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Spontaneous Formation of Cellular Chemical System that Sustains Itself far from Thermodynamic Equilibrium
Abstract
We report the observation of the spontaneous formation of a cellular structure in a simple inorganic system. The system is obtained by immersing a pellet of calcium and copper chlorides in an alkali solution containing sodium carbonate, sodium iodide, and hydrogen peroxide. The system produces a cell surrounded by a semipermeable membrane. Reactants diffuse and react inside the cell with copper ions serving as catalyst. The products diffuse out of the cell. The system sustains itself far from thermodynamic equilibrium.
... Self-assembled carbonate-based mineral precipitations have implications for biomineralization and bio-inspired materials design (Cardoso et al., 2016;Birkedal and Chen, 2020), origin of life, and prebiotic chemistry (Cardoso et al., 2019;Chin et al., 2020;Angelis et al., 2021), and life detection , 2020McMahon, 2019). Owing to their rich applicability, several studies have reported the formation and characterization of carbonate-based tubular and vesicular structures synthesized by immersion of metal-containing salt seeds and pellets in Na2CO3 solutions (Maselko and Strizhak, 2004;Maselko et al., 2005;Cardoso et al., 2016Cardoso et al., , 2019, by injection of metal salt solutions into carbonate solutions (Kiehl et al., 2015;Takács et al., 2019), by growth on cation exchange membranes (Takiguchi et al., 2006;Igarashi et al., 2008) and gel/liquid interfaces (Steenbjerg Ibsen et al., 2014;Birkedal and Chen, 2020). Metal carbonate membranes have been also produced in quasi-2D confined Hele-Shaw cell by injecting carbonate solution into a solution containing metal salts Schuszter and De Wit, 2016). ...
... Despite the tubes are synthesized in a mix of hydroxide and carbonate solutions, the carbonate didn't contribute to the precipitate and the membrane is purely aluminium hydroxide (Kiehl et al., 2015). Maselko and Strizhak (2004) could grow relatively wider tubular calcium-based carbonate tubes by immersing pressed pellets of calcium chloride in sodium carbonate solutions (Figure 13d). ...
... (a) Calcium carbonate tubes grown on cation-exchange membrane; (b) electron microscope image of tubes grown on cation-exchange membrane (afterTakiguchi et al., 2006); (c) time lapse photos of tubes synthesized by injecting saturated AlCl3 into 0.3 M NaOH and 0.22 M Na2CO3 (afterKiehl et al., 2015); (d) membrane formed by submerging calcium chloride pellet in 1.5 M of sodium carbonate solution, pellet diameter 6 mm (afterMaselko and Strizhak, 2004); (e) CaCO3 patterns obtained by injecting 0.26 M carbonate solution into 0.68 M calcium salt solution, field of view 123 mm×98 mm (after Schuszter and De Wit, 2016); (f) CaCO3 patterns obtained by injecting 1.5 M carbonate solution into 0.5 M Ca solution, field of view 123 mm×98 mm (after Schuszter et al., 2016b); (g) BaCO3 patterns obtained by injecting 0.26 M carbonate solution into 0.68 M barium solution, field of view 123 mm×98 mm (after Schuszter and De Wit, 2016); (h) filaments obtained by injecting 1 M CoCl2 solution into 2.5 M Na2CO3, field of view 15 cm×15 cm (taken from Haudin et al., 2015a) Recently, carbonate-based self-assembled structures attracted the attention of origin of life, ...
... [2,3,[9][10][11] Consequently, the interest in chemical gardens in the context of self-fueled microreactors has also increased in the last years. [12][13][14][15][16] Clearly, the idea of having a "battery" of hundreds of millivolts for at least several hours is worth to be explored with respect to synthetic chemistry. Indeed, recent work could show that tubular chemical gardens and osmosis-driven mineral vesicles catalyze the conversion of formamide into nucleobases and amino acids. ...
