Chemical Gardens Research Articles

Fe/Mg-Silicate Chemical Gardens as Analogs to Silicate-Rich Hydrothermal Chimneys on Early Earth and Mars

Fe/Mg-Silicate Chemical Gardens as Analogs to Silicate-Rich Hydrothermal Chimneys on Early Earth and Mars

Chemical gardens as analogs for prebiotic chemistry on ocean worlds

Chemical gardens as analogs for prebiotic chemistry on ocean worlds

Enzymes on chemical gardens: Chemobrionics-based electrochemical biosensor

The relationship between biological materials and the immobilization matrix is a critical point in attaching biomolecules onto transducers in the preparation of biosensors. Various chemical molecules are used to conjugate biological compounds in the design of biofunctional surfaces. Among them, chemobrionics (CBCs) are good alternatives as an immobilization matrix to improve performance parameters such as linear range, limit of detection (LOD), stability, reproducibility, etc. Here, CBCs are used to develop enzymatic biosensor, and glucose oxidase (GOx) is selected as a model enzyme. Firstly, CBC is functionalized using (3-Aminopropyl)triethoxysilane (APTES) to obtain free amine groups for immobilization of GOx via covalent bonds. The synthesized CBC-APTES is used as a matrix for the conjugation of GOx using glutaraldehyde as a crosslinker. The proposed CBC-APTES/GOx is formed on the glassy carbon electrode, and its performance is checked for glucose detection. The linear range is 0.025–1.25 mM with an LOD of 0.024 mM glucose. After finding no effect of some potential interference on the current response, CBC-APTES/GOx is successfully applied to analyze glucose in artificial samples such as serum, urine, sweat, and saliva. The objective here is to outline the integration of CBC in biosensor preparation, which has been successfully carried out for the first time in the literature.

Effect of Temperature on Calcium‐Based Chemical Garden Growth

AbstractHydrothermal vents maintain far‐from equilibrium conditions that may have provided the necessary settings for the origin of life. To understand reactions under these physicochemical conditions, scientists have turned to the classic demonstration experiment, chemical gardens. The self‐organization of precipitate tubes separates high and low pH environments similarly to the naturally occurring geological structures. Here, we report calcium‐based chemical gardens forming in solutions containing anions of silicate, carbonate, or a mixture of the two in 100 °C and 23 °C environments. Under high temperature conditions, chemical gardens tend to have faster average growth velocities and form taller structures. We measure the composition of the precipitate tubes using Fourier transform infrared spectroscopy and find the formation of all polymorphs of calcium carbonate along with calcium silicates.

Magnesium silicate chimneys at the Strytan hydrothermal field, Iceland, as analogues for prebiotic chemistry at alkaline submarine hydrothermal vents on the early Earth

The Strytan Hydrothermal Field (SHF) in basaltic terrain in Iceland is one of the extant alkaline submarine hydrothermal vent systems favoured as analogues for where life on Earth may have begun. To test this hypothesis we analyse the composition, structure, and mineralogy of samples from hydrothermal chimneys generated at the SHF. We find that the chimney precipitates are composed of Mg-silicates including clays of the saponite-stevensite group (high Mg and Si, low Fe and Al), Ca-carbonates and Ca-sulfates. The chimneys comprise permeable structures with pores sizes down to 1 µm or less. Their complex interiors as observed with SEM (Scanning Electron Microscopy) and X-ray CT (computed tomography scanning), exhibit high internal surface areas. EDX (energy-dispersive X-ray spectroscopy) analysis reveals an increase in the Mg/Si ratio toward the chimney exteriors. Chemical garden analogue experiments produce similar Mg–silicate chimneys with porous internal structures, indicating that injection-precipitation experiments can be high-fidelity analogues for natural hydrothermal chimneys at the SHF. We conclude that SHF chimneys could have facilitated prebiotic reactions comparable to those proposed for clays and silica gels at putative Hadean to Eoarchean alkaline vents. Analysis of the fluid dynamics shows that these chimneys are intermediate in growth rate compared to faster black smokers though slower than those at Lost City. The SHF is proposed as a prebiotic alkaline vent analogue for basaltic terrains on the early Earth.

Coiling of Secondary Tubes Formed from the Colloidal Exhaust of Primary Chemical Gardens.

