Alvaro Lopez-Acosta, Jorge S. Valera, Rafal Klajn, Thomas M. Hermans
{"title":"Photoacid-Mediated Controllable Gelation in a Chemical Reaction Cycle","authors":"Alvaro Lopez-Acosta, Jorge S. Valera, Rafal Klajn, Thomas M. Hermans","doi":"10.1002/syst.70037","DOIUrl":"https://doi.org/10.1002/syst.70037","url":null,"abstract":"<p>We explore the use of a photoacid in a chemical reaction cycle, which allows for the controlled sol-to-gel transition of a saccharide aldehyde-based self-assembling system. The modulation of the pH with light enables to generate chemical fuels in situ, thus triggering monomer activation and gelation. Our efforts represent a promising step toward dissipative self-assembled systems with a higher degree of spatiotemporal control.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70037","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147715031","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 : 2026-04-01DOI: 10.1002/syst.202500060
Peter Agbo
{"title":"Self-Replicating Fuels via Autocatalytic Molecular Bond Fission","authors":"Peter Agbo","doi":"10.1002/syst.202500060","DOIUrl":"https://doi.org/10.1002/syst.202500060","url":null,"abstract":"<div>\u0000 \u0000 <p>This computational study introduces a conceptual framework for practical, electrochemical fuel generation schemes that display exponential product yields as functions of time. Exponential reaction scaling for formate replication is simulated through an autocatalytic cycle that emulates the process of DNA replication facilitated by the polymerase chain reaction (PCR). Here, an initial buildup of formate into a two-carbon chain through CO<sub>2</sub> carboxylation forms oxalate. A subsequent two-electron reduction yields glyoxylate, with base-mediated hydrolysis driving C─C bond breakage of glyoxylate into two formate equivalents. These products are then recycled to serve as reactants. This recursive process chemistry drives formate evolution that scales as 2<i><sup>n</sup></i>, where <i>n</i> is the cycle number. Each step of the proposed fuel cycle is analogized to the steps of DNA annealing, nucleotide polymerization and hybridized strand fission that are responsible for the exponential product yields observed in PCR-mediated DNA synthesis. As a consequence of this replication behavior, rapid rates of fuel production become accessible even when the individual rate constants for the cycle's constituent reactions are slow. Practical barriers to realizing this system are discussed, particularly the difficulty of formate carboxylation and the energy demands of chemical amplification.</p>\u0000 </div>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147714944","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 : 2026-03-26DOI: 10.1002/syst.202500076
Paula De Dios Andres, Ankush Garg, Ramy Alam, Isabella N. Westensee, Magnus Kjaergaard, Brigitte Städler
{"title":"Transmembrane Condensation in Albumin-Loaded Giant Vesicles Induced by an Intrinsically Disordered Protein","authors":"Paula De Dios Andres, Ankush Garg, Ramy Alam, Isabella N. Westensee, Magnus Kjaergaard, Brigitte Städler","doi":"10.1002/syst.202500076","DOIUrl":"https://doi.org/10.1002/syst.202500076","url":null,"abstract":"<p>The interplay between biomolecular condensates and cellular membranes is central to understanding dynamic intracellular organization and membrane repair. Here, we present a minimal synthetic system to examine how membrane composition and curvature govern condensate–membrane interactions within this model platform. We demonstrate that the exposure of either lipid or polymer–lipid hybrid giant vesicles with encapsulated bovine serum albumin to a resilin-inspired intrinsically disordered protein (IDP), which undergoes liquid–liquid phase separation, results in in situ formation of transmembrane condensates. This observation of cargo-triggered condensation across giant vesicle membranes directly links encapsulated protein crowding to condensate nucleation and insertion. The condensation morphology was tunable by vesicle size and membrane elasticity where smaller vesicles and stiffer hybrid membranes favored transmembrane condensation, whereas larger or softer membranes promoted membrane wetting and deformation. Condensate formation locally reorganized lipids and facilitated leaflet coupling without compromising overall membrane integrity or cargo retention. This mechanistic understanding offers a unique opportunity to gain insight into the complex cell biological process of membrane repair using a minimal system.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202500076","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147569432","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 : 2026-03-14DOI: 10.1002/syst.202500081
