ChemSystemsChem最新文献_第2页

The Role of Kinetic Asymmetry in Chemical and Thermodynamic Coupling

IF 3.1

ChemSystemsChem Pub Date : 2024-10-15 DOI: 10.1002/syst.202400066

R. Dean Astumian

引用次数: 0

A Pseudo-catalytic Network Motif for Thiol-based Chemical Reaction Networks

IF 3.1

ChemSystemsChem Pub Date : 2024-10-14 DOI: 10.1002/syst.202400072

Ekaterina A. Zhigileva, Ilia A. Puchkin, Sergey N. Semenov

{"title":"A Pseudo-catalytic Network Motif for Thiol-based Chemical Reaction Networks","authors":"Ekaterina A. Zhigileva, Ilia A. Puchkin, Sergey N. Semenov","doi":"10.1002/syst.202400072","DOIUrl":"https://doi.org/10.1002/syst.202400072","url":null,"abstract":"The construction of chemical reaction networks (CRNs) is a formidable challenge because of their holistic and nonlinear nature. One approach to constructing CRNs involves combining fragments with distinctive properties, known as network motifs. Thiol chemistry is widely used in the construction of CRNs, with motifs available for positive and negative feedback loops. However, a simple catalytic motif has been lacking. Here, we developed a pseudo-catalytic motif using the reaction between cystamine and organic thiocyanates, which operates through a nucleophilic chain mechanism. Although similar to thiol autocatalytic systems, this reaction does not involve a doubling of the number of thiol species at any stage. The reaction is high-yielding and produces 2-amino-2-thiazoline. Its pseudo-catalytic nature manifests itself in the nearly linear relationship between the reaction rate and the amount of free thiols added at the beginning of the reaction. We demonstrated that this reaction can be regulated by external, time-dependent thiol signals and integrated into larger CRNs. We believe that this system will be a valuable addition to thiol chemistry, enabling the construction of CRNs with interesting functionalities.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"7 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400072","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629916","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

Charge-Mediated Interactions Affect Enzymatic Reactions in Peptide Condensates

IF 3.1

ChemSystemsChem Pub Date : 2024-10-04 DOI: 10.1002/syst.202400055

Rif Harris, Nofar Berman, Ayala Lampel

{"title":"Charge-Mediated Interactions Affect Enzymatic Reactions in Peptide Condensates","authors":"Rif Harris, Nofar Berman, Ayala Lampel","doi":"10.1002/syst.202400055","DOIUrl":"https://doi.org/10.1002/syst.202400055","url":null,"abstract":"Biomolecular condensates, formed through liquid-liquid phase separation (LLPS), serve as enzymatic reaction centers in cells by increasing local concentrations of enzymes and substrates, thereby facilitating reaction kinetics and regulatory mechanisms. Inspired by these natural systems, synthetic condensates are being developed for diverse applications, including payload delivery, sensing, and as microreactors where enzymatic reaction kinetics can be modulated by factors like pH, viscosity, and enzyme-substrate co-localization. Here, we investigate how the physicochemical properties of enzymes and substrates influence condensate formation and function as microreactors. Focusing on cellulase and alkaline phosphatase, which differ in molecular weight and isoelectric point, we employed a minimalistic complex coacervation system of oppositely charged LLPS-promoting peptides. Our findings show how electrostatic forces within condensates influence their role as microreactors. Specifically, the ability of condensates to encapsulate or exclude phosphatase, cellulase, and their substrates, which is pivotal for the regulation of reaction kinetics, is determined by the enzyme surface charge, substrate charge, and condensate charge stoichiometry. These results highlight the potential of utilizing electrostatic forces within condensates to modulate enzymatic reactions, providing critical insights for developing synthetic condensates as microreactors in biotechnology and materials science.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"7 1","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400055","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143111993","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

Empowering Chemical AI Through Systems Chemistry 通过系统化学提高化学人工智能的能力

IF 3.1

ChemSystemsChem Pub Date : 2024-09-19 DOI: 10.1002/syst.202400054

Prof. Pier Luigi Gentili, Prof. Pasquale Stano

引用次数: 0

Prebiotic Environmental Conditions Impact the Type of Iron-Sulfur Cluster Formed

IF 3.1

ChemSystemsChem Pub Date : 2024-09-18 DOI: 10.1002/syst.202400051

Luca Valer, Yin Juan Hu, Alberto Cini, Marco Lantieri, Craig R. Walton, Oliver Shorttle, Maria Fittipaldi, Sheref S. Mansy

