ABSTRACT Active compartmentalization is a fundamental property of life, as well as a key element in cell regulation. In order to build synthetic systems with emergent cell‐like properties, we need to develop active compartments that form, disappear, and change properties autonomously over time. Here, we report a new strategy to induce temporal changes in coacervates using the urea‐urease reaction. This reaction triggers the dissolution of complex coacervates after a controllable delay, as it increases ionic strength through the production of ammonium carbonate. This delayed dissolution can be directly used for a broad range of complex coacervates without any synthetic effort. Furthermore, ammonium carbonate can also decompose over time, evaporating from the solution. This combination of enzymatic synthesis and spontaneous decomposition of salt leads to transient coacervate dissolution, which can be used for the controlled release of cargo and for the modulation of a compartmentalized reaction. Cycles of dissolution/reformation can be repeated multiple times without any waste generation, although the number of cycles is limited by the denaturation of urease. Finally, by combining polyelectrolytes with a protected dipeptide, ureolysis can trigger the formation of multiphase coacervates, as well as the sequential formation, dissolution, and aggregation of simple and complex coacervates.

ABSTRACT Large‐amplitude co‐conformational motions are a unique characteristic of catenanes and related mechanical interlocked molecules that underlie their applications as molecular switches and machines. Due to the challenging synthesis, precise incorporation of multiple macrocycles of different properties into a single [n]catenane and studies on the dynamics of the interlocked components are, however, scarce. In this work, a water‐soluble radial [7]catenane was obtained in one step in high yield (95% formation, 80% isolated yield). Dynamics of the four β‐cyclodextrins (β‐CD) and two cucurbit[6]urils (CB[6]) interlocked on a central macrocycle were also studied by variable temperature NMR. While the motions of the β‐CDs can be modulated by external stimuli, those of the CB[6]s are found to be unaffected.

ABSTRACT The origin of life, marking the transition from nonliving to living matter, remains one of the unresolved mysteries in Earth's history. Despite significant progress, many aspects of this process are still poorly understood, particularly given that the environmental conditions of early Earth differ substantially from those of the present. This review examines the surface‐driven formation of protocells in geologically relevant early Earth settings, focusing on the interplay between geological substrates and prebiotic biochemistry. Rather than emphasizing homogeneous bulk reactions, it aims to highlight how solid–liquid interfaces could have facilitated the emergence of life. Recent theoretical and experimental advances prove that catalytic properties, surface charges, and organic molecule upconcentration capacities of mineral surfaces were crucial in enabling the synthesis of organics and compartmentalization of protocells. Multiple geological environments, including hydrothermal vents, volcanic terrains, and surface waters, will be considered in this review and examined as dynamic arenas fostering complex chemical networks. Environmental challenges such as molecular dilution and ultraviolet radiation are also discussed, along with the protective mechanisms that could have mitigated them. Linking geology to biology, this review offers a comprehensive framework for understanding the origins of life on Earth and how it could arise on other planets.

ABSTRACT The pharaoh's serpent reaction, the thermodecomposition of mercury thiocyanate in air, is a classic chemical demonstration. We analyse and characterize the reaction products, composed of two different phases, graphitic carbon nitride, , and metacinnabar, HgS. We show that two growth modes are involved in forming the sinuous solid product; the more common one, jack‐up growth, forms a solid cylinder from the base up. This is accompanied by a rarer second mode, chimney growth, in which fluid mechanics plays a fundamental role. In this second growth mode, reagents are transported in gaseous form in a reactive plume to be precipitated remotely on the growing rim of a tube templated around the plume. Such templated tube growth, while common in a liquid environment, for example, in the chemical‐garden reaction, has not been reported in a gaseous medium.

