ChemSystemsChem最新文献

Reaction–Diffusion and Diffusion-Driven Fronts in Reversible Redox Autocatalytic Networks 可逆氧化还原自催化网络中的反应-扩散和扩散驱动前沿

IF 2.5

ChemSystemsChem Pub Date : 2026-08-16 DOI: 10.1002/syst.70046

Stevan Maćešić, Ágota Tóth, Dezső Horváth

{"title":"Reaction–Diffusion and Diffusion-Driven Fronts in Reversible Redox Autocatalytic Networks","authors":"Stevan Maćešić, Ágota Tóth, Dezső Horváth","doi":"10.1002/syst.70046","DOIUrl":"https://doi.org/10.1002/syst.70046","url":null,"abstract":"Autocatalysis plays a critical role in the self-organization of chemical and biological systems, influencing phenomena such as bistability and reaction–diffusion front formation. In the rhizosphere, the regulation of reactive oxygen species (ROS) is mediated by intricate networks of reversible autocatalytic reactions, yet the mechanisms governing their spatiotemporal dynamics remain unclear. Here, we perform comprehensive numerical simulations of a reaction–diffusion model for ROS dynamics incorporating redox couples, sodium borohydride, and oxygen. We identify oxidation-driven autocatalysis as the primary mechanism responsible for the emergence of stable reaction–diffusion fronts that propagate with constant velocity and shape, whereas reduction fronts display diffusive broadening attenuated by the local oxygen concentration. Furthermore, we demonstrate that reversible quadratic autocatalytic cycles coupled to a simple autocatalyst removal and diffusion are sufficient to reproduce these characteristic front behaviors. These results also provide insights that are transferable to a wide range of autocatalytic networks exhibiting spatiotemporal pattern formation.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 5","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784262","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}

引用次数: 0

Tuning Membrane Binding and Lipid Phase Preference of DNA Nanostructures via Synergistic Multi-Lipidation 通过协同多脂化调节膜结合和DNA纳米结构的脂相偏好

IF 2.5

ChemSystemsChem Pub Date : 2026-08-10 DOI: 10.1002/syst.70052

Subhasini Singh, Henri G. Franquelim

{"title":"Tuning Membrane Binding and Lipid Phase Preference of DNA Nanostructures via Synergistic Multi-Lipidation","authors":"Subhasini Singh, Henri G. Franquelim","doi":"10.1002/syst.70052","DOIUrl":"https://doi.org/10.1002/syst.70052","url":null,"abstract":"Lipophilic anchors are essential biomolecular modifications that mediate membrane-dependent functions by tethering associated biomolecules, such as peripheral proteins, to the lipid bilayer. Inspired by natural multi-lipidation systems, we introduce a DNA origami platform functionalized with lipophilic anchors spanning a wide hydrophobicity range to systematically investigate how anchor hydrophobicity governs membrane binding and lateral organization. By varying anchor type, number, and spatial arrangement, we evaluated the interactions of anchor-modified DNA origami across homogeneous and phase-separated giant unilamellar vesicles (GUVs). On homogeneous lipid membranes, stable attachment required a minimum per-anchor hydrophobicity (cLogP ≈ 5) below which binding of origami to the membrane was ineffective regardless of anchor type or number. However, combining weak and strong anchors on a single nanostructure synergistically enhances binding through cooperative effects that exceed additive contributions of either anchor type. On phase-separated GUVs, our combined-anchor system revealed that anchor molecular identity and intrinsic hydrophobicity regulate membrane partitioning. Notably, weak anchors drive the nanostructure localization from the liquid-ordered (Lo) to the liquid-disordered (Ld) phase, with this shift inversely related to the hydrophobicity of the strong anchor. Collectively, our results establish design principles for multi-anchor strategies enabling tunable membrane binding and controlled phase-specific localization of DNA nanostructures.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 5","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70052","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753310","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}

引用次数: 0

Time-Resolved Chemical Logic in Dissipative Multicomponent Systems 耗散多组分系统中的时间分辨化学逻辑

IF 2.5

ChemSystemsChem Pub Date : 2026-08-06 DOI: 10.1002/syst.70051

Amit Ghosh

{"title":"Time-Resolved Chemical Logic in Dissipative Multicomponent Systems","authors":"Amit Ghosh","doi":"10.1002/syst.70051","DOIUrl":"https://doi.org/10.1002/syst.70051","url":null,"abstract":"<div>\u0000 \u0000 Multicomponent chemical systems have enabled increasingly complex behavior through self-sorting and communication. In most cases, however, these systems operate under equilibrium or quasi-equilibrium conditions, where outputs are defined by stable states. A different regime emerges when multicomponent networks are coupled to transient chemical fuels, introducing dissipative operation and time-resolved behavior. Under such conditions, fuel-driven chemical reaction cycles drive ion redistribution, generating transient network states that evolve and relax autonomously, giving rise to dynamic outputs and time-encoded signals. This Review focuses on the emergence of time-resolved chemical logic in dissipative multicomponent systems, with particular emphasis on acid-fuel-driven networks, ion translocation, and time-encoded signaling, including single and multi-pulse (waveform) responses and time-gated catalytic activity. The mechanistic origins of time-resolved behavior, including kinetic asymmetry, competitive binding, and fuel consumption, are discussed, and emerging design principles for programming chemical logic and function in time are outlined, highlighting parallels with biological signaling processes. By linking molecular logic, dissipative operation, and multicomponent communication, this Review highlights how chemical information and function can be programmed through time.\u0000 </div>","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 5","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753178","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}