Shana Shirin Valapra, Malak Jaber, Tsvetomir Ivanov, Lucas Caire da Silva, Guillermo Monreal Santiago
{"title":"Temporal Control Over Complex, Simple, and Multiphase Coacervates Using Ureolysis and Ammonium Carbonate Decomposition","authors":"Shana Shirin Valapra, Malak Jaber, Tsvetomir Ivanov, Lucas Caire da Silva, Guillermo Monreal Santiago","doi":"10.1002/syst.202500081","DOIUrl":"https://doi.org/10.1002/syst.202500081","url":null,"abstract":"<p>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.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202500081","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147565807","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 : 2026-03-03DOI: 10.1002/syst.202500072
Olivia J. Armendarez, Wei-Ting Chang, Leila F. Deravi
{"title":"Protein-based Photoswitches: From Natural Systems to Engineered Materials","authors":"Olivia J. Armendarez, Wei-Ting Chang, Leila F. Deravi","doi":"10.1002/syst.202500072","DOIUrl":"https://doi.org/10.1002/syst.202500072","url":null,"abstract":"<div>\u0000 \u0000 <p>Protein-based photoswitches undergo reversible binding and/or conformational changes when exposed to light to transduce signals required for homeostatic control of living systems. While decades of research, discovery, and testing have highlighted important roles for these transducing elements in nature, the nuanced differences in their compositions, structures, and subsequent functions have limited their broader adoption in targeted materials applications. This review surveys the structure/property relationships of protein-based photoswitches in nature. Similarities and distinguishing features that enable their dynamic function are discussed, where variables including activation energy, composition, response time, and recovery dynamics are used to guide criteria outlined for consideration in the rational selection of photoswitches for materials.</p>\u0000 </div>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147562902","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}
{"title":"Front Cover: Surface-Driven Protocell Formation in Geologically Relevant Early Earth Environment (ChemSystemsChem 2/2026)","authors":"Pamela Knoll, Silvia Holler","doi":"10.1002/syst.70033","DOIUrl":"https://doi.org/10.1002/syst.70033","url":null,"abstract":"<p>Illustration of a plausible early-Earth or extraterrestrial prebiotic environment, showcasing volcanic landscapes and mineral-rich substrates spanning surfaces and subsurface niches. These dynamic geochemical interfaces likely catalyzed the assembly and evolution of protocellular systems (purple spheres), bridging geology and life's origins across planets. More in the Review (e00062) by Pamela Knoll and Silvia Holler.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147569811","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 : 2026-02-28DOI: 10.1002/syst.202500071
Masato Suzuki, Koki Kamiya
{"title":"Synthetic Cells on Demand: From Molecular Stimuli to Cellular Functions","authors":"Masato Suzuki, Koki Kamiya","doi":"10.1002/syst.202500071","DOIUrl":"https://doi.org/10.1002/syst.202500071","url":null,"abstract":"<p>Synthetic cells constructed via bottom-up approaches using lipid or polymer vesicles have become essential tools for mimicking cellular functions and studying synthetic biological systems. These vesicles can undergo morphological changes and trigger internal reactions in response to external stimuli, such as osmotic pressure, temperature, pH, light, and chemical signals. This review highlights recent advances in the design of stimulus-responsive artificial cells, with a focus on lipid or polymer vesicle deformation, division, and signal-triggered biochemical activity. Special emphasis is placed on multivesicular vesicle systems that emulate organelle-level compartmentalization and allow precise control of internal functions. Additionally, artificial cell−cell communication systems have been developed using DNA-based adhesion, nanopores, and cell-penetrating peptides to facilitate molecular exchange between lipid or polymer vesicles. These developments have paved the way for the construction of autonomous artificial cells capable of sensing their environment and performing programmable functions. Such systems hold great promise for applications in synthetic biology, including therapeutic delivery, biosensing, and biomolecular robot development.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202500071","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147569810","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 : 2026-02-18DOI: 10.1002/syst.202500075
Antony Wing Hung Ng, Yu Hin Leung, Ho Yu Au-Yeung
