ChemSystemsChem最新文献

Biological translation is a universal process taking place in the ribosome. It involves the synthesis of a protein with a particular sequence from the information encoded in a messenger RNA and the amino acids carried by transfer RNAs with the assistance of specific enzymes. However, the origin of translation in the prebiotic world and, thus, in the absence of enzymes is difficult to envisage. Past and recent studies proposed different prebiotic models, following top-down and bottom-up approaches, for the origin and evolution of a primitive ribosome. The bottom-up models made use of distinct covalent linkages to connect RNA strands with amino acids and peptides. In this review, I focus on the covalent linkages used in these prebiotic models: acyl phosphate mixed anhydrides, phosphoramidates and ureas. I describe their syntheses under prebiotically plausible reaction conditions, as well as include their main conventional preparation methods. I also comment on their properties and chemical stabilities in aqueous solution. Finally, I examine the functions of the described covalent linkages in prebiotic processes involving RNA-templated amino acid transfer and peptide synthesis.

Hydrothermal vents maintain far-from equilibrium conditions that may have provided the necessary settings for the origin of life. To understand reactions under these physicochemical conditions, scientists have turned to the classic demonstration experiment, chemical gardens. The self-organization of precipitate tubes separates high and low pH environments similarly to the naturally occurring geological structures. Here, we report calcium-based chemical gardens forming in solutions containing anions of silicate, carbonate, or a mixture of the two in 100 °C and 23 °C environments. Under high temperature conditions, chemical gardens tend to have faster average growth velocities and form taller structures. We measure the composition of the precipitate tubes using Fourier transform infrared spectroscopy and find the formation of all polymorphs of calcium carbonate along with calcium silicates.

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.

The intricate interplay between self-assembly and phase separation orchestrates biomolecular organization inside cells, thereby dictating the formation of vital structures such as protein assemblies and membraneless organelles (MLOs). However, in the context of supramolecular polymerization, these fundamental processes have traditionally been studied separately. This study reevaluates the supramolecular polymerization process to unveil the presence of phase-separated droplet state. Utilizing the well-studied benzene-1,3,5-tricarboxamide (BTA) supramolecular motif, we explore its thermally driven liquid-liquid phase separation (LLPS). Thermodynamic and kinetic analysis, employing temperature-dependent spectroscopic and microscopic techniques, elucidates the distinct BTA states and their evolution towards the thermodynamic fiber state. This research sheds light on the existence of hidden phases of supramolecular monomers, emphasizing the delicate balance of non-covalent interactions among monomers and with solvents in governing self-assembly vs. phase separation. This is particularly important in comprehending phase separation in the biological realm such as in MLOs, and for applications such as condensate-modifying therapeutics.

The Front Cover illustrates a robot communicating with surrounding entities using various (chemical) signals. Not all communication and signal processing is 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. More information can be found in the Concept by Michael M. Lerch and co-workers.

The Cover Feature shows a Maxwell's Demon opening a trapdoor in a lipid-bilayer membrane to allow ions to move in one direction but not the other. This Concept underpins ratchet mechanisms, which have been used to develop small-molecule machines, and might soon enable the construction of artificial transmembrane pumps. More information can be found in the Concept by Stefan Borsley.

At the earliest development of prebiotic chemistry, bacterial cells were primarily viewed as “bags of molecules.” This longstanding viewpoint shaped and biased early research about life's origins, setting an initial target when considering the path from prebiotic chemistry to modern life. The two fields of systems chemistry and bacterial cell biology seem like oil and water, but each brings their own perspectives and methods to consider “what is life?”. Here, we review the most recent discoveries in bacterial cell biology, focusing on biomolecular condensates to consider how they may impact our thinking of matter-to-life transitions. The presence of condensate compartments in the bacterial domain of life strengthens the hypothesis that condensates play roles in coordinating chemical systems in life's origins. Bacterial condensates have been shown to enhance enzymatic reactions, tune substrate specificity, and be responsive to environmental conditions and metabolites. Systems chemistry studies have further illuminated the unique chemical environment within condensates and strategies for logically tying chemical processes to the formation and dissolution of condensates. We consider the potential of biomolecular condensates to provide “incubator spaces” where new chemistries can develop and examine future challenges regarding the capability of condensates to yield emergent chemical systems capable of selection.

Bio-inspired approaches in materials science and systems chemistry are yielding a variety of stimuli-responsive and dynamic materials that are gradually changing our everyday life. However, the ability to chemically program these materials to exhibit macroscopic higher-order behaviours such as self-assembly, contractility, swarming, taxis, chemical communication, or predator-prey dynamics remains an ongoing challenge. While still in its infancy, the successful fabrication of bio-inspired materials displaying higher-order behaviours not only will help bridging the gap between living and non-living matter, but it will also contribute to the development of advanced materials for potential applications ranging from tissue engineering and biotechnology, to soft robotics and regenerative medicine. Our Mini-Review will systematically discuss the higher-order behaviours developed thus far in bio-inspired systems, namely (i) polymer networks (ii) microbots, (iii) protocells, and (iv) prototissues. For each system it will provide key examples and highlight how the emergent behaviour could be chemically programmed.

The knowledge regarding the origins of life from inanimate materials is still elusive. It was proposed that biological building blocks evolved from the inorganic substances present in the early earth conditions. However, the process by which chemistry can be converted into biology has not yet been achieved in the laboratory. The artificial system in the out-of-equilibrium state must maintain a few critical features of life, like compartmentalization, metabolism, and replication, to be considered alive. In this direction, working with cysteine (Cys)-based molecules is strategic to understand the life evolution process. The presence of the sulphydryl (−SH) group in the Cys-residue can build a dynamic equilibrium state through disulfide redox chemistry under the proper guidance of oxidizing and reducing agents. In this review article, our primary focus is to discuss the Cys-containing short-peptide-based self-assembly and disassembly processes. The formation of disulfide bonds sometimes helps in the self-assembly process and gelation, but the reverse is also true in some cases. In the later part of this article, we cover the fact that these sulphydryl-based systems have shown their adaptability to mimic different life-essential criteria to participate in Darwinian evolution.

It has long been thought that abiogenesis requires a process of selection and evolution at the molecular level, but this process is hard to explore experimentally. One solution could be the use of automation in experiments which could allow for traceability and the ability to explore a larger reaction space. We report a fully programmable and automated platform to explore the reactions of amino acids in the presence of mineral environments. The robotic system is based upon the Chemputer system which has well defined modules, software, and a chemical programming language to orchestrate the chemical processes, including analysis. The reaction mixtures were analysed with tandem mass spectrometry and a peptide sequencing algorithm. Each experiment was screened for 1,398,100 possible unique sequences, and more than 550 specifically defined sequences were confirmed experimentally. This work aimed to develop a new understanding of selection in repeated cycles of polymerisation reactions to explore the emergence of well-defined amino acid sequences. We found that the outcome of oligomerisation was significantly influenced by the presence of different minerals, and that a serpentine environment selects glycine and phenylalanine rich fragments that enable the formation of longer oligomers with well-defined sequences as a function of cycle number.