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.

Information, Coding, and Biological Function: The Dynamics of Life.

In the mid-20th century, two new scientific disciplines emerged forcefully: molecular biology and information-communication theory. At the beginning, cross-fertilization was so deep that the term genetic code was universally accepted for describing the meaning of triplets of mRNA (codons) as amino acids. However, today, such synergy has not taken advantage of the vertiginous advances in the two disciplines and presents more challenges than answers. These challenges not only are of great theoretical relevance but also represent unavoidable milestones for next-generation biology: from personalized genetic therapy and diagnosis to Artificial Life to the production of biologically active proteins. Moreover, the matter is intimately connected to a paradigm shift needed in theoretical biology, pioneered a long time ago, that requires combined contributions from disciplines well beyond the biological realm. The use of information as a conceptual metaphor needs to be turned into quantitative and predictive models that can be tested empirically and integrated in a unified view. Successfully achieving these tasks requires a wide multidisciplinary approach, including Artificial Life researchers, to address such an endeavour.

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.

Archimedean Spirals Form at Low Flow Rates in Confined Chemical Gardens.

We describe and study the formation of confined chemical garden patterns. At low flow rates of injection of cobalt chloride solution into a Hele-Shaw cell filled with sodium silicate, the precipitate forms with a thin filament wrapping around an expanding "candy floss" structure. The result is the formation of an Archimedean spiral structure. We model the growth of the structure mathematically. We estimate the effective density of the precipitate and calculate the membrane permeability. We set the results within the context of recent experimental and modeling work on confined chemical garden filaments.

The Effect of the Presence of Amino Acids on the Precipitation of Inorganic Chemical-Garden Membranes: Biomineralization at the Origin of Life.

If life developed in hydrothermal vents, it would have been within mineral membranes. The first proto-cells must have evolved to manipulate the mineral membranes that formed their compartments in order to control their metabolism. There must have occurred a biological takeover of the self-assembled mineral structures of the vents, with the incorporation of proto-biological molecules within the mineral membranes to alter their properties for life's purposes. Here, we study a laboratory analogue of this process: chemical-garden precipitation of the amino acids arginine and tryptophan with the metal salt iron chloride and sodium silicate. We produced these chemical gardens using different methodologies in order to determine the dependence of the morphology and chemistry on the growth conditions, as well as the effect of the amino acids on the formation of the iron-silicate chemical garden. We compared the effects of having amino acids initially within the forming chemical garden, corresponding to the internal zones of hydrothermal vents, or else outside, corresponding to the surrounding ocean. The characterization of the formed chemical gardens using X-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis, and scanning electron microscopy demonstrates the presence of amino acids in these structures. The growth method in which the amino acid is initially in the tablet with the iron salt is that which generated chemical gardens with more amino acids in their structures.

Downward fingering accompanies upward tube growth in a chemical garden grown in a vertical confined geometry.

Chemical gardens are self-assembled structures of mineral precipitates enabled by semi-permeable membranes. To explore the effects of gravity on the formation of chemical gardens, we have studied chemical gardens grown from cobalt chloride pellets and aqueous sodium silicate solution in a vertical Hele-Shaw cell. Through photography, we have observed and quantitatively analysed upward growing tubes and downward growing fingers. The latter were not seen in previous experimental studies involving similar physicochemical systems in 3-dimensional or horizontal confined geometry. To better understand the results, further studies of flow patterns, buoyancy forces, and growth dynamics under schlieren optics have been carried out, together with characterisation of the precipitates with scanning electron microscopy and X-ray diffractometry. In addition to an ascending flow and the resulting precipitation of tubular filaments, a previously not reported descending flow has been observed which, under some conditions, is accompanied by precipitation of solid fingering structures. We conclude that the physics of both the ascending and descending flows are shaped by buoyancy, together with osmosis and chemical reaction. The existence of the descending flow might highlight a limitation in current experimental methods for growing chemical gardens under gravity, where seeds are typically not suspended in the middle of the solution and are confined by the bottom of the vessel.

Filament dynamics in vertical confined chemical gardens.