Chemical gardens are self-organized precipitate structures such as thin-walled tubes and membrane-bound cells reminiscent of biological shapes. These usually inorganic precipitates compartmentalize the reaction system and allow the study of materials synthesis in very steep concentration gradients. We create such tubes by steadily injecting a mixture of MnCl2 and CuSO4 solutions into a large reservoir of sodium silicate solution. The growing tube is open at its tip and ejects a stream of colloidal particles that aggregate to form a secondary tube above the original one. This secondary tube can coil into a tightly wound nest-like structure, freely suspended underneath the solution-air interface. Using three-dimensional image reconstruction, we analyze the onset of coiling and show that the structure is helical with a helix radius that increases in the vertical direction. The height at which the coiling begins is lowered with each successive repeat of the growth experiment, suggesting that coiling is induced by small variations in the density of the silicate solution.

Interface Engineering Enables Multilevel Resistive Switching in Ultra-Low-Power Chemobrionic Copper Silicate.

Memristor is assuming prominence due to its exceptionally low power consumption, adaptable, and parallel signal processing capabilities that address the limitations of the von Neumann architecture to meet the growing demand for advanced technologies such as artificial intelligence, Internet of Things (IoTs), and neuromorphic computation. In this work, we demonstrate resistive switching in copper silicate-based hollow tube-forming self-organized membrane structures belonging to the category of chemobrionics or chemical gardens to demonstrate cost-effective and highly efficient memristor devices. The device architecture is configured as ITO/PEDOT:PSS/active layer (copper silicate)/PMMA/Ag, an arrangement that serves to stabilize current-voltage hysteresis and exhibit a low SET voltage ∼0.2 V with a 0.8 nJ power consumption while manifesting robust data endurance and multilevel resistive switching. The inherent self-rectifying behavior, characterized by a high rectification ratio of 60, underscores the potential utility of these devices across a spectrum of electronic applications. To emulate the functionality of biological synapses, fundamental synaptic characteristics are assessed, including paired-pulse facilitation (PPF) and potentiation and depression (P&D). We validate the potential of copper silicate chemical garden-based memristor devices for applications that require real-time synaptic processing. Importantly, the fabrication of these devices was accomplished through a comprehensive solution-based, low-temperature process conducted under ambient environmental conditions, obviating the need for specialized glovebox facilities.

Comparative Evaluation of Chemical Garden Growth Techniques.

Chemical gardens are an exciting area of self-organized precipitation structures that form nano- and micro-sized structures in different shapes. This field has attracted great interest from researchers due to the specific characteristics and potential applications of these structures. Today, research on chemical gardens has provided deeper information regarding the formation mechanisms of these structures, and several techniques have been developed for chemical garden growth. However, they all show different growth patterns and lead to the formation of structures with a variety of morphological, chemical, or physical properties. This study aimed to evaluate the effects of different production techniques on chemical garden growth, taking into consideration the growth patterns, morphology, microstructure, and chemical composition. The chemical garden structures obtained in seed and injection experiments, two common methods, showed highly similar surface structures, void formation, and chemical composition. The membrane growth method has a small number of applications; thus, it was comprehensively evaluated to add new insights to the existing limited data. It produced the most stable and standard structures in a flat sheet-like shape and showed different morphologies than those observed in other two methods. Overall, this study presented significant results about the effect of growth techniques on chemical garden structures and similar systems.

White and green rust chimneys accumulate RNA in a ferruginous chemical garden.

Mechanisms of nucleic acid accumulation were likely critical to life's emergence in the ferruginous oceans of the early Earth. How exactly prebiotic geological settings accumulated nucleic acids from dilute aqueous solutions, is poorly understood. As a possible solution to this concentration problem, we simulated the conditions of prebiotic low-temperature alkaline hydrothermal vents in co-precipitation experiments to investigate the potential of ferruginous chemical gardens to accumulate nucleic acids via sorption. The injection of an alkaline solution into an artificial ferruginous solution under anoxic conditions (O2 < 0.01% of present atmospheric levels) and at ambient temperatures, caused the precipitation of amakinite ("white rust"), which quickly converted to chloride-containing fougerite ("green rust"). RNA was only extractable from the ferruginous solution in the presence of a phosphate buffer, suggesting RNA in solution was bound to Fe2+ ions. During chimney formation, this iron-bound RNA rapidly accumulated in the white and green rust chimney structure from the surrounding ferruginous solution at the fastest rates in the initial white rust phase and correspondingly slower rates in the following green rust phase. This represents a new mechanism for nucleic acid accumulation in the ferruginous oceans of the early Earth, in addition to wet-dry cycles and may have helped to concentrate RNA in a dilute prebiotic ocean.

