Fig 1 - uploaded by J. R. Lyons
Content may be subject to copyright.
(A) Crystal structure of H-ZSM-5 zeolite in which the linkages of tetrahedra define large cages (pores) with 0.55 nm diameter connected by tunnels. It can incorporate molecules no larger than these cages. (B) Crystal structure of MCM-41 mesoporous SiO 2 with periodically spaced unidimensional parallel channels typically 2 to 10 nm in diameter. (C) Schematic of SBA-15 mesoporous silica with hexagonally arranged large pores 5 to 15 nm in diameter, surrounded by largely amorphous silica walls. (D) Schematic of cubic mesoporous KIT-6 silica (pore size larger than 5 nm) with gyroid minimal surface and Ia3d symmetry composed of two interpenetrating chiral channels which result in an interpenetrating network of cylindrical mesopores.

(A) Crystal structure of H-ZSM-5 zeolite in which the linkages of tetrahedra define large cages (pores) with 0.55 nm diameter connected by tunnels. It can incorporate molecules no larger than these cages. (B) Crystal structure of MCM-41 mesoporous SiO 2 with periodically spaced unidimensional parallel channels typically 2 to 10 nm in diameter. (C) Schematic of SBA-15 mesoporous silica with hexagonally arranged large pores 5 to 15 nm in diameter, surrounded by largely amorphous silica walls. (D) Schematic of cubic mesoporous KIT-6 silica (pore size larger than 5 nm) with gyroid minimal surface and Ia3d symmetry composed of two interpenetrating chiral channels which result in an interpenetrating network of cylindrical mesopores.

Source publication
Article
Full-text available
Significance Although catalysis by mineral surfaces has been considered to be important in prebiotic chemistry, the role of porous silica phases, with reactions taking place within specific confined environments, has not been explored. This paper proposes that structure direction through interaction of dissolved silica with organic species in aqueo...

Contexts in source publication

Context 1
... synthesis, taking advantage of the interaction of silica with organic SDA, has produced hundreds of new porous highsilica zeolitic materials, both emulating natural zeolites and having totally new structures (11). They contain (Fig. 1A) frameworks of linked silicate tetrahedra, but now these define much larger cages and tunnels which can absorb and perform catalytic chemistry on organic molecules converting them into value-added chemicals. Though much commercial zeolite synthesis uses high temperature and high pH to speed reaction and increase yield, a number of ...
Context 2
... postsynthesis modification confirms the chemical flexibility of porous silicate materials and, if true for silica, can provide further pathways for silica-organic interactions under prebiotic conditions. Mesoporous silica phases ( Fig. 1 B-D) form a family of materials synthesized using common organic surfactants as SDA (9). These surfactants, rather than being uniformly dissolved in the aqueous solution, form micelles above a critical surfactant concentration. ...
Context 3
... synthesis, taking advantage of the interaction of silica with organic SDA, has produced hundreds of new porous highsilica zeolitic materials, both emulating natural zeolites and having totally new structures (11). They contain (Fig. 1A) frameworks of linked silicate tetrahedra, but now these define much larger cages and tunnels which can absorb and perform catalytic chemistry on organic molecules converting them into value-added chemicals. Though much commercial zeolite synthesis uses high temperature and high pH to speed reaction and increase yield, a number of ...
Context 4
... postsynthesis modification confirms the chemical flexibility of porous silicate materials and, if true for silica, can provide further pathways for silica-organic interactions under prebiotic conditions. Mesoporous silica phases ( Fig. 1 B-D) form a family of materials synthesized using common organic surfactants as SDA (9). These surfactants, rather than being uniformly dissolved in the aqueous solution, form micelles above a critical surfactant concentration. ...

Similar publications

Article
Full-text available
Dynamic interplay between peptide synthesis and membrane assembly would have been crucial for the emergence of protocells on the prebiotic Earth. However, the effect of membrane-forming amphiphiles on peptide synthesis, under prebiotically plausible conditions, remains relatively unexplored. Here we discern the effect of a phospholipid on peptide s...