When confined to a Hele-Shaw cell, chemical gardens can grow as filaments, narrow structures with an erratic and tortuous trajectory. In this work, the methodology applied to studies with horizontal Hele-Shaw cells is adapted to a vertical configuration, thus introducing the effect of buoyancy into the system. The motion of a single filament tip is modeled by taking into account its internal pressure and the variation of the concentration of precipitate that constitutes the chemical garden membrane. While the model shows good agreement with the results, it also suggests that the concentration of the host solution of sodium silicate also plays a role in the growth of the structures despite being in stoichiometric excess.

Filament dynamics in planar chemical gardens.

Filaments in a planar chemical garden grow following tortuous, erratic paths. We show from statistical mechanics that this scaling results from a self-organized dispersion mechanism. Effective diffusivities as high as 10-5 m2 s-1 are measured in 2D laboratory experiments. This efficient transport is four orders of magnitude larger than molecular diffusion in a liquid, and ensures widespread contact and exchange between fluids in the chemical-garden structure and its surrounding environment.

Stokes' law, viscometry, and the Stokes falling sphere clock.

Clocks run through the history of physics. Galileo conceived of using the pendulum as a timing device on watching a hanging lamp swing in Pisa cathedral; Huygens invented the pendulum clock; and Einstein thought about clock synchronization in his Gedankenexperiment that led to relativity. Stokes derived his law in the course of investigations to determine the effect of a fluid medium on the swing of a pendulum. I sketch the work that has come out of this, Stokes drag, one of his most famous results. And to celebrate the 200th anniversary of George Gabriel Stokes' birth I propose using the time of fall of a sphere through a fluid for a sculptural clock-a public kinetic artwork that will tell the time. This article is part of the theme issue 'Stokes at 200 (part 2)'.

Nonlinear dynamics determines the thermodynamic instability of condensed matter in vacuo.

Condensed matter is thermodynamically unstable in a vacuum. That is what thermodynamics tells us through the relation showing that condensed matter at temperatures above absolute zero always has non-zero vapour pressure. This instability implies that at low temperatures energy must not be distributed equally among atoms in the crystal lattice but must be concentrated. In dynamical systems such concentrations of energy in localized excitations are well known in the form of discrete breathers, solitons and related nonlinear phenomena. It follows that to satisfy thermodynamics such localized excitations must exist in systems of condensed matter at arbitrarily low temperature and as such the nonlinear dynamics of condensed matter is crucial for its thermodynamics. This article is part of the theme issue 'Stokes at 200 (Part 1)'.

The fluid mechanics of poohsticks.

The year 2019 marked the bicentenary of George Gabriel Stokes, who in 1851 described the drag-Stokes drag-on a body moving immersed in a fluid, and 2020 is the centenary of Christopher Robin Milne, for whom the game of poohsticks was invented; his father A. A. Milne's The House at Pooh Corner, in which it was first described in print, appeared in 1928. So this is an apt moment to review the state of the art of the fluid mechanics of a solid body in a complex fluid flow, and one floating at the interface between two fluids in motion. Poohsticks pertains to the latter category, when the two fluids are water and air. This article is part of the theme issue 'Stokes at 200 (part 2)'.

Stokes, Tyndall, Ruskin and the nineteenth-century beginnings of climate science.

Although we humans have known since the first smokey campfires of prehistory that our activities might alter our local surroundings, the nineteenth century saw the first indications that humankind might alter the global environment; what we currently know as anthropogenic climate change. We are now celebrating the bicentenaries of three figures with a hand in the birth of climate science. George Stokes, John Tyndall and John Ruskin were born in August 1819, August 1820 and February 1819, respectively. We look back from the perspective of two centuries following their births. We outline their contributions to climate science: understanding the equations of fluid motion and the recognition of the need to collect global weather data together with comprehending the role in regulating terrestrial temperature played by gases in the atmosphere. This knowledge was accompanied by fears of the Earth's regression to another ice age, together with others that industrialization was ruining humankind's health, morals and creativity. The former fears of global cooling were justified but seem strange now that the balance has tipped so far the other way towards global warming; the latter, on the other hand, today seem very prescient. This article is part of the theme issue 'Stokes at 200 (Part 1)'.

Stokes at 200 (part 2).

We present the second half of the papers from the Stokes200 symposium celebrating the bicentenary of George Gabriel Stokes. This article is part of the theme issue 'Stokes at 200 (part 2)'.

Geometric mixing.