Hybrid organic–inorganic structures trigger the formation of primitive cell-like compartments

Alkaline hydrothermal vents have become a candidate setting for the origins of life on Earth and beyond. This is due to several key features including the presence of gradients of temperature, redox potential, pH, the availability of inorganic minerals, and the existence of a network of inorganic pore spaces that could have served as primitive compartments. Chemical gardens have long been used as experimental proxies for hydrothermal vents. This paper investigates-10pc]Please note that the spelling of the following author name in the manuscript differs from the spelling provided in the article metadata: Richard J. G. Löffler. The spelling provided in the manuscript has been retained; please confirm. a set of prebiotic interactions between such inorganic structures and fatty alcohols. The integration of a medium-chain fatty alcohol, decanol, within these inorganic minerals, produced a range of emergent 3 dimensions structures at both macroscopic and microscopic scales. Fatty alcohols can be considered plausible prebiotic amphiphiles that might have assisted the formation of protocellular structures such as vesicles. The experiments presented herein show that neither chemical gardens nor decanol alone promote vesicle formation, but chemical gardens grown in the presence of decanol, which is then integrated into inorganic mineral structures, support vesicle formation. These observations suggest that the interaction of fatty alcohols and inorganic mineral structures could have played an important role in the emergence of protocells, yielding support for the evolution of living cells.

Nonclassical Crystallization Causes Dendritic and Band-Like Microscale Patterns in Inorganic Precipitates.

The self-organization of complex solids can create patterns extending hierarchically from the atomic to the macroscopic scale. A frequently studied model is the chemical garden system which consists of life-like precipitate shapes. In this study, we examine the thin walls of chemical gardens using microfluidic devices that yield linear Ni(OH)2 precipitate membranes. We observe distinct light-scattering patterns within the compositionally pure membranes, including disorganized spots, dendrites, and parallel bands. The bands are tilted with respect to the membrane axis and their spacing (20-100 μm) increases with increasing flow rates. Scanning electron microscopy reveals that the bands consist of submicron particles embedded in a denser material and these particles are also found in the reactant stream. We propose that dendrites and bands arise from the attachment of solution-borne nanoparticles. The bands are generated by particle-aggregation zones moving upstream along the slowly advancing membrane surface. The speed of the aggregation zones is proportional to the band distance and defines the system's dispersion relation. This speed-wavelength dependence and the flow-opposing motion of the aggregation zones are likely caused by low particle concentrations in the wake of the zones that only slowly recover due to Brownian motion and particle nucleation.

Nonclassical Crystallization Causes Dendritic and Band‐Like Microscale Patterns in Inorganic Precipitates

AbstractThe self‐organization of complex solids can create patterns extending hierarchically from the atomic to the macroscopic scale. A frequently studied model is the chemical garden system which consists of life‐like precipitate shapes. In this study, we examine the thin walls of chemical gardens using microfluidic devices that yield linear Ni(OH)2 precipitate membranes. We observe distinct light‐scattering patterns within the compositionally pure membranes, including disorganized spots, dendrites, and parallel bands. The bands are tilted with respect to the membrane axis and their spacing (20–100 μm) increases with increasing flow rates. Scanning electron microscopy reveals that the bands consist of submicron particles embedded in a denser material and these particles are also found in the reactant stream. We propose that dendrites and bands arise from the attachment of solution‐borne nanoparticles. The bands are generated by particle‐aggregation zones moving upstream along the slowly advancing membrane surface. The speed of the aggregation zones is proportional to the band distance and defines the system's dispersion relation. This speed‐wavelength dependence and the flow‐opposing motion of the aggregation zones are likely caused by low particle concentrations in the wake of the zones that only slowly recover due to Brownian motion and particle nucleation.