... [17][18][19] Furthermore, experimental evidence suggesting that chemical gardens are geochemically plausible structures [20][21][22] triggers a new view of the likely relevance of these self-assembled microreactors in the context of the origin of life. [17][18][19] While chemical gardens can be grown with various anions such as aluminate, [12,23,24] oxalate, [25] carbonate, [13,26,27] phosphate, [28,29] hydroxide, [16] or oxometallate, [30,31] most research efforts have been devoted to systems based on silicate solutions, the so-called silica gardens. These structures are typically made by soaking small solid particles of soluble metal salts in a concentrated, strongly alkaline silicate solution. ...
... Tubular structures and mineral vesicles consisting of iron, cobalt, manganese, magnesium, zinc, barium, and calcium carbonate have been confirmed to form with waters of the Magadi lake (Kenya), [22] which is considered a modern analogue of the early soda oceans. Several previous studies have reported the formation and ex situ characterization of calcium carbonate-based tubular structures synthesized by immersion of Ca 2 + -containing salts pellets in Na 2 CO 3 solutions, [13,26,27] or by growth on cationexchange membranes [38,39] and gel/liquid interfaces. [40] However, dynamic diffusion and precipitation processes occurring during the growth and subsequent ripening have not been studied yet in this system. ...
Calcium carbonate chemical gardens are tubular mineral structures precipitated upon the addition of sodium carbonate solution to calcium chloride pellets. The tubes are composed of texturally distinct bilayers of aggregates of rhombohedral and cone‐shaped calcite on their exterior and interior surfaces, respectively. These highly crystalline and dense bilayers prohibit the development of significant electrochemical potential differences across the tube walls. More information can be found in the Full Paper by M. Kellermeier, J. M. García‐Ruiz et al. (DOI: 10.1002/chem.202101417).
... [2,3,[9][10][11] Consequently, the interest in chemical gardens in the context of self-fueled microreactors has also increased in the last years. [12][13][14][15][16] Clearly, the idea of having a "battery" of hundreds of millivolts for at least several hours is worth to be explored with respect to synthetic chemistry. Indeed, recent work could show that tubular chemical gardens and osmosis-driven mineral vesicles catalyze the conversion of formamide into nucleobases and amino acids. ...
... [17][18][19] Furthermore, experimental evidence suggesting that chemical gardens are geochemically plausible structures [20][21][22] triggers a new view of the likely relevance of these self-assembled microreactors in the context of the origin of life. [17][18][19] While chemical gardens can be grown with various anions such as aluminate, [12,23,24] oxalate, [25] carbonate, [13,26,27] phosphate, [28,29] hydroxide, [16] or oxometallate, [30,31] most research efforts have been devoted to systems based on silicate solutions, the so-called silica gardens. These structures are typically made by soaking small solid particles of soluble metal salts in a concentrated, strongly alkaline silicate solution. ...
... Tubular structures and mineral vesicles consisting of iron, cobalt, manganese, magnesium, zinc, barium, and calcium carbonate have been confirmed to form with waters of the Magadi lake (Kenya), [22] which is considered a modern analogue of the early soda oceans. Several previous studies have reported the formation and ex situ characterization of calcium carbonate-based tubular structures synthesized by immersion of Ca 2 + -containing salts pellets in Na 2 CO 3 solutions, [13,26,27] or by growth on cationexchange membranes [38,39] and gel/liquid interfaces. [40] However, dynamic diffusion and precipitation processes occurring during the growth and subsequent ripening have not been studied yet in this system. ...
