ChemSystemsChemPub Date : 2024-05-22DOI: 10.1002/syst.202400027
Dr. Oliver R. Maguire
{"title":"The Many-Chemicals Problem of Systems Chemistry","authors":"Dr. Oliver R. Maguire","doi":"10.1002/syst.202400027","DOIUrl":"10.1002/syst.202400027","url":null,"abstract":"<p>An <i>E. coli</i> cell contains ~2500 different chemicals which combine into an ordered biochemical reaction network out of which emerges a living system. A chemist taking 2500 different chemicals from a laboratory chemical cabinet and combining them together will likely cause an explosive disaster and produce an intractable chemical sludge. Systems Chemistry aspires to construct systems whose complexity rivals that of life. However, to do this we will need to learn how to combine hundreds or thousands of different chemicals together to form a functional system without descending into a disordered chemical sludge. This is the Many-Chemicals Problem of Systems Chemistry. I explore a key strategy life employs to overcome this challenge. Namely, the combination of kinetically stable and thermodynamically activated molecules (e. g. ATP) with enzyme catalysts (e. g. histidine kinases). I suggest how the strategy could have begun at the origin of life. Finally, I assess the implications of this strategy for Systems Chemistry and how it will enable systems chemists to construct systems whose complexity rivals that of life.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 5","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141108586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-05-14DOI: 10.1002/syst.202400025
Dr. Natsumi Noda, Kohei Nomura, Naho Takahashi, Dr. Fumitaka Hashiya, Prof. Dr. Hiroshi Abe, Prof. Dr. Tomoaki Matsuura
{"title":"Slow Freeze-Thaw Cycles Enhanced Hybridization of Kilobase DNA with Long Complementary Sticky Ends","authors":"Dr. Natsumi Noda, Kohei Nomura, Naho Takahashi, Dr. Fumitaka Hashiya, Prof. Dr. Hiroshi Abe, Prof. Dr. Tomoaki Matsuura","doi":"10.1002/syst.202400025","DOIUrl":"10.1002/syst.202400025","url":null,"abstract":"<p>The creation of large information molecules may have played an essential role in the origins of life. In this study, we conducted slow freeze-thaw (F/T) experiments to test the possibility of enhanced hybridization between the complementary sticky ends attached to kilobase-sized DNA fragments at sub-nanomolar concentrations. DNA fragments of 2- and 3-kilobase pairs (kbp) with 50-base complementary sticky ends that can form 5 kbp-sized hybridization products were mixed. While simple incubation provided little hybridization product, significantly effective hybridization was observed after freezing and thawing at a controlled time rate (<0.3 K min<sup>−1</sup>), even with small DNA concentrations (<1 nM). Furthermore, slow thawing had a more effect on hybridization than slow freezing. The reaction efficiency was reduced by rapid thawing instead of slow thawing, suggesting that the eutectic phase concentration played an important role in hybridization. A slow F/T cycle was effective even for the hybridization reaction between two 10 kbp DNA fragments, which yielded a 20 kbp product at sub-nanomolar concentrations. Repeating the slow F/T cycle significantly improved the reaction efficiency. The possible role of the F/T cycles in early Earth environments is discussed here.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140979943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-05-12DOI: 10.1002/syst.202400029
Dr. İrep Gözen, Prof. Stephen Mann, Prof. Aldo Jesorka
{"title":"Autonomous Development of Compositional Diversity in Self-Spreading Flat Protocells","authors":"Dr. İrep Gözen, Prof. Stephen Mann, Prof. Aldo Jesorka","doi":"10.1002/syst.202400029","DOIUrl":"10.1002/syst.202400029","url":null,"abstract":"<p>An experimental pathway to the spontaneous generation of compositionally diverse synthetic protocells is presented. The pathway is initiated by flat giant unilamellar vesicles (FGUVs) that originate from compositionally different multilamellar lipid reservoirs and undergo spontaneous spreading across solid surfaces. On contact, the spreading FGUVs merge to produce a concentration gradient in membrane lipids across the fusion interface. Subsequent reconstruction through a series of shape transformations produces a network of nanotube-connected lipid vesicles that inherit different ratios of the membrane constituents derived from the bilayers of the parent FGUVs. The fusion process leads to the engulfment of small FGUVs by larger FGUVs, mimicking predator-prey behavior in which the observable characteristics of the prey are lost but the constituents are carried by the predator FGUV to the next generation of lipid vesicles. We speculate that our results could provide a feasible pathway to autonomous protocell diversification in origin of life theories and highlight the possible role of solid surfaces in the development of diversity and rudimentary speciation of natural protocells on the early Earth.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 6","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400029","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140987127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-05-10DOI: 10.1002/syst.202400021
