Exploring the Synthesis of Self-Organization and Active Motion.

Proteins, genetic material, and membranes are fundamental to all known organisms, yet these components alone do not constitute life. Life emerges from the dynamic processes of self-organization, assembly, and active motion, suggesting the existence of similar artificial systems. Against this backdrop, our Perspective explores a variety of chemical phenomena illustrating how nonequilibrium self-organization and micromotors contribute to life-like behavior and functionalities. After explaining key terms, we discuss specific examples including enzymatic motion, diffusiophoretic and bubble-driven self-propulsion, pattern-forming reaction-diffusion systems, self-assembling inorganic aggregates, and hierarchically emergent phenomena. We also provide a roadmap for combining self-organization and active motion and discuss possible outcomes through biological analogs. We suggest that this research direction, deeply rooted in physical chemistry, offers opportunities for further development with broad impacts on related sciences and technologies.

Patterns Lead the Way to Far-from-Equilibrium Materials.

The universe is a complex fabric of repeating patterns that unfold their beauty in system-specific diversity. The periodic table, crystallography, and the genetic code are classic examples that illustrate how even a small number of rules generate a vast range of shapes and structures. Today, we are on the brink of an AI-driven revolution that will reveal an unprecedented number of novel patterns, many of which will escape human intuition and expertise. We suggest that in the second half of the 21st century, the challenge for Physical Chemistry will be to guide and interpret these advances in the broader context of physical sciences and materials-related engineering. If we succeed in this role, Physical Chemistry will be able to extend to new horizons. In this article, we will discuss examples that strike us as particularly promising, specifically the discovery of high-entropy and far-from-equilibrium materials as well as applications to origins-of-life research and the search for life on other planets.

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.

Front-like expansion and arrest of programmed cell death in brown banana spots.

The spot patterns on bananas are a striking case of biological pattern formation and-as a qualitative ripeness indicator-linked to 50 million tons of wasted food per year. Ripening bananas develop these senescent spots as phenolic compounds are enzymatically oxidized and cellular integrity is lost. We characterize the dynamics of the spot expansion and their nucleation rates based on time-lapse movies. Spots nucleate for about 2 days yielding a typical density of 8 spots/cm2. The expansion is initially diffusion controlled and the effective diffusion coefficient decreases with nucleation time from 1.3 to 0.4 mm2d-1. During and after expansion, the browning fronts maintain a steep and constant intensity gradient. We quantitatively reproduce these features by a reaction-diffusion model that considers the local oxygen concentration and browning degree of the peel. All model parameters are based on measurements and front stalling is explained by decreasing oxygen levels in the nucleation sites.

Self-Propelled Chemical Garden Tubes.

Synthetic autonomous locomotion shows great promise in many research fields, including biomedicine and environmental science, because it can allow targeted drug/cargo delivery and the circumvention of kinetic and thermodynamic limitations. Creating such self-moving objects often requires advanced production techniques as exemplified by catalytic, gas-forming microrockets. Here, we grow such structures via the self-organization of precipitate tubes in chemical gardens by simply injecting metal salts into silicate solutions. This method generates hollow, cylindrical objects rich in catalytic manganese oxide that also feature a partially insulating outer layer of inert silica. In dilute H2O2 solution, these structures undergo self-propulsion by ejecting streams of oxygen bubbles. Each emission event pushes the tube forward by 1-2 tube radii. The ejection frequency depends linearly on the peroxide concentration as quantified by acoustic measurements of bursting bubbles. We expect our facile method and key results to be applicable to a diverse range of materials and reactions.

Dubiofossils from a Mars-analogue subsurface palaeoenvironment: The limits of biogenicity criteria.