Chemical gardens are self‐assembled tubular precipitates formed by a combination of osmosis, buoyancy, and chemical reaction, and thought to be capable of catalyzing prebiotic condensation reactions. In many cases, the tube wall is a bilayer structure with the properties of a diaphragm and/or a membrane. The interest in silica gardens as microreactors for materials science has increased over the past decade because of their ability to create long‐lasting electrochemical potential. In this study, we have grown single macroscopic tubes based on calcium carbonate and monitored their time‐dependent behavior by in situ measurements of pH, ionic concentrations inside and outside the tubular membranes, and electrochemical potential differences. Furthermore, we have characterized the composition and structure of the tubular membranes by using ex situ X‐ray diffraction, infrared and Raman spectroscopy, as well as scanning electron microscopy. Based on the collected data, we propose a physicochemical mechanism for the formation and ripening of these peculiar CaCO3 structures and compare the results to those of other chemical garden systems. We find that the wall of the macroscopic calcium carbonate tubes is a bilayer of texturally distinct but compositionally similar calcite showing high crystallinity. The resulting high density of the material prevents macroscopic calcium carbonate gardens from developing significant electrochemical potential differences. In the light of these observations, possible implications in materials science and prebiotic (geo)chemistry are discussed.
... 21,[23][24][25][26] In the present paper, we use camphor-based self-propulsion exploited for guided growth of chemical gardens. [27][28][29][30][31][32] Chemical gardens are multi-scaled, tubular structures arising from a complex, self-organizing non-equilibrium process involving complex chemical and hydrodynamic events. The characteristic spatial scales observed in the study of chemical gardens start from nano-meters [33][34] and extend to centimeters. ...
... The characteristic spatial scales observed in the study of chemical gardens start from nano-meters [33][34] and extend to centimeters. [26][27][28][29][30][31] Chemical gardens, described first in 1646 by Johann Glauber, still attract considerable interest among researchers. A broad diversity of systems form chemical gardens, including the chemical processes occurring in Portland cement. ...
A micro-boat self-propelled by a camphor engine, carrying seed crystals of FeCl3, promoted the evolution of chemical gardens when placed on the surface of aqueous solutions of potassium hexacyanoferrate. Inverse chemical gardens (growing from the top downward) were observed. The growth of the inverse chemical gardens was slowed down with an increase in the concentration of the potassium hexacyanoferrate. Heliciform precipitates were formed under the self-propulsion of the micro-boat. A phenomenological model, satisfactorily describing the self locomotion of the camphor-driven micro-boat, is introduced and checked.
... In this reaction we present how few simple inorganic compounds will create spontaneously chemical cell and how inorganic chemicals move to the cell where produce another one that will diffuse outside 27,28 . A pellet of CaCl2 was inversed to solution of Na2CO3 producing a spontaneous formation of a cell surrounded by a semi permeable membrane. ...
First Law of Thermodynamics states that every cannot be self-created or destroyed in an isolated system. Chemical systems spontaneously move to steady state. However chemical systems that are open, will create new systems and moving far and far from equilibrium. The simple compounds will spontaneously create unusually complex structures and behaviors. Surprising, general theory of these systems has not been well understanding. Chemical simplest compounds can spontaneously produce complex arrangements, including chemical structures and dynamical behavior. They are building chemical cells that take chemical compounds from outside, next move to the cell, react, and new compounds move outside. Two other compounds may form more tubes that will create tower and next create metropolis. Machines can switch from one system to another. It can move like a snail. It is basic Law of chemical self-creation. We present simple chemical systems that will spontaneously create very complex structured and machines that may be on level of biology and above. In this paper, simple experiments will show that evolution in Universe is simple and create incredible chemical processes. Universal Chemical Machine can produce an infinite number of entities. Chemical organisms are self-created. It is the most important property of matter.
Hypothesis
Chemical gardens are tubular inorganic structures exhibiting complex morphologies and interesting dynamic properties upon ageing, with coupled diffusion and precipitation processes keeping the systems out of equilibrium for extended periods of time. Calcium-based silica gardens should comprise membranes that mimic the microstructures occurring in ordinary Portland cement and/or silicate gel layers observed around highly reactive siliceous aggregates in concrete.
Experiments
Single macroscopic silica garden tubes were prepared using pellets of calcium chloride and sodium silicate solution. The composition of the mineralized tubes was characterized by means of various ex-situ techniques, while time-dependent monitoring of the solutions enclosed by and surrounding the membrane gives insight into the spatiotemporal distribution of the different ionic species. The latter data reflect transport properties and precipitation reactions in the system, thus allowing its complex dynamic behaviour to be resolved.