引用次数: 0

Artificial Catch Bonds: From Molecular Design to Network Mechanics 人工捕获键：从分子设计到网络力学

IF 2.5

ChemSystemsChem Pub Date : 2026-08-04 DOI: 10.1002/syst.70049

Hengfeng Jiang, Micah Yang, Isaac T. S. Li

引用次数: 0

Synchrotron-Based X-Ray Tomography of Strontium Phosphate Chemical Gardens 基于同步加速器的磷酸锶化学园x射线断层扫描

IF 2.5

ChemSystemsChem Pub Date : 2026-08-03 DOI: 10.1002/syst.70048

Tan-Phat Huynh, Emilia Ares, Parastoo Vahdatiyekta, Anne Marie Møller Faaborg, Henrik Birkedal, Thorbjørn Erik Køppen Christensen

引用次数: 0

Theoretical Model of Chemomechanical Self-Oscillation in a Two-Enzyme Core–Shell Hydrogel With pH-Gated Microcapsules ph门控微胶囊双酶核壳水凝胶化学力学自振荡的理论模型

IF 2.5

ChemSystemsChem Pub Date : 2026-08-03 DOI: 10.1002/syst.70050

Shohei Shinbo, Taro Sukegawa, Yuhei Yamada, Shingo Maeda

{"title":"Theoretical Model of Chemomechanical Self-Oscillation in a Two-Enzyme Core–Shell Hydrogel With pH-Gated Microcapsules","authors":"Shohei Shinbo, Taro Sukegawa, Yuhei Yamada, Shingo Maeda","doi":"10.1002/syst.70050","DOIUrl":"https://doi.org/10.1002/syst.70050","url":null,"abstract":"A chemo–mechanical coupled oscillator integrating catalytic reactions with stimuli-responsive hydrogels is a promising platform for autonomous soft actuators. We propose a theoretical model of a pH-responsive hydrogel system where pH and gel volume are autonomously regulated by internal chemical reactions without external flow control. In a core–shell multilayered hydrogel, an acid-producing enzyme and a base-producing enzyme are spatially separated in the core and shell layers, respectively, while slowed proton transport between the two regions introduces a characteristic time delay into the system. By coupling these enzymatic reactions with the hysteretic volume phase transition of the pH-responsive hydrogel, dynamic swelling–deswelling behavior is controlled. Using nondimensionalization and bifurcation analysis, we classify regimes of monostability, bistability, and sustained oscillations as a function of key parameters: substrate concentration, permeability, and the ratio between gel relaxation time and chemical reaction timescale. Unlike single-enzyme models, where oscillations require the reaction timescale to exceed the gel relaxation time, our dual-enzyme model enables sustained oscillations even when these timescales are comparable. These results provide design guidelines for biocompatible autonomous oscillating hydrogels, offering greater flexibility in selecting gel size and relaxation properties for soft robotic applications.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 5","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70050","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652476","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}

引用次数: 0

Tubular Precipitation Structures From Alum-Copper(II) Sulfate Crystals 铝-铜（II）硫酸盐晶体的管状沉淀结构

IF 2.5

ChemSystemsChem Pub Date : 2026-07-27 DOI: 10.1002/syst.70044

Christopher J. Ross, Joel P. Blodgett, Hien T. Nguyen, Cole B. Roys, Madison J. Rase, Richard J. Staples, Jason J. Pagano

引用次数: 0

Freeze-thaw Fusion Enables Multi-component Delivery and Protein Synthesis in POPG-containing Lipid Vesicles 冻融融合使含popg脂质囊泡中的多组分传递和蛋白质合成成为可能