{"title":"Dynamics of the Interlocked Rings in a Water-Soluble Radial [7]Catenane","authors":"Antony Wing Hung Ng, Yu Hin Leung, Ho Yu Au-Yeung","doi":"10.1002/syst.202500075","DOIUrl":"https://doi.org/10.1002/syst.202500075","url":null,"abstract":"<p>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.</p>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202500075","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320872","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}
{"title":"Enhanced Ribose-Forming Pathways in the Formose Reaction by Oxometalate Catalysts","authors":"Hiroaki Nishijima, Taizo Ikuta, Hiro Tabata, Takashi Harada, Rika Miyake, Shuji Nakanishi, Yoko Hase","doi":"10.1002/syst.202500077","DOIUrl":"https://doi.org/10.1002/syst.202500077","url":null,"abstract":"<div>\u0000 \u0000 <p>Controlling product selectivity in complex chemical reaction networks (CRNs) remains a major challenge in rational catalyst design, as multiple competing pathways often yield diverse products. The formose reaction, an autocatalytic process that converts formaldehyde (HCHO) into monosaccharides, represents a prototypical nonenzymatic CRN. It has long been investigated in the context of prebiotic chemistry and, more recently, as a system that transforms a C1 compound into higher-carbon species. In this study, we examined the influence of catalysts on pathway selectivity within this reaction network. Sodium tungstate (Na<sub>2</sub>WO<sub>4</sub>), which we have previously investigated, produces a product distribution distinct from that obtained with conventional strong base catalysts. Analysis of the aldopentose (C5a) formation pathway revealed that xylose formation predominates under NaOH catalysis, whereas Na<sub>2</sub>WO<sub>4</sub> selectively promotes ribose production. Mechanistic experimental studies and density functional theory (DFT) calculations indicate that WO<sub>4</sub><sup>2−</sup> preferentially stabilizes the transition state leading to ribose. These findings demonstrate that understanding catalyst–substrate interactions and identifying the reaction pathways they govern in the formose reaction network enables the prediction of product distributions in complex CRNs.</p>\u0000 </div>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147288306","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 : 2026-02-11DOI: 10.1002/syst.202500037
Sophia Riazi-Sekowski, Kamilah Bundang, Jordan L. Chastain, Nancy Carman, Seneca J. Velling, John Aguilera, Matt Luna, Cathy Trejo, Osama Alian, Bronwyn L. Teece, Katherine A. Dzurilla, Laura M. Barge, Jessica M. Weber
{"title":"Organic Cofactors in the Electron Transport Chain: Properties and Connection to the Prebiotic World","authors":"Sophia Riazi-Sekowski, Kamilah Bundang, Jordan L. Chastain, Nancy Carman, Seneca J. Velling, John Aguilera, Matt Luna, Cathy Trejo, Osama Alian, Bronwyn L. Teece, Katherine A. Dzurilla, Laura M. Barge, Jessica M. Weber","doi":"10.1002/syst.202500037","DOIUrl":"https://doi.org/10.1002/syst.202500037","url":null,"abstract":"<div>\u0000 \u0000 <p>Metabolism is a critical process for biology and is of great interest to those researching geobiological processes and the origins of life. A metabolism comprises a network of chemical reactions for molecular synthesis, energy conversion pathways, and cellular function. Understanding the mechanisms underlying metabolic processes provides insight into the evolution of electrochemical processes in complex systems and informs the possible pathways by which abiotic chemistry transitioned to biochemistry. Modern enzymes utilize cofactors to mediate chemical reactions and overcome energetic limitations. While enzymes are specific, large, and complex biological proteins, cofactors are simpler ions and molecules incorporated within the larger protein complex. Cofactors play a fundamental role in supplementing an enzyme's catalytic role and may represent a convergence between abiotic and biotic chemistry, allowing studies of cofactors to reveal potential prebiotic processes. Here, we review some of the organic / nucleotide cofactors participating in the electron transport chain (ETC): their structures, capacity for energy conversion, and their putative role in the origins of life. We choose to focus on four specific organic cofactors that have evolved to be key in extant mitochondrial ETCs—adenosine triphosphate (ATP), nicotinamide adenine dinucleotide (NADH), flavins (FAD, FMN), and quinones (ubiquinone)—to conceptually bridge the gap between the earliest inorganic cofactors and the protein complexes of modern biochemistry. We then make recommendations for future research topics and avenues.</p>\u0000 </div>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147268906","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}