The search for a fossil record of Earth's deep biosphere, partly motivated by potential analogies with subsurface habitats on Mars, has uncovered numerous assemblages of inorganic microfilaments and tubules inside ancient pores and fractures. Although these enigmatic objects are morphologically similar to mineralized microorganisms (and some contain organic carbon), they also resemble some abiotic structures. Palaeobiologists have responded to this ambiguity by evaluating problematic filaments against checklists of "biogenicity criteria". Here, we describe material that tests the limits of this approach. We sampled Jurassic calcite veins formed through subseafloor serpentinization, a water-rock reaction that can fuel the deep biosphere and is known to have occurred widely on Mars. At two localities ~4 km apart, veins contained curving, branched microfilaments composed of Mg-silicate and Fe-oxide minerals. Using a wide range of analytical techniques including synchrotron X-ray microtomography and scanning transmission electron microscopy, we show that these features meet many published criteria for biogenicity and are comparable to fossilized cryptoendolithic fungi or bacteria. However, we argue that abiotic processes driven by serpentinization could account for the same set of lifelike features, and report a chemical garden experiment that supports this view. These filaments are, therefore, most objectively described as dubiofossils, a designation we here defend from criticism and recommend over alternative approaches, but which nevertheless signifies an impasse. Similar impasses can be anticipated in the future exploration of subsurface palaeo-habitats on Earth and Mars. To avoid them, further studies are required in biomimetic geochemical self-organization, microbial taphonomy and micro-analytical techniques, with a focus on subsurface habitats.

Flow-Induced Precipitation in Thin Capillaries Creates Helices, Lamellae, and Tubes.

Precipitation reactions under flow in confined media are relevant to the control of pathological biomineralization, processes affecting aquifers, and challenges in the petroleum industry. Here we show that for a simple geometry, such conditions create macroscopic structures including helices, tubes, lamellae, slugs, and disordered patterns. All structures emerge when salt solution is slowly injected into thin capillaries filled with hydroxide solution. For the helices, the pitch is proportional to the pump rate revealing a constant period of 0.63 s. Different morphologies of the insoluble metal hydroxide can co-exist causing random transitions along the capillary. On average, 15 % of the final system contains residual hydroxide solution. While mechanically stable for flow speeds above 25 mm min-1 , structures collapse and sediment for slower injection speeds. Some of the observed features share similarities with precipitate tubes in chemical gardens and the dynamics of liquid-liquid pipe flow.

From nonlinear reaction-diffusion processes to permanent microscale structures.

Biomorphs are polycrystalline aggregates that self-assemble during inorganic precipitation reactions. The shape repertoire of these microstructures include hemispherical objects with complicated internal features such as radial spikes and cones as well as folded sheets reminiscent of corals. We propose that at the microscale, some of these patterns are caused by nonlinear reaction-diffusion processes and present a simple model for this unconventional type of precipitation. The model consists of three reaction steps that convert a reactant species autocatalytically into an intermediate and eventually into a solid, immobile product. Numerical simulations of the model in three space dimensions reveal product structures that are similar to the experimentally observed biomorphs.

Systematic characterization of polycrystalline silica-carbonate helices.

Biomorphs are complex, life-like structures that emerge from the precipitation of barium carbonate and amorphous silica in alkaline media. Despite their inorganic nature, these microstructures have non-crystallographic morphologies such as helices and cardioid sheets. At the nanoscale, biomorphs arrange thousands of crystalline nanorods as hierarchical assemblies that resemble natural biominerals suggesting novel approaches towards the production of biomimetic materials. We report the synthesis of silica-carbonate biomorphs in single-phase, gradient-free solutions that differ markedly from the typical solution-gas or gel-solution setups. Our experimental approach significantly increases the duration of biomorph growth and hence assembles networks in which individual helices extend to several millimeters. These unusually long biomorphs allow the first quantitative measurements of mesoscopic parameters such as the helix wavelength, period, width, and linear as well as tangential growth velocities. We find that the latter quantities are system-specific and tightly conserved during many hours of growth. Moreover, the average double helix wavelength of (19 ± 3) µm and width of (9.6 ± 0.8) µm vary by less than 12% when the initial carbonate concentration is changed by three orders of magnitude. We also delineate the single helix growth mechanism and report the occurrence of ribbon-like structures and highly regular "superhelices". Our experiments clearly demonstrate the robustness and consistency of biomorph growth under stable chemical conditions.

Biomorph growth in single-phase systems: expanding the structure spectrum and pH range.

Biomorphs are life-like microstructures of selfassembled barium carbonate nanorods and silica. In a departure from established approaches, we produce biomorphs in CO2- and gradient-free solutions. Our study reveals novel structural motifs for solution-grown biomorphs, reduces pH transients, and expands the upper pH limit for biomorph formation to over 12 where silica is essentially soluble.