Citations

... These results provide examples of possible synthesis of prebiotic molecules in high-temperature environments. It is worth mentioning the study of the role of porous silica environments in prebiotic organic transformations, especially from amino acids to peptides to proteins, on the early Earth (Navrotsky et al., 2021) and studies of the formation of organic compounds in meteorites (acting as catalysts) at high temperatures (Anders et al., 1973;Rotelli et al., 2016). There are also chemical applications of the catalytic properties of silicate materials at high temperatures (e.g., (Fazlinia and Sheikh, 2018;Ramanathan and Subramaniam, 2018;Bawaked and Narasimharao, 2020)). ...
Article
Full-text available
The study of exoplanetary atmospheres extends the frontiers of astronomy, astrophysics, and astrochemistry. Moreover, studies of exoplanets as being linked to the search for extraterrestrial life and other habitable planets are of interest not only for scientists, but for a much wider public audience. There is much evidence that clouds exist and are common in the exoplanetary atmospheres at high temperatures. Their origin can be gas-phase condensation of silicate materials and other refractory materials. Clouds have a major impact on the planets’ observable properties. Models describing atmospheres of exoplanets and brown dwarfs point to the necessity of including nanometer-to micrometer-sized grains of silicates. Observational mid-IR spectra have also provided tentative evidence of silicate grain absorption. Thus, silicates seem to be the first target for future astronomical observations of cloudy atmospheres and for laboratory studies supporting these observations. However, high-temperature laboratory studies of optical and structural properties of refractory materials, including silicates, and of gas-grain and grain surface chemistry needed for the decoding of astronomical spectra and for the development of reliable atmospheric models present practically uncharted territory. The aim of our paper is to review previous studies of optical and chemical properties of silicate materials and to emphasize the importance and perspective of high-temperature measurements of laboratory analogues of atmospheric silicate grains for exoplanet atmosphere characterization. This is particularly important in the light of new advanced astronomical instruments, which, as we expect, will bring comprehensive information on exoplanetary atmospheres.
... If life originated in quenches of hot fluids from ocean rifts, then a much justified concern is that the fluids emitted would be rapidly dispersed from their origin by hydrodynamic processes, which would dilute them so much that any kind of lifelike process might be impossible. Examples of suggestions for trapping mechanisms which might prevent this are found, for example, in [52,53]. However, it appears that one might look for signs of prebiotic chemistry in contexts in which the bath of water into which the fluids were emitted was less turbulent and of smaller volume than around most ocean ridges. ...
Article
Full-text available
Some standard arguments are reviewed supporting deep ocean trenches as a likely location for the origin of terrestrial life. An analysis of proteomes of contemporary prokaryotes carried out by this group is cited as supporting evidence, indicating that the original proteins were formed by quenching from temperatures close to the boiling point of water. Coarse-grained simulations of the network formation process which agree quite well with experiments of such quenches both in drying and rapid fluid emission from a hot to a cold fluid are also described and cited as support for such a scenario. We suggest further experiments, observations and theoretical and simulation work to explore this hypothesis.
... [7]. Navrotsky et al. 2021 suggested that amino acids, small peptides and fatty acids might acted as structure directing agents for functional porous silica structure gathering that promotes polymerization of amino acids and peptides along with other organic reactions [10]. Amino acids are the building block, as well as essential components for the formation and growth of life.Proteins act as catalyst in biochemical reactions, building materials for living cell, structural role inside the cell and found within the cell membrane. ...
... [7]. Navrotsky et al. 2021 suggested that amino acids, small peptides and fatty acids might acted as structure directing agents for functional porous silica structure gathering that promotes polymerization of amino acids and peptides along with other organic reactions [10]. Amino acids are the building block, as well as essential components for the formation and growth of life.Proteins act as catalyst in biochemical reactions, building materials for living cell, structural role inside the cell and found within the cell membrane. ...
Preprint
Full-text available
Double metal cyanide (DMC), a heterogeneous catalyst, is a key factor for polymerization of amino acids. Based on the hypothesis, the present study is designed to evaluate favorable environmental conditions for the chemical evolution and origin of life such as effects of temperature and time for the oligomerization of glycine and alanine on Metal(II) Hexacyanocobaltate(III), MHCCo. It has been shown that MHCCo is porous and because of high surface area it has outstanding catalytic properties. Our results revealed that the Manganese(II) Hexacyanocobaltate(III) (MnHCCo), Iron(II) Hexacyanocobaltate(III) (FeHCCo), Nickel(II) Hexacyanocobaltate(III) (NiHCCo) complexes condense the glycine up to trimer and alanine up to dimer while ZnHCCo showed most valuable catalytic properties that changes glycine into tetramer and alanine into dimer with the high yield. High-Performance liquid chromatography (HPLC) and Electron Spray Ionizations-Mass spectroscopy (ESI-MS) techniques were used to confirm the oligomer products of glycine and alanine formed on MHCCo complexes. The results also exposed the catalytic role of MHCCo for the oligomerization of biomolecules thus supports the chemical evolution.
