ChemSystemsChem最新文献

Creation of tissue-like materials termed prototissues has recently been garnering attention in the field of systems chemistry as a step towards bioinspired complex chemical systems mimicking multicellular organisms. Aiming at such life-like chemical systems, motility is one of the key properties. Although recent research has focused on inducing motility of individual protocells, motility of prototissues remained to be difficult because it is challenging to induce driving forces which are sufficient for motility of huge prototissues at a millimeter-/centimeter-scale. In this study, we demonstrate new strategies to induce motility of vesicle-based prototissue fibers by generating oxygen bubbles. Since enzyme catalase was incorporated into vesicles, the prototissue fibers composed of multiple vesicles exhibited enzymatic reactions where hydrogen peroxide was decomposed to generate oxygen. After supersaturation of the oxygen, heterogeneous nucleation occurred at the surface of the prototissue fibers to form oxygen bubbles. The buoyancy due to the oxygen bubbles induced flotation of the prototissue fibers, realizing directional motion. Additionally, since oxygen has a paramagnetic property, the prototissue fibers with oxygen bubbles exhibited magnetotaxis where they moved toward magnets. This study provides a potential for prototissues to be applied as smart soft robots with fine-tuned motility in response to chemicals and magnets.

We outline the “prebiotic gel-first” framework, which considers how the origin of life (OoL) could have potentially emerged within surface-attached gel matrices. Drawing on concepts from soft-matter chemistry and using modern microbial biofilms as a framing device, we review the physicochemical features of prebiotic gels and discuss how prebiotic gels could have provided the means for localized environments conducive to chemical complexification and evolutionary potential well before cellularization. Such prebiotic gels may have allowed primitive chemical systems to overcome key barriers in prebiotic chemistry by enabling molecular concentration, selective retention, reaction efficiency, and environmental buffering. Furthermore, we explore how gel matrices could have supported proto-metabolic activity through redox chemistry, light-driven processes, chemo-mechanical coupling—and proto-replication via autocatalytic networks or template-directed synthesis. We then briefly extend this model into the domain of extraterrestrial life detection, discussing the potential existence of “Xeno-films,” i.e., alien biofilm-like structures composed of non-terrestrial (or with some terrestrial) building blocks, and emphasize the relevance of agnostic life-detection strategies in the search for life as we know it, and do not know it.

The Review by Ana S. Pina and co-workers discusses how liquid-liquid phase separation (LLPS) enhances catalysis across natural and synthetic systems. In nature, LLPS forms dynamic membraneless organelles such as carboxysomes that control enzymatic efficiency through physical, chemical, and dynamic design principles. Synthetic systems replicate these mechanisms by using peptides, proteins, and polymers to create coacervate microreactors with tunable catalytic environments that enhance reaction rates.

ChemSystemsChem, 2025, 7, e202400072.

https://doi.org/10.1002/syst.202400072

During the production phase of this article, errors were accidentally introduced in the citation of references throughout the text. Accordingly, the original article has been updated to correct the citation of references.

Membraneless organelles, also known as biomolecular condensates, lack a surrounding membrane and are formed through liquid-liquid phase separation (LLPS). This process enhances reaction efficiency by compartmentalizing and concentrating reactants. Coacervates, a class of condensates, provide promising synthetic alternatives for improving enzymatic reactions. This review examines how LLPS enhances reaction efficiency in both natural and artificial systems, explores the design principles of coacervate-based artificial organelles employed in (bio)catalysis, and discusses challenges and future directions for leveraging LLPS in catalysis.

Inspired by biological systems that can visualize damage through optical signal such as bruising or bleeding, microcapsule-based self-reporting materials offer a promising strategy for autonomous detection of mechanical stress. These systems embed dye-filled microcapsules in polymer matrices, which rupture under stress to release optical signals. However, most of these systems only indicate whether damage has occurred, without providing information about how much damage or force was involved. This concept paper introduces self-reporting microcapsule systems and explores how they can be further developed to quantify microscale mechanical damage. Recent innovations enable force quantification through intensity-based outputs, ratiometric spectral shifts, multilayer capsule architectures, and rupture threshold engineering. By overcoming the current limitation of damage detection, force-resolved self-reporting materials open new possibilities for smarter, safer, and more durable systems in aerospace and infrastructure.

A key question in the transition from an abiotic chemical system to a biotic one is how selectively structures and functions emerged. Did previously unknown precursor structures exist, giving rise to the biochemical system we know today through a gradual evolutionary process? The RNA-world hypothesis suggests an early form of life based only on RNA oligomers. Although prebiotic reactions toward the canonical RNA-nucleosides are known, their synthesis is difficult in a simple prebiotic scenario. Therefore, proto-RNAs, which contain simplified RNA nucleosides as RNA precursors, are of considerable interest in the field of prebiotic chemistry. Here we show a simplified prebiotic synthesis of the Wöhler-RNA-nucleosides without the use of ribose but from aldehydes and the urea derivatives biuret and triuret. We demonstrate the formation of not only the α- and β-biuret furanosides but also the α- and β-pyranosides. The study of biuret isomerization shows fast anomerization between the furanosides, the kinetically favored reaction products, and a slower conversion to the thermodynamically more stable pyranosides. For the triuret nucleosides, only pyranoside product formation occurs in the prebiotic synthesis. These findings could be supported by the high instability of the triuret furanosides at elevated temperatures shown by kinetic studies. A detailed reaction network analysis of the Wöhler-RNA system reveals further insides, excluding Wöhler-RNA as proto-RNA-candidate.

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.

Activated Carboxylic Acids (ACAs) have been extensively used to drive dissipative systems relying on the acid-base reaction. This concept illustrates in detail the three possible kind of systems whose operation is enabled by ACAs: i) systems operating under dissipative conditions, ii) energy ratchets, and iii) systems operating under non-equilibrium steady state (NESS). More in the concept article by Matteo Valentini, Gianfranco Ercolani, and Stefano Di Stefano.

Carbodiimide-fueled reaction networks offer a versatile platform for nonequilibrium chemical systems. Typically, the carbodiimide converts a carboxylic acid to its anhydride, called “activation,” which subsequently undergoes hydrolysis, called “deactivation.” Here, we investigate pyridines with variable nucleophilicity as catalysts to control deactivation (pyridine, 4-methylpyridine, 4-methoxypyridine, and 4-dimethylaminopyridine). Reactions have been monitored by NMR spectroscopy. Although this reaction network is simple, determination of well-defined rate constants from kinetic modeling is challenging because of correlation between the parameters. This issue can be addressed by analyzing the anhydride hydrolysis independently. The rate of attack of the pyridines on the anhydride follows expected nucleophilicity trends, although this is offset by increased protonation of more-nucleophilic pyridines at typical pH's. The optimized parameters can be used to model the full carbodiimide-driven process, although the presence of the common carbodiimide EDC has unanticipated effects on the anhydride hydrolysis rate. The results offer context for controlling carbodiimide-fueled reaction networks through the choice of suitable catalysts and pH.