Pattern selection by material aging: Modeling chemical gardens in two and three dimensions

Chemical gardens are complex, often macroscopic, structures formed by precipitation reactions. Their thin walls compartmentalize the system and adjust in size and shape if the volume of the interior reactant solution is increased by osmosis or active injection. Spatial confinement to a thin layer is known to result in various patterns including self-extending filaments and flower-like patterns organized around a continuous, expanding front. Here, we describe a cellular automaton model for this type of self-organization, in which each lattice site is occupied by one of the two reactants or the precipitate. Reactant injection causes the random replacement of precipitate and generates an expanding near-circular precipitate front. If this process includes an age bias favoring the replacement of fresh precipitate, thin-walled filaments arise and grow-like in the experiments-at the leading tip. In addition, the inclusion of a buoyancy effect allows the model to capture various branched and unbranched chemical garden shapes in two and three dimensions. Our results provide a model of chemical garden structures and highlight the importance of temporal changes in the self-healing membrane material.

A self-sustaining serpentinization mega-engine feeds the fougerite nanoengines implicated in the emergence of guided metabolism.

The demonstration by Ivan Barnes et al. that the serpentinization of fresh Alpine-type ultramafic rocks results in the exhalation of hot alkaline fluids is foundational to the submarine alkaline vent theory (AVT) for life's emergence to its 'improbable' thermodynamic state. In AVT, such alkaline fluids ≤ 150°C, bearing H2 > CH4 > HS--generated and driven convectively by a serpentinizing exothermic mega-engine operating in the ultramafic crust-exhale into the iron-rich, CO2> > > NO3--bearing Hadean ocean to result in hydrothermal precipitate mounds comprising macromolecular ferroferric-carbonate oxyhydroxide and minor sulfide. As the nanocrystalline minerals fougerite/green rust and mackinawite (FeS), they compose the spontaneously precipitated inorganic membranes that keep the highly contrasting solutions apart, thereby maintaining redox and pH disequilibria. They do so in the form of fine chimneys and chemical gardens. The same disequilibria drive the reduction of CO2 to HCOO- or CO, and the oxidation of CH4 to a methyl group-the two products reacting to form acetate in a sequence antedating the 'energy-producing' acetyl coenzyme-A pathway. Fougerite is a 2D-layered mineral in which the hydrous interlayers themselves harbor 2D solutions, in effect constricted to ~ 1D by preferentially directed electron hopping/tunneling, and proton Gröthuss 'bucket-brigading' when subject to charge. As a redox-driven nanoengine or peristaltic pump, fougerite forces the ordered reduction of nitrate to ammonium, the amination of pyruvate and oxalate to alanine and glycine, and their condensation to short peptides. In turn, these peptides have the flexibility to sequester the founding inorganic iron oxyhydroxide, sulfide, and pyrophosphate clusters, to produce metal- and phosphate-dosed organic films and cells. As the feed to the hydrothermal mound fails, the only equivalent sustenance on offer to the first autotrophs is the still mildly serpentinizing upper crust beneath. While the conditions here are very much less bountiful, they do offer the similar feed and disequilibria the survivors are accustomed to. Sometime during this transition, a replicating non-ribosomal guidance system is discovered to provide the rules to take on the incrementally changing surroundings. The details of how these replicating apparatuses emerged are the hard problem, but by doing so the progenote archaea and bacteria could begin to colonize what would become the deep biosphere. Indeed, that the anaerobic nitrate-respiring methanotrophic archaea and the deep-branching Acetothermia presently comprise a portion of that microbiome occupying serpentinizing rocks offers circumstantial support for this notion. However, the inescapable, if jarring conclusion is drawn that, absent fougerite/green rust, there would be no structured channelway to life.

From Balloon to Crystalline Structure in the Calcium Phosphate Flow-Driven Chemical Garden.

We have studied the calcium phosphate precipitation reaction by producing chemical gardens in a controlled manner using a three-dimensional flow-driven technique. The injection of the phosphate containing solution into the calcium ion reservoir has resulted in structures varying from membranes to crystals. Dynamical phase diagrams are constructed by varying chemical composition and flow rates from which three different growth mechanisms have been revealed. The microstructural analysis by scanning electron microscopy and powder X-ray diffraction confirmed the morphological transition from membrane tubes to crystalline branches upon decreasing pH.

