Controlled self-assembly of chemical gardens enables fabrication of heterogeneous chemobrionic materials

Chemical gardens are an example of a chemobrionic system that typically result in abiotic macro-, micro- and nano- material architectures, with formation driven by complex out-of-equilibrium reaction mechanisms. From a technological perspective, controlling chemobrionic processes may hold great promise for the creation of novel, compositionally diverse and ultimately, useful materials and devices. In this work, we engineer an innovative custom-built liquid exchange unit that enables us to control the formation of tubular chemical garden structures grown from the interface between calcium loaded hydrogel and phosphate solution. We show that systematic displacement of phosphate solution with water (H2O) can halt self-assembly, precisely control tube height and purify structures in situ. Furthermore, we demonstrate the fabrication of a heterogeneous chemobrionic composite material composed of aligned, high-aspect ratio calcium phosphate channels running through an otherwise dense matrix of poly(2-hydroxyethyl methacrylate) (pHEMA). Given that the principles we derive can be broadly applied to potentially control various chemobrionic systems, this work paves the way for fabricating multifunctional materials that may hold great potential in a variety of application areas, such as regenerative medicine, catalysis and microfluidics.

Experimental Approaches for Testing the Hypothesis of the Emergence of Life at Submarine Alkaline Vents

Since the pioneering experimental work performed by Urey and Miller around 70 years ago, several experimental works have been developed for approaching the question of the origin of life based on very few well-constructed hypotheses. In recent years, attention has been drawn to the so-called alkaline hydrothermal vents model (AHV model) for the emergence of life. Since the first works, perspectives from complexity sciences, bioenergetics and thermodynamics have been incorporated into the model. Consequently, a high number of experimental works from the model using several tools have been developed. In this review, we present the key concepts that provide a background for the AHV model and then analyze the experimental approaches that were motivated by it. Experimental tools based on hydrothermal reactors, microfluidics and chemical gardens were used for simulating the environments of early AHVs on the Hadean Earth (~4.0 Ga). In addition, it is noteworthy that several works used techniques from electrochemistry to investigate phenomena in the vent–ocean interface for early AHVs. Their results provided important parameters and details that are used for the evaluation of the plausibility of the AHV model, and for the enhancement of it.

Oscillatory budding dynamics of a chemical garden within a co-flow of reactants

The oscillatory growth of chemical gardens is studied experimentally in the budding regime using a co-flow of two reactant solutions within a microfluidic reactor.

Filament dynamics in planar chemical gardens

Modelling describes oscillatory dynamics of precipitate filaments; growth of an ensemble of filaments is a self-organized dispersion mechanism.

Chemobrionics: From Self-Assembled Material Architectures to the Origin of Life

Self-organizing precipitation processes, such as chemical gardens forming biomimetic micro- and nanotubular forms, have the potential to show us new fundamental science to explore, quantify, and understand nonequilibrium physicochemical systems, and shed light on the conditions for life's emergence. The physics and chemistry of these phenomena, due to the assembly of material architectures under a flux of ions, and their exploitation in applications, have recently been termed chemobrionics. Advances in understanding in this area require a combination of expertise in physics, chemistry, mathematical modeling, biology, and nanoengineering, as well as in complex systems and nonlinear and materials sciences, giving rise to this new synergistic discipline of chemobrionics.

Mineral Vesicles and Chemical Gardens from Carbonate-Rich Alkaline Brines of Lake Magadi, Kenya

Mineral vesicles and chemical gardens are self-organized biomimetic structures that form via abiotic mineral precipitation. These membranous structures are known to catalyze prebiotic reactions but the extreme conditions required for their synthesis has cast doubts on their formation in nature. Apart from model solutions, these structures have been shown to form in serpentinization-driven natural silica-rich water and by fluid-rock interaction of model alkaline solutions with granites. Here, for the first time, we demonstrate that self-assembled hollow mineral vesicles and gardens can be synthesized in natural carbonate-rich soda lake water. We have synthesized these structures by a) pouring saturated metal salt solutions, and b) by immersing metal salt pellets in brines collected from Lake Magadi (Kenya). The resulting structures are analyzed by using SEM coupled with EDX analysis, Raman spectroscopy, and powder X-ray diffraction. Our results suggest that mineral self-assembly could have been a common phenomenon in soda oceans of early Earth and Earth-like planets and moons. The composition of the obtained vesicles and gardens confirms the recent observation that carbonate minerals in soda lakes sequestrate Ca, thus leaving phosphate behind in solution available for biochemical reactions. Our results strengthens the proposal that alkaline brines could be ideal sites for “one-pot” synthesis of prebiotic organic compounds and the origin of life.