Prof. Dr. Yusuke Sato
{"title":"Artificial Molecular Systems for Complex Functions Based on DNA Nanotechnology and Cell-Sized Lipid Vesicles","authors":"Prof. Dr. Yusuke Sato","doi":"10.1002/syst.202400021","DOIUrl":"10.1002/syst.202400021","url":null,"abstract":"<p>Cells are highly functional and complex molecular systems. Artificially creating such systems remains a challenge, which has been extensively studied in various research fields, including synthetic biology and molecular robotics. DNA nanotechnology is a powerful tool for bottom-up engineering for constructing functional nanostructures or chemical reaction networks which can be utilized as components for artificial molecular systems. Encapsulation of these components into a giant unilamellar vesicle (GUV) composed of a lipid bilayer, the base structure of the cellular membrane, results in a functional cell-sized structure that partially mimics some cellular functions. This review discusses the studies contributing to the construction of GUV-based artificial molecular systems based on DNA nanotechnology. Molecular transport and signal transduction through lipid membranes are essential to uptake molecules from the environment and respond to stimuli. Membrane shaping relates to various functions, including motility and signaling. A chemical reaction network is required to autonomously regulate the system‘s functions. This review describes the functions realized using DNA nanostructures and DNA reaction networks. Given the designability and programmability of DNA nanotechnology, it may be possible that the functionality of artificial molecular systems could be comparable to or even surpass that of natural molecular systems.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140991172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-05-08DOI: 10.1002/syst.202400030
Dr. Luis Escobar
{"title":"Covalent Linkages Used in Prebiotic Chemistry for RNA-Templated Amino Acid Transfer and Peptide Synthesis","authors":"Dr. Luis Escobar","doi":"10.1002/syst.202400030","DOIUrl":"10.1002/syst.202400030","url":null,"abstract":"<p>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.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 5","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140998488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-04-29DOI: 10.1002/syst.202400012
Dr. Pamela Knoll, Dr. Corentin C. Loron
{"title":"Effect of Temperature on Calcium-Based Chemical Garden Growth","authors":"Dr. Pamela Knoll, Dr. Corentin C. Loron","doi":"10.1002/syst.202400012","DOIUrl":"https://doi.org/10.1002/syst.202400012","url":null,"abstract":"<p>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.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 5","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400012","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142233176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-04-29DOI: 10.1002/syst.202400036
P. Jarne de Jong, Foteini Trigka, Dr. Michael M. Lerch
{"title":"Towards Autonomous Materials–Challenges in Chemical Communication","authors":"P. Jarne de Jong, Foteini Trigka, Dr. Michael M. Lerch","doi":"10.1002/syst.202400036","DOIUrl":"https://doi.org/10.1002/syst.202400036","url":null,"abstract":"<p>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.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400036","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140949172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-04-23DOI: 10.1002/syst.202400013
Mohit Kumar, Job. N. S. Hanssen, Prof. Dr. Shikha Dhiman
{"title":"Unveiling the Liquid-Liquid Phase Separation of Benzene-1,3,5-Tricarboxamide in Water","authors":"Mohit Kumar, Job. N. S. Hanssen, Prof. Dr. Shikha Dhiman","doi":"10.1002/syst.202400013","DOIUrl":"10.1002/syst.202400013","url":null,"abstract":"<p>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.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140669487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-04-22DOI: 10.1002/syst.202400032
P. Jarne de Jong, Foteini Trigka, Dr. Michael M. Lerch
{"title":"Front Cover: Towards Autonomous Materials–Challenges in Chemical Communication (ChemSystemsChem 3/2024)","authors":"P. Jarne de Jong, Foteini Trigka, Dr. Michael M. Lerch","doi":"10.1002/syst.202400032","DOIUrl":"https://doi.org/10.1002/syst.202400032","url":null,"abstract":"<p><b>The Front Cover</b> 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.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400032","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140949318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemSystemsChemPub Date : 2024-04-22DOI: 10.1002/syst.202400033
Dr. Stefan Borsley
{"title":"Membrane Transport, Molecular Machines, and Maxwell's Demon","authors":"Dr. Stefan Borsley","doi":"10.1002/syst.202400033","DOIUrl":"https://doi.org/10.1002/syst.202400033","url":null,"abstract":"<p><b>The Cover Feature</b> 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.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140949319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}