Chemobrionics Database: Categorisation of Chemical Gardens According to the Nature of the Anion, Cation and Experimental Procedure**

AbstractConsidering the growing importance of the field of chemobrionics since the term was coined in 2015 and the increase in the number of published papers, it has become necessary to catalogue all the papers published to date. Here, we present the chemobrionics database, which lists all the chemical gardens synthesised according to their anion, cation and experimental protocol. The aim of this database is to encourage the study and dissemination of chemical gardens in order to find new experimental avenues in the field of chemobrionics. As this is such a fruitful field, the database is continuously updated.

Shape Evolution of Precipitate Membranes in Flow Systems

Chemical gardens are macroscopic structures that form when a salt seed is submerged in an alkaline solution. Their thin precipitate membranes separate the reactant partners and slow down the approach toward equilibrium. During this stage, a gradual thickening occurs, which is driven by steep cross-membrane gradients and governed by selective ion transport. We study these growth dynamics in microfluidic channels for the case of Ni(OH)2 membranes. Fast flowing reactant solutions create thickening membranes of a nearly constant width along the channel, whereas slow flows produce wedge-shaped structures that fail to grow along their downstream end. The overall dynamics and shapes are caused by the competition of reactant consumption and transport replenishment. They are reproduced quantitatively by a two-variable reaction-diffusion-advection model which provides kinetic insights into the growth of precipitate membranes.

A Further Study on Calcium Phosphate Gardens Grown from the Interface of κ-Carrageenan-based Hydrogels and Counterion Solutions.

Originating from the concept of classical chemical gardens, a new field coined 'chemobrionics' has recently emerged. In the present work, two chemobrionic systems grown from a hydrogel/liquid interface at different time scales (for 1, 7, 14 or 28 days) were investigated, i. e., a calcium-based hydrogel with a phosphate counterion solution (Ca-gel) and a phosphate-based hydrogel with a calcium counterion solution (P-gel). The initial pH changes of the systems were investigated, and the obtained tubular structures were studied using optical microscopy, SEM, AFM, PXRD and TGA. One of the important findings is that the tubes obtained in the Ca-gel system were straight and long, which could be explained by the larger pH difference observed between the hydrogel and the counterion solution in this system (ΔpH∼2.1) compared to the P-gel system (ΔpH∼0). The Ca-gel structures remained overall more amorphous even though increased crystallinity was observed in both systems with increased time spent in counterion solution. Both systems contained hydroxyapatite phases, with additional calcite phases observed for the P-gel structures and traces of κ-carrageenan for the Ca-gel structures. Our study provides a promising method for controlling tubular macrostructures through adjusting the reaction conditions such as maturation time and pH.

A microfluidic labyrinth self-assembled by a chemical garden.

Chemical gardens, self-assembling precipitates that spontaneously form when a metal salt is added to a solution of another precipitating anion, are of interest for various applications including producing reactive materials in controlled structures. Here, we report on two chemical garden reaction systems (CuCl2 and Cu(NO3)2 seed crystals submerged in sodium silicate) that produced self-assembled microfluidic labyrinths in a vertical 2D Hele-Shaw reactor. The formation of labyrinths as well as the specific growth modes of the precipitate were dependent on the silicate concentration: CuCl2 labyrinths formed only at 3 and 4 M silicate and Cu(NO3)2 labyrinths formed only at 4 and 5 M silicate. The labyrinth structures contained silicate on the exterior and crystalline material interpreted as hydrated minerals from the metal salt in their interiors. The bubble-guided tubes that form labyrinths can be controlled by changing the angle of the 2D reaction cell; this suggests that future experiments of this type could form self-organizing structures with controlled composition and orientation for use in microfluidics and various materials science applications.

Characteristic growth of chemical gardens from mixtures of two salts.

Chemical gardens formed from two metal salts (MCl2 or MSO4) have been investigated to understand the effects of mixing on the growth of precipitate tubes. The growth of tubes can be classified into three types, i.e., collaborative, inhibited, and individual growth, depending on the combination of the two metal salts. Characteristic features of tube growth are discussed in relation to the flow near the tip of the tube controlled by osmotic pressure and the solubility product, Ksp, for M(OH)2. The present study can be interpreted as an inanimate model system of symbiosis among different species, such as mixed cropping systems and survival among different kinds of microbial cells.