Findings
The results show that in contrast to the previously studied cases of iron- and cobalt-based silica gardens, the formed calcium silicate membrane is homogeneous and ultimately becomes impermeable to all species except water, hydroxide and sodium ions, resulting in the permanent conservation of considerable concentration gradients across the membrane. The insights gained in this work may help elucidate the nature and mechanisms of ion diffusion in Portland cements and concrete, especially those occurring during initial hydration of calcium silicates and the so-called alkali-silica reaction (ASR), one of the major concrete deterioration mechanisms causing serious problems with respect to the durability of concrete and the restricted use of many potential sources of raw materials.
The oscillatory growth of chemical gardens is studied experimentally in the budding regime using aco-flow of two reactant solutions within a microfluidic reactor. The confined environment of the reactortames the erratic budding growth and the oscillations leave their imprint with the formation of orderlyspaced membranes on the precipitate surface. The average wavelength of the spacing betweenmembranes, the growth velocity of the chemical garden and the oscillations period are measured as afunction of the velocity of each reactant. By means of materials characterization techniques, the micro-morphology and the chemical composition of the precipitate are explored. A mathematical model isdeveloped to explain the periodic rupture of droplets delimitated by a shell of precipitate and growingwhen one reactant is injected into the other. The predictions of this model are in good agreement withthe experimental data.
The formation of closed chemical gardens that resemble quasibiological cells at the macroscale (> 1 cm) is demonstrated. The cells are produced by injecting lanthanide salts in alkaline solutions and do not require silicates. The cells can encapsulate chemicals and enzymes and carry out reactions.
A micro-boat self-propelled by a camphor engine, carrying seed crystals of FeCl3, promoted the evolution of chemical gardens when placed on the surface of aqueous solutions of potassium hexacyanoferrate. Inverse chemical gardens (growing from the top downward) were observed. The growth of the “inverse” chemical gardens was slowed down with an increase in the concentration of the potassium hexacyanoferrate. Heliciform precipitates were formed under the self-propulsion of the micro-boat. A phenomenological model, satisfactorily describing the self-locomotion of the camphor-driven micro-boat, is introduced and checked.
The silica garden Brønsted acid catalyst is a framework aluminosilicate derived from silica by isomorphous substitution of 4-coordinate silicon by 4-coordinate aluminium. 6-coordinate aluminate cationic units and Brønsted protons balance the net charge of the polyanionic network.
Hydrogen peroxide is a chemical that is becoming increasingly fashionable as an oxidant, both in industry and in academia and whose production is expected to increase significantly in the next few years. This growth in interest is largely due to environmental considerations related to the clean nature of hydrogen peroxide as an oxidant, its by-product being only water.
To date this chemical has largely been employed as a non-selective oxidant in operations like the bleaching of paper, cellulose and textiles, or in the formulation of detergents, and only to a minimal extent in the manufacture of organic chemicals.
This book has been organized to cover the different aspects of the chemistry of hydrogen peroxide. The various chapters into which the book is divided have been written critically by the authors with the general aim of stimulating new ideas and emphasizing those aspects that are likely to lead to new developments in organic synthesis in the coming future.
