Abstract RNA is an information‐carrying molecule that instructs protein synthesis, but it also functions as a catalyst in so‐called ribozymes. Here, we study this multifunctional character using a dynamic combinatorial library powered by chemical fuel. On the one hand, we demonstrate that RNA templates the oligomerization and inhibits deoligomerization. On the other hand, we show that RNA can be a structural element in the formation of hydrogels. Moreover, in its hydrogel, RNA degradation by nucleases is accelerated. Thus, templates have a role beyond blueprints, protectors, and selectors. Template‐oligomer interactions can create new (micro)environments that might affect evolutionary dynamics.

Abstract The functions of living organisms are emergent from networks of biomolecules. In this review, we discuss the creation of synthetic life‐like systems based on the interplay of peptides and porphyrins in the supramolecular chemical systems. In particular, we focus on the spatiotemporal control of self‐assembly processes, which allows for the development of hierarchical structures for biomimetic catalysis and adaptive dynamics for stimulus‐responsive structural transformations. Notably, when operating in a nonequilibrium regime–characterized by kinetic traps, feedback loops, and dissipative conditions–the structural landscape expands and system‐level properties emerge, including transient catalysis, metabolic self‐replication, and Darwinian‐like evolution. Controlling these systems at the biointerface would facilitate intelligent therapeutic interventions in the anti‐tumor phototherapy. Supramolecular systems chemistry provides a valuable framework for exploring new physicochemical spaces of peptides and porphyrins, and may offer distinct advantages and extensive applications across diverse fields.

This work investigates the influence of dielectrophoretic forces on the structural features and the resulting aggregates of a chromogenic model system, peptide-diacetylene (D3GV-DA) amphiphiles. Here, we systematically investigate how non-uniform electric fields impact the (i) peptide-directed supramolecular assembly stage and (ii) topochemical photopolymerization stage of polydiacetylenes (PDAs) in a quadrupole-based dielectrophoresis (DEP) device, as well as the (iii) manipulation of D3GV-DA aggregates in a light-induced DEP (LiDEP) platform. The conformation-dependent chromatic phases of peptide-PDAs are utilized to probe the chain-level effect of DEP exposure after the supramolecular assembly or after the topochemical photopolymerization stage. Steady-state spectroscopic and microscopy analyses show that structural features such as the chirality and morphologies of peptidic 1-D nanostructures are mostly conserved upon DEP exposure, but applying mild, non-uniform fields at the self-assembly stage is sufficient for fine-tuning the chromatic phase ratio in peptide-PDAs and manipulating their aggregates via LiDEP. Overall, this work provides insights into how non-uniform electric fields offer a controllable approach to fine-tune or preserve the molecularly preset assembly order of DEP-responsive supramolecular or biopolymeric assemblies, as well as manipulate their aggregates using light projections, which have future implications for the precision fabrication of macromolecular systems with hierarchical structure-dependent function.

Abstract Chemical gradients provide spatiotemporal signaling fields in various cellular processes, driving complex dynamic behaviours such as differentiation and spatial organization. Here we employ opposing gradients of two artificial morphogens (sodium dodecyl sulfate (SDS) and sodium phosphotungstate (polyoxometalate; POM)) to systematically investigate morphological differentiation in organized populations of coacervate microdroplet‐based protocells. Using a matrix of 16 sets of counter‐diffusive gradients, we classify the differentiated protocells into five phenotypes and encode their spontaneous organization into different spatially patterned protocell consortia using a 3‐bit binary information system. We show that a predominant SDS gradient produces a diversity of differentiated phenotypes to generate complex spatially coded 2D protocell organizations. In contrast, a prevailing POM gradient decreases morphological differentiation, resulting in population homogenization. Our results improve our understanding of gradient concentration‐dependent collective responses in synthetic microscale agents and provide a step to a new spatially resolved information encoding method with 3‐bit binary outputs.