... Numerous experimental and computational studies can be found in the literature involving the mechanism of silica speciation and nucleation in the context of porous material synthesis 2,3,14,[17][18][19][20][21][22][23][24][25][26][27][28][29] . Therefore, the mechanisms that govern the oligomerization of silica in simple aqueous solutions are often assumed to be well understood. ...
Article
Full-text available
We report a molecular modeling paradigm to describe silica polymerization reactions in aqueous solutions at conditions that are representative of realistic experimental processes like biosilicification or porous silica synthesis – i.e. at close to ambient temperatures and over a wide range of pH. The key point is to describe the Si-O-Si chemical bond formation and breakage processes through a continuous potential with a balance between attractive and repulsive interactions between suitably placed virtual sites and sticky particles. The simplicity of the model, its applicability in standard parallelized molecular dynamics codes, and its compatibility with the widely used MARTINI coarse-grained force-field allows for the study of systems containing millions of atoms over microsecond time scales. The model is calibrated to match experimental results for the temporal evolution of silica polymerization in aqueous solution close to the isoelectric point, and can describe silica polymerization and self-assembly processes during encapsulation of a surfactant micelle.
Chapter
Abiogenesis is a prebiotic evolution, an interacting network of primordial prebiomolecules. We can gain insight into how this network developed by examining molecular fossils available on Earth and in space. Initial investigations were limited to studies that could be conducted from the Earth’s surface, the composition of meteorites, particularly the carbonaceous chondrites, and spectroscopy within the optical, infrared, and radio bands. Radio astronomy revealed the rich mix present in the interstellar medium, from which spectroscopic measurements have detected more than 300 molecular fossils that occupy niches on the path to life. Mass spectrometry of meteorites showed that many prebiomolecules spontaneously self-assembled protected by shadowing from the radiation environment of outer space. With the advent of space exploration, several other important sources of molecular fossils became available, including the compositions of planets, comets, and asteroids. The result of this data storm was to find that prebiomolecules were found everywhere one looked. Polycyclic aromatic hydrocarbons, the kind that are produced in your charcoal grill, were found to be ubiquitous. Early parallel laboratory experiments, begun by Stanley Miller, showed how easy it was to form amino acids, the constituents of proteins. The self-assembly of amino acids into peptides was subsequently demonstrated. The presence on Earth of phosphorus, a rate-limiting ingredient in life, is examined. Recent data from the sample-return mission to Ryugu indicates that nucleic acid bases spontaneously formed during the 4.5-GYa asteroid-forming epoch in the evolution of the solar system. We also review the formation of nucleic acids, the purines and the pyrimidines, as well as the synthesis of essential ribose and both the nucleosides and nucleotides, and the nucleic acid polymers. The prebiotic synthesis of carbohydrates and lipids is presented as a fait accompli.
Article
Basalt reservoirs offer the potential for carbon mineralization, aiding in achieving net-zero emissions. However, debates persist about microscopic crystallization mechanisms due to limited characterization techniques under high-temperature and pressure conditions. By using Identical Location Transmission Electron Microscopy (IL-TEM) and cryo-TEM, this study reveals nanoscale interfacial carbonation processes of forsterite and diopside nanoparticles in water-saturated supercritical carbon dioxide under realistic reservoir conditions. Both minerals undergo preferential metal cation dissolution into a thin water film, forming porous Si-rich amorphous layers, supporting the leached layer mechanism as the dominant mineral reactivity process. Diopside’s amorphous layer has lower porosity and growth rate relative to forsterite, likely related to the connectivity of silicate tetrahedra. Kinetically favorable nesquehonite and aragonite nanocrystals form on the amorphous layers. These findings support the development of accurate reservoir simulations and help enable commercial-scale carbon storage deployment.
Article
Full-text available
Mesoporous silica has been applied in catalysis, separations, and drug delivery. It has generally been made using organosilicon precursors such as tetraethyl orthosilicate. For sustainability, it is necessary to find readily accessible mineral sources for making mesoporous silica. In this work, we demonstrate the successful synthesis of mesoporous silica with 10 nm average pore size using the mineral forsterite (Mg2SiO4) as a silica source, providing a potentially cheaper and more Earth‐friendly route to making technologically important porous silica materials. Pure forsterite was synthesized by a solid‐state chemistry route at 1000°C and underwent dissolution–reprecipitation in aqueous hydrochloric acid containing the soft template surfactant, Pluronic P123. Variations of initial reaction pH (−0.2 to 0.6), reaction time (12–24 h), reaction temperature (50 to 90°C), and silica precursor (forsterite and fumed silica) were performed. The mesoporous silica aged at 70°C for 24 h had the highest porosity, with a surface area of 735 m²/g and a pore volume of 1.4 ml/g, comparable to mesoporous silica made using conventional starting materials. This novel geomimetic synthesis route supports the possibility of analogous formation of structured (mesoporous or zeolitic) silica in nature under abiotic or prebiotic conditions.