Le mecanisme reactionnel initie par l'action de l'eau oxygenee sur les ions iodure est relativement bien connu; cependant certaines etapes elementaires de ce systeme sont encore mal definies. En particulier, les deux etapes inverses de la reaction de l'hydrolyse de l'iode, ainsi que la reaction de l'eau oxygenee avec l'acide hypoiodeux doivent etre precisees. De nouvelles donnees cinetiques experimentales ont ete obtenues concernant le systeme I − /H 2 O 2 ([I − ] 0 = 10 −2 a 5 × 10 −1 M, [H 2 O 2 ] 0 = 0,9 × 10 −5 a 7,4 × 10 −4 × 10 −4 M)a different pH (4,7, 7,8 et 9), et le systeme I − /I 3 − /H 2 O 2 [I − ] 0 = 10 −1 M, [H 2 O 2 ] 0 = 1,1 a 7,4 × 10 −4 M, [I 3 − ] 0 = 3 × 10 −4 M) a pH 8. D'apres les resultats eperimentaux nous avons mis en evidence (1l) l'importance des reactivites des formes basiques (HO 2 − et/ou IO − ), meme a des pH inferieurs au pKa correspondant (10,6-11,2), (2) la competition entre les deux reactions inverses de l'equilibre d'hydrolyse de l'iode et les autres reactions elementaires du mecanisme (cette competition n'avait pas ete prise en consideration auparavant). En simulant par le calcul toutes les courbes experimentales, les constantes de vitesse suivantes ont ete determinees: k (I 2 + OH − ) = (7 ± 0,5) × 10 7 M −1 s −1 , k (I − + IOH) = (7,5 ± 0,5) × 10 5 M −1 s −1 (K(I 2 hydrolyse) = 93), et k (IOH + HO 2 − ) = (1 ± 0,2) × 10 8 M −1 s −1
Traces of copper(II) ion in 10−7—10−5 M (M = mol dm−3) catalytically accelerated the oxidation reactions of iodide ion to iodine in relatively strong acid solutions (pH ≤ 2) in the presence of molecular oxygen under conditions containing relatively high concentrations of I−. When a copper(II) solution was mixed with an iodide solution, after a rapid formation of iodine, it gradually increased according to the reaction times. For about 5 min after mixing, plots of [I3−]formed vs. t showed a good straight line; the formation rate of I2 (or I3−) increased proportionally with increasing concentrations of copper(II) ion and oxygen, with increasing concentrations of hydrogen ion and iodide ion, and with increasing temperature and with decreasing the ionic strength in the reaction solution. The formation rate of I2 was extremely inhibited by the presence of either radical scavengers or ethylenediaminetetraacetic acid (EDTA). A chain mechanism is presented to account for the obtained results.
The kinetics of the oxidation of iodine by hydrogen peroxide catalyzed by MoO2−4 ions with a ‘clock’ behaviour is described and the corresponding reaction scheme is proposed. The ‘clock’ behaviour is explained by the assumption that the oxidation of iodine cannot proceed until the iodide concentration drops to a certain treshold, since this reaction can only through the HOI species proceed. The noncatalyzed, direct oxidation of iodine by H2O2 is too slow to become one of the main two processes of the Bray-Liebhafsky oscillatory reaction.
Conditions are described under which vesicles formed by caprylic acid and oleic acid in water are able to undergo autopoietic self-reproduction-namely an increase of their population number due to a reaction which takes place within the spherical boundary of tile vesicles themselves. This is achieved by letting a certain amount of the neat water-insoluble caprylic or oleic anhydride hydrolyze at alkaline pH: the initial increase of the concentration of the released acid/carboxylate is extremely slow (several days to reach the conditions for spontaneous vesicle formation), but afterwards, the presence of vesicles brings about a rapid second phase leading to more and more vesicles being formed in an overall autocatalytic process. The catalytic power of the caprylic acid and oleic acid vesicles toward the hydrolysis of the corresponding anhydride is documented in a set of independent experiments. In these experiments, the hydrolysis was carried out in the presence of vesicles at a pH corresponding approximately to the pK of the acid in the vesicles. The process of autopoietic self-reproduction of caprylic acid and oleic acid vesicles is studied as a function of temperature: by increasing temperature (up to 70 degrees C), the exponential time progress of vesicle formation tends to become steeper while the long initial slow phase is significantly shortened. The caprylic acid and oleic acid vesicles are characterized by electron microscopy and by determining their internal volume. The question whether and to what extent these vesicles form a classic chemical equilibrium system-in which namely the free surfactant is in equilibrium with the aggregates-is also investigated.