Abstract Asymmetric chemical reactions on the surfaces of colloidal particles are known to propel them into directional motion. The dynamics of such chemical micromotors are sensitive to their local chemical environments, which also continually evolve with the reactions on motor surfaces. This two‐way coupling between the motor dynamics and the local environment may result in complex nonlinear behaviors. As an example, we report that Janus Ag microspheres, which self‐propel in hydrogen peroxide (H 2 O 2 ), spontaneously reverse their direction of motion two or more times. We hypothesize that two distinct chemical reactions between Ag and H 2 O 2 drive the micromotor in opposite directions, and which reaction dominates depends on the local pH. Interestingly, the local pH near a Ag micromotor oscillates spontaneously in H 2 O 2 , likely due to a complex interplay between the kinetics of the reaction between Ag and H 2 O 2 and the diffusion of chemical species. Consequently, the pH‐sensitive Ag micromotor reverses its direction of motion in response to these pH oscillations. This study introduces a new mechanism for regulating the speed and directionality of micromotors, highlights the potential of Ag micromotors in chemical sensing, and sheds new light on the interplay between chemical kinetics and micromotor dynamics.

Abstract We previously reported collective behavior in colloidal aggregates of silver phosphate in H 2 O 2 and under UV light. Diffusiophoretic interactions between aggregates lead to non‐linear behavior such as oscillations and synchronization, in which oscillation frequencies increase with H 2 O 2 concentration. The aggregates transition between schooling and dispersed behaviors with incipient spatiotemporal correlations. We identified a kinetic model that maps the chemical species that are thought to underlie non‐linear phenomena in the colloidal aggregates, i. e. adsorbed oxygen species *OOH − and *O. We investigate the emergent dynamics for the simplest case, the coupling of two otherwise bistable clusters. Two coupling schemes are proposed and we find that – depending on whether the coupling is excitatory or inhibitory – the clusters may oscillate with zero or π phase shift.

Abstract The front cover artwork is provided by the Lerch group at the Stratingh Institute for Chemistry at the University of Groningen, The Netherlands. The cover illustrates a robot communicating with surrounding entities using various (chemical) signals. Not all communication and signal processing are successful, hence the slight confusion on the robot′s face. The cover alludes to the breadth of and future challenges for chemical communication within autonomous materials and robots. Cover design by Dr. Kaja Sitkowska. Read the full text of the Concept at 10.1002/syst.202400005 .

Abstract The spontaneous generation of transmembrane gradients is an important fundamental research goal for artificial nanotechnology. The active transport processes that give rise to such gradients directly mirror the famous Maxwell's Demon thought experiment, where a Demon partitions particles between two chambers to generate a nonequilibrium state. Despite these similarities, discussion of Maxwell's Demon is absent in the literature on artificial membrane transport. By contrast, the emergence of rational design principles for nonequilibrium artificial molecular motors can trace its intellectual roots directly to this famous thought experiment. This perspective highlights the links between Maxwell's Demon and nonequilibrium machines, and argues that understanding the implications of this 19 th century thought experiment is crucial to the future development of transmembrane active transport processes.

The Front Cover depicts a microfluidic channel with multilayer polylysine surfaces, which provide the potential to bestow an acid–base equilibrium with the capacity of signal transduction. Cover design by Niels van der Velde (University of Twente, NL). More information can be found in the Research Article by Jurriaan Huskens, Albert S. Y. Wong, and co-workers.

Abstract Rotaxanes are interlocked molecules that consist of a macrocycle encircling a stoppered thread. The ability to control relative component positions makes rotaxanes ideal building blocks for constructing functional and responsive molecular machines. Despite the potential of rotaxanes, their challenging synthesis limits their application. One approach to construct rotaxanes is to use an active template synthesis, where a reaction that forms the thread is accelerated in the cavity of a macrocycle. An emerging method of active template synthesis that exploits the ability of crown ether macrocycles to accelerate simple organic reactions is discussed herein. Crown ether active template synthesis (CEATS) permits the rapid and simple synthesis of rotaxanes containing a wide range of functionality. Integrating rotaxane formation with chemical reaction networks has permitted the construction of molecular machines. The simplification of rotaxane synthesis will facilitate their widespread study and application.