ABSTRACT Synthetic biology has enabled the development of new strategies for creating artificial cells that can sense and respond to external stimuli. This study introduces the bottom‐up construction of globular protein vesicles (GPVs) that incorporate elastin‐like peptide (ELP) bolaamphiphiles as transmembrane components. To enable this strategy, we devised a Golden Gate‐based cloning strategy to streamline the design, expression, and purification of ELP bolaamphiphiles. Three ELP bolamphiphiles with varying structural complexity were developed, incorporating fluorescent proteins to facilitate visualization and characterization. The self‐assembly of these bolaamphiphiles into GPVs was optimized by varying the molar ratios of recombinant building blocks. Structural characterization confirmed vesicle formation, dynamic light scattering analysis revealed size distributions dependent on modular complexity, and atomic force microscopy demonstrated that the vesicles exhibited MPa‐range Young's moduli, indicative of high mechanical robustness. Our findings demonstrate that multifunctional ELP bolaamphiphiles can be incorporated into GPVs, enabling modular vesicle engineering. This work provides a foundation for designing synthetic cells with customizable bi‐functionalities and modularity, advancing compartmentalized systems.

Abstract Spatiotemporal phenomena that develop in autocatalytic reaction networks are essential for the operation of nonequilibrium chemical and biochemical systems. Designing complex chemical systems with appropriate kinetic and transport properties is a challenging task. The discovery of small organic molecule‐based autocatalytic networks opens a unique way due to the structural diversity of carbon‐containing compounds. Here, we study the front propagation in the autocatalytic 9‐fluorenylmethoxycarbonyl (Fmoc)‐piperidine reaction in the presence of p ‐nitrophenyl acetate inhibitor and bromothymol blue indicator. We demonstrate that the color change of the indicator is driven not only by piperidine but also by the product of the inhibitory reaction, p ‐nitrophenol. Numerical simulations support the experimental observations. Front propagation was observed at 50, 60, and 70 ℃ in thin solution layers. In the latter case, a convective instability is coupled to the reaction–diffusion phenomena. We anticipate that our results pave the way for discovering more complex spatiotemporal phenomena in networks of small organic molecules.

Abstract Designing synthetic chemical systems capable of mimicking life‐like behavior surely will help to understand the basic principles sustaining life, but also to create advanced materials potentially going beyond nature. Herein, we report the synthesis of a family of lipoamino acids from their individual components, which are free amino acids and lipid precursors, that allow us to study competition and selection in their formation. Octanoyl‐ L ‐histidine outcompetes from a pool of natural amino acids and a family of lipids, emerging as the fittest, where the observed selectivity is the result of a very efficient autocatalytic mechanism.

Abstract Lipid membranes are important components of all living organisms. Giant unilamellar vesicles (GUVs) with diameters ranging from several to a few hundred micrometers provide a unique opportunity to study physical chemistry of biomembranes.In this paper, the response behaviors of GUVs under acoustic radiation force is investigated. The temperature‐mediated deformation of GUVs and GUVs deformation with binary lipid composition under acoustic field were studied in detail. We believe that the deformation behavior of GUVs under acoustic radiation force will provide a new platform for membrane mechanical properties research and can be used in biotechnology.

Learning and memory, once associated only with intelligent life forms, are now increasingly recognized in both physical and virtual systems, such as simple organisms, machines, and even designed chemical systems. The Perspective by Kübra Kaygisiz and Rein V. Ulijn explores how molecular components can be engineered to create supramolecular systems capable of learning, with potential applications in materials science and next-generation computing.

Abstract Research across various disciplines shows the benefits of learning and memory for gaining functionality and improving performance. It is increasingly clear that learning and memory can be found in both physical and virtual systems, from intelligent life forms to machines, simple organisms, and even designed chemical systems. We are interested in understanding to what extent physical embodiments of these processes can be synthesized and engineered from the bottom up by using molecular components. In this perspective, we raise and attempt to answer conceptual questions about supramolecular systems as the smallest units capable of learning. We define learning as a process where a complex system of interacting components modifies itself in response to an applied stress or stimulus, resulting in structural changes and information gain. We highlight the potential of systems chemistry and molecular networks to design systems that meet this definition by encoding, decoding, and storing information as memory within the system′s composition. Understanding the physical basis of molecular memory and learning could inform the development of materials and chemical systems that autonomously acquire new properties in response to their environment. This could also provide insights for next‐generation computing and physical, rather than virtual, learning systems.