+-ion interactions. Cyanide apparently acts as a protective agent for magnetite production; however, thiocyanate and seawater 4.0 Gy ions produced goethite and ferrihydrite at different ratios. These results validate that Fe3+ oxides/hydroxides were possibly present in primitive Earth, even under anoxic conditions or in the absence of UV radiation. In addition, the results show that the composition of water in early oceans should not be neglected in prebiotic chemistry experiments, since this composition directly influences mineral formation.

In-Situ Direct Synthesis of HKUST-1 in Wool Fabric for the Improvement of Antibacterial Properties.

The use of Metal-Organic Frameworks (MOF) such as HKUST-1 in textiles is an alternative with regard to the development of technologies that are increasingly seeking for functionalities, mainly in the fields of health and hygiene, named biofunctional fabrics. However, the application of the MOF under the surface of the wool fiber can lead to a low durability finish due to its low fixation. Thus, this project aims to perform the direct synthesis of HKUST in the wool fiber, so that a product with good washing durability can be obtained. The purpose of this study was to incorporate metal-organic frameworks, composed of copper and trimesic acid, into woolen fabrics, to improve the antibacterial properties. The synthesis was performed directly in the wool fabric, at time intervals of 24 and 48 h. The resulting fabrics were characterized by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X-Ray Diffractometry (XRD), Fourier Transform Spectroscopy Infrared-Attenuated Total Reflectance (FTIR-ATR), and colorimetric analysis (CIElab), and the Antimicrobial Activity Test (American Association of Textile Chemist and Colourists - AATCC Test Method 61-2007-2A) was performed. The results suggested that the application produced textiles with antibacterial properties, showing activity against Escherichia coli.