{"title":"Prebiotic Environmental Conditions Impact the Type of Iron-Sulfur Cluster Formed","authors":"Luca Valer, Yin Juan Hu, Alberto Cini, Marco Lantieri, Craig R. Walton, Oliver Shorttle, Maria Fittipaldi, Sheref S. Mansy","doi":"10.1002/syst.202400051","DOIUrl":"https://doi.org/10.1002/syst.202400051","url":null,"abstract":"Iron-sulfur clusters are ancient cofactors that could have played a role in the prebiotic chemistry leading to the emergence of protometabolism. Previous research has shown that certain iron-sulfur clusters can form from prebiotically plausible components, such as cysteine-containing oligopeptides. However, it is unclear if these iron-sulfur clusters could have survived in prebiotically plausible environments. To begin exploring this possibility, we tested the stability of iron-sulfur clusters coordinated to a tripeptide and to N-acetyl-L-cysteine methyl ester in a variety of solutions meant to mimic prebiotically plausible environments. We also assessed the impact of individual chemical components on stability. We find that iron-sulfur clusters form over a wide variety of conditions but that the type of iron-sulfur cluster formed is strongly impacted by the chemical environment and the coordinating scaffold. These findings support the general hypothesis that iron-sulfur clusters were present on the prebiotic Earth and that different types of iron-sulfur cluster predominated in different environments.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"7 1","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400051","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143116266","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

Front Cover: Effect of Temperature on Calcium-Based Chemical Garden Growth (ChemSystemsChem 5/2024) 封面：温度对钙基化学花园生长的影响（ChemSystemsChem 5/2024）

IF 3.1

ChemSystemsChem Pub Date : 2024-09-13 DOI: 10.1002/syst.202480501

Dr. Pamela Knoll, Dr. Corentin C. Loron

引用次数: 0

Oscillations of the Local pH Reverses Silver Micromotors in H2O2 局部 pH 值的振荡可逆转 H2O2 中的银微电机

IF 3.1

ChemSystemsChem Pub Date : 2024-09-09 DOI: 10.1002/syst.202400046

Xianghong Liu, Yixin Peng, Zuyao Yan, Dezhou Cao, Shifang Duan, Wei Wang

{"title":"Oscillations of the Local pH Reverses Silver Micromotors in H2O2","authors":"Xianghong Liu, Yixin Peng, Zuyao Yan, Dezhou Cao, Shifang Duan, Wei Wang","doi":"10.1002/syst.202400046","DOIUrl":"https://doi.org/10.1002/syst.202400046","url":null,"abstract":"Asymmetric chemical reactions on the surfaces of colloidal particles are known to propel them into directional motion. The dynamics of such chemical micromotors are sensitive to their local chemical environments, which also continually evolve with the reactions on motor surfaces. This two-way coupling between the motor dynamics and the local environment may result in complex nonlinear behaviors. As an example, we report that Janus Ag microspheres, which self-propel in hydrogen peroxide (H2O2), spontaneously reverse their direction of motion two or more times. We hypothesize that two distinct chemical reactions between Ag and H2O2 drive the micromotor in opposite directions, and which reaction dominates depends on the local pH. Interestingly, the local pH near a Ag micromotor oscillates spontaneously in H2O2, likely due to a complex interplay between the kinetics of the reaction between Ag and H2O2 and the diffusion of chemical species. Consequently, the pH-sensitive Ag micromotor reverses its direction of motion in response to these pH oscillations. This study introduces a new mechanism for regulating the speed and directionality of micromotors, highlights the potential of Ag micromotors in chemical sensing, and sheds new light on the interplay between chemical kinetics and micromotor dynamics.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"6 6","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665742","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

Transport-Limited Growth of Flow-Driven Rare-Earth Silicate Tubes 流动驱动的稀土硅酸盐管的传输限制生长