Mixing fluids often involves a periodic action, like stirring one's tea. But reciprocating motions in fluids at low Reynolds number, in Stokes flows where inertia is negligible, lead to periodic cycles of mixing and unmixing, because the physics, molecular diffusion excepted, is time reversible. So how can fluid be mixed in such circumstances? The answer involves a geometric phase. Geometric phases are found everywhere in physics as anholonomies, where after a closed circuit in the parameters, some system variables do not return to their original values. We discuss the geometric phase in fluid mixing: geometric mixing. This article is part of the theme issue 'Stokes at 200 (part 2)'.

Stokes at 200: a celebration of the remarkable achievements of Sir George Gabriel Stokes two hundred years after his birth.

Sir George Gabriel Stokes PRS was for 30 years an inimitable Secretary of the Royal Society and its President from 1885 to 1890. Two hundred years after his birth, Stokes is a towering figure in physics and applied mathematics; fluids, asymptotics, optics, acoustics among many other fields. At the Stokes200 meeting, held at Pembroke College, Cambridge from 15-18th September 2019, an invited audience of about 100 discussed the state of the art in all the modern research fields that have sprung from his work in physics and mathematics, along with the history of how we have got from Stokes' contributions to where we are now. This theme issue is based on work presented at the Stokes200 meeting. In bringing together people whose work today is based upon Stokes' own, we aim to emphasize his influence and legacy at 200 to the community as a whole. This article is part of the theme issue 'Stokes at 200 (Part 1)'.

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.

Chaos and periodicities in a climatic time series of the Iberian Margin.

We analyze the time series of the temperature of the sedimentary core MD01-2443 originating from the Iberian Margin with a duration of 420 kyr. The series has been tested for unit-root and a long term trend is estimated. We identify four significant periodicities together with a low climatic activity every 100 kyr, and these were associated with internal and external forcings. Also, we identify a high-frequency fast component that acts on top of a nonlinear, irreversible slow-changing dynamics. We find the presence of chaos in the climate of the Iberian Margin by means of a neural network asymptotic test on the largest Lyapunov exponent. The analysis suggests that the chaotic dynamics is associated with the fast high-frequency component. We also carry out a statistical analysis of the dimensionality of the attractor. Our results confirm the possibility that periodic behavior and chaos may coexist on different time scales. This could lead to different degrees of predictability in the climate system according to the characteristic time scales and/or phase-space locations.

Filiform corrosion as a pressure-driven delamination process.

Filiform corrosion produces long and narrow trails on various coated metals through the detachment of the coating layer from the substrate. In this work, we present a combined experimental and theoretical analysis of this process with the aim to describe quantitatively the shape of the cross-section, perpendicular to the direction of propagation, of the filaments produced. For this purpose, we introduce a delamination model of filiform corrosion dynamics and show its compatibility with experimental data where the coating thickness has been varied systematically.

Wavy membranes and the growth rate of a planar chemical garden: Enhanced diffusion and bioenergetics.

To model ion transport across protocell membranes in Hadean hydrothermal vents, we consider both theoretically and experimentally the planar growth of a precipitate membrane formed at the interface between two parallel fluid streams in a 2D microfluidic reactor. The growth rate of the precipitate is found to be proportional to the square root of time, which is characteristic of diffusive transport. However, the dependence of the growth rate on the concentrations of hydroxide and metal ions is approximately linear and quadratic, respectively. We show that such a difference in ionic transport dynamics arises from the enhanced transport of metal ions across a thin gel layer present at the surface of the precipitate. The fluctuations in transverse velocity in this wavy porous gel layer allow an enhanced transport of the cation, so that the effective diffusivity is about one order of magnitude higher than that expected from molecular diffusion alone. Our theoretical predictions are in excellent agreement with our laboratory measurements of the growth of a manganese hydroxide membrane in a microfluidic channel, and this enhanced transport is thought to have been needed to account for the bioenergetics of the first single-celled organisms.

Exploding Chemical Gardens: A Phase-Change Clock Reaction.

Chemical gardens and clock reactions are two of the best-known demonstration reactions in chemistry. Until now these have been separate categories. We have discovered that a chemical garden confined to two dimensions is a clock reaction involving a phase change, so that after a reproducible and controllable induction period it explodes.