IF 2.5

ChemSystemsChem Pub Date : 2026-07-17 DOI: 10.1002/syst.70045

Tsubasa Yamashina, Masaya Oki, Gakushi Tsuji

{"title":"Freeze-thaw Fusion Enables Multi-component Delivery and Protein Synthesis in POPG-containing Lipid Vesicles","authors":"Tsubasa Yamashina, Masaya Oki, Gakushi Tsuji","doi":"10.1002/syst.70045","DOIUrl":"https://doi.org/10.1002/syst.70045","url":null,"abstract":"Fusion between giant unilamellar vesicles (GUVs) provides a simple way to deliver and mix biochemical substrates within compartments surrounded by phospholipid membrane. Negatively charged phospholipids such as 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1′-rac-glycerol) (POPG) have recently been shown to improve vesicle robustness during freeze-thaw (F/T) treatments by suppressing membrane rupture and reducing leakage of encapsulated contents. Here we show that incorporating POPG into phospholipid membranes markedly enhances macromolecular encapsulation and supports efficient cell-free protein synthesis using the reconstituted PURE translation system within GUVs. Moreover, we demonstrate that a single F/T-mediated fusion event is sufficient to deliver the dozens of protein components required for the PURE system into preformed vesicles, enabling robust protein synthesis after fusion. POPG-containing membranes yielded higher protein output and a larger fraction of translation-active compartments, consistent with improved substrate retention during the freezing process. These results establish freeze-thaw fusion as a useful method for supplying complex biochemical components into phospholipid vesicles. This strategy expands the functional capabilities of artificial cell models and provides a general framework for constructing artificial compartments capable of sustained gene expression and multi-component biochemical activity.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 4","pages":""},"PeriodicalIF":2.5,"publicationDate":"2026-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70045","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148467336","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}

引用次数: 0

Autocatalytic Deprotection of Diboronate-Protected Quinones via Redox Cross-Catalysis: Mechanistic Insights Into Double Masking Strategies 通过氧化还原交叉催化对二硼酸保护醌的自催化脱保护：双重掩蔽策略的机制见解

IF 3.1

ChemSystemsChem Pub Date : 2026-05-29 DOI: 10.1002/syst.70042

Pan Hui, Alexandra Pastor, Mathieu Branca, Benoît Limoges, François Mavré

{"title":"Autocatalytic Deprotection of Diboronate-Protected Quinones via Redox Cross-Catalysis: Mechanistic Insights Into Double Masking Strategies","authors":"Pan Hui, Alexandra Pastor, Mathieu Branca, Benoît Limoges, François Mavré","doi":"10.1002/syst.70042","DOIUrl":"https://doi.org/10.1002/syst.70042","url":null,"abstract":"We report an autocatalytic molecular amplification system based on the double masking of benzoquinones with boronate ester protecting groups (i.e., diboronate ester probes). This design extends a previously described redox cross-catalytic (RCC) reaction scheme, in which hydrogen peroxide (H2O2) and quinones are exponentially co-generated through coupled catalytic loops. The double protection aims to enhance the chemical stability of the diboronate probes while preserving their ability to undergo autocatalytic deprotection. Through kinetic modeling and experimental validation, we demonstrate that complete deprotection to the corresponding quinones can occur even under substoichiometric H2O2 conditions, thereby sustaining autocatalytic behavior. Comparative studies of symmetric and asymmetric diboronate probes reveal how molecular structure and electronic effects control the kinetics of each deprotection step and so the overall amplification efficiency. Finally, we show that these doubly protected systems enable efficient responses to H2O2 across more than two orders of magnitude in concentration (from µM to sub-millimolar range) and within minutes, while providing improved probe stability and tunable reactivity. This work offers mechanistic insights and design principles for next-generation autocatalytic redox amplification systems with enhanced analytical performance.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70042","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148097293","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}

引用次数: 0

Oligomerization of Non-Activated Nucleotides Under Hot Acidic Wet–Dry Cycling Without Catalytic Agents 无催化剂的热酸性干湿循环条件下非活化核苷酸的寡聚反应

IF 3.1

ChemSystemsChem Pub Date : 2026-05-29 DOI: 10.1002/syst.70043

Simon H. J. Eiby, Morten J. Bjerrum, Bálint Hajdu, Laura Da Silva, Peter W. Thulstrup, Tue Hassenkam

{"title":"Oligomerization of Non-Activated Nucleotides Under Hot Acidic Wet–Dry Cycling Without Catalytic Agents","authors":"Simon H. J. Eiby, Morten J. Bjerrum, Bálint Hajdu, Laura Da Silva, Peter W. Thulstrup, Tue Hassenkam","doi":"10.1002/syst.70043","DOIUrl":"https://doi.org/10.1002/syst.70043","url":null,"abstract":"The emergence of genetic polymers such as RNA and DNA from prebiotically available building blocks represents a key step toward the origin of life. Nucleotides, the building blocks of RNA and DNA, may have existed on the prebiotic Earth, but their oligomerization is energetically unfavorable in aqueous solution. Consequently, chemically activated nucleotides and/or catalytic agents have typically been invoked. The extent of oligomerization of non-activated nucleotides is sensitive to experimental subtleties, and detection uncertainties and potential artefacts complicate its interpretation. Further clarification is therefore required. Here, we present experimental evidence for the oligomerization of non-activated RNA and DNA nucleotides in hot, acidic wet-dry cycling environments, resembling a simplified model of geothermal pools on the prebiotic Earth. No catalytic agents were added, and pH was naturally buffered by the nucleotides, minimizing external interferences. The resulting oligonucleotides were short (≤4 nt), with yields up to ∼3%. While previous studies under similar conditions usually employ catalytic agents such as minerals, lipids, or salts, our findings demonstrate that phosphodiester bonds form in their absence. However, generating and sustaining long, genetically capable polymers in acidic hot wet-dry cycling environments remains challenging.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"8 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.70043","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148097292","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}

引用次数: 0