IF 3.1

ChemSystemsChem Pub Date : 2024-09-04 DOI: 10.1002/syst.202400053

Panna E. Farkas, Emese Lantos, Dezső Horváth, Agota Tóth

引用次数: 0

Performance Comparison of Traditional, Nanopolymerized, and Entangled Belousov−Zhabotinsky Self-Oscillating Gels

IF 3.1

ChemSystemsChem Pub Date : 2024-08-26 DOI: 10.1002/syst.202400060

Zhenfang Cheng, Ling Yuan, Hui Wang, Haodi Yu, Meng Zhang, Irving R Epstein, Tan Gao, Lin Ren, Qingyu Gao

{"title":"Performance Comparison of Traditional, Nanopolymerized, and Entangled Belousov−Zhabotinsky Self-Oscillating Gels","authors":"Zhenfang Cheng, Ling Yuan, Hui Wang, Haodi Yu, Meng Zhang, Irving R Epstein, Tan Gao, Lin Ren, Qingyu Gao","doi":"10.1002/syst.202400060","DOIUrl":"https://doi.org/10.1002/syst.202400060","url":null,"abstract":"Belousov−Zhabotinsky (BZ) self-oscillating gels exhibit periodic volumetric swelling−deswelling, providing the basis for autonomous soft robots without external control. However, traditional BZ self-oscillating gels suffer from degradation and slow chemo−mechanical response. Here, three types of BZ self-oscillating gels were prepared by adjusting the monomer/crosslinker ratio and using N-isopropylacrylamide nanogels as crosslinker. Compared with traditional gels, the toughness of nanopolymerized and entangled gels was markedly improved and their response to the Ru (III)/Ru (II) alternation was accelerated. The three self-oscillating gels showed different periodic responses in a BZ reaction solution. Entangled gels, as a result of their greater spatial uniformity in energy dissipation and enhanced interconnection between mesopores, respectively, showed the longest lifetime and shortest chemo-mechanical oscillation delay. The synthesis of tougher and faster responding entangled gels expands the function and application of BZ self-oscillating gels.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"7 1","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143119445","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

Phase-Separated Droplets Can Direct the Kinetics of Chemical Reactions Including Polymerization, Self-Replication and Oscillating Networks

IF 3.1

ChemSystemsChem Pub Date : 2024-08-21 DOI: 10.1002/syst.202400056

Iris B. A. Smokers, Brent S. Visser, Dr. Wojciech P. Lipiński, Dr. Karina K. Nakashima, Dr. Evan Spruijt

{"title":"Phase-Separated Droplets Can Direct the Kinetics of Chemical Reactions Including Polymerization, Self-Replication and Oscillating Networks","authors":"Iris B. A. Smokers, Brent S. Visser, Dr. Wojciech P. Lipiński, Dr. Karina K. Nakashima, Dr. Evan Spruijt","doi":"10.1002/syst.202400056","DOIUrl":"https://doi.org/10.1002/syst.202400056","url":null,"abstract":"Phase-separated compartments can localize (bio)chemical reactions and influence their kinetics. They are believed to play an important role both in extant life in the form of biomolecular condensates and at the origins of life as coacervate protocells. However, experimentally testing the influence of coacervates on different reactions is challenging and time-consuming. We therefore use a numerical model to explore the effect of phase-separated droplets on the kinetics and outcome of different chemical reaction systems, where we vary the coacervate volume and partitioning of reactants. We find that the rate of bimolecular reactions has an optimal dilute/coacervate phase volume ratio for a given reactant partitioning. Furthermore, coacervates can accelerate polymerization and self-replication reactions and lead to formation of longer polymers. Lastly, we find that coacervates can ‘rescue’ oscillating reaction networks in concentration regimes where sustained oscillations do not occur in a single-phase system. Our results indicate that coacervates can direct the outcome of a wide range of reactions and impact fundamental aspects such as yield, reaction pathway selection, product length and emergent functions. This may have far-reaching implications for origins of life, synthetic cells and the fate and function of biological condensates.","PeriodicalId":72566,"journal":{"name":"ChemSystemsChem","volume":"7 1","pages":""},"PeriodicalIF":3.1,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/syst.202400056","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143117525","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