Artificial Homeostasis Systems Based on Feedback Reaction Networks: Design Principles and Future Promises

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Jan. 16, 2024

Abstract Feedback‐controlled chemical reaction networks (FCRNs) are indispensable for various biological processes, such as cellular mechanisms, patterns, and signaling pathways. Through the intricate interplay of many feedback loops (FLs), FCRNs maintain a stable internal environment. Currently, creating minimalistic synthetic cells is long‐term objective systems chemistry, which motivated by natural integrity. The design, kinetic optimization, analysis to exhibit functions akin those cell still pose significant challenges. Indeed, reaching homeostasis essential engineering components. However, maintaining in artificial against agitations difficult task. Several events can provide us with guidelines conceptual understanding homeostasis, be further applicable designing systems. In this regard, we organize our review driven at different length scales, including homogeneous, compartmentalized, soft material First, stretch quick overview molecular supramolecular systems, toolbox nonlinear homeostatic Moreover, existing history their advanced self‐correcting, regulating properties also emphasized.

Language: Английский

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Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(26)

Published: March 8, 2022

This work reports that the composition of a dynamic library (DL) interconverting imines can be controlled over time in dissipative fashion by addition an activated carboxylic acid used as chemical fuel. When fuel is added to DL, which initially under thermodynamic equilibrium, mixture dramatically changes and new, (out equilibrium) state reached persists until exhaustion. Thus, transient (DDL) generated that, eventually, reverts back initial DL when consumed, closing DL→DDL→DL cycle. The larger amount fuel, longer spent system DDL state. transimination reaction shown optimal candidate for realization covalent chemistry (DDCvC).

Language: Английский

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Evolution at the Origins of Life?

Life, Journal Year: 2024, Volume and Issue: 14(2), P. 175 - 175

Published: Jan. 24, 2024

The role of evolutionary theory at the origin life is an extensively debated topic. and early development usually separated into a prebiotic phase protocellular phase, ultimately leading to Last Universal Common Ancestor. Most likely, Ancestor was subject Darwinian evolution, but question remains what extent evolution applies phases. In this review, we reflect on current status in origins research by bringing together philosophy science, biology, empirical field. We explore various ways which has been extended beyond biology; look how these extensions apply (proto)metabolism; investigate terminology from currently being employed state-of-the-art research. doing so, identify some obstacles account life, as well open up new avenues

Language: Английский

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Light, Switch, Action! The Influence of Geometrical Photoisomerization in an Adaptive Self-Assembled System

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31892 - 31900

Published: Nov. 5, 2024

The ubiquitous ability of natural dynamic nanostructures to adapt environmental changes is a highly desirable property for chemical systems, particularly in the development complex matter, molecular machines, and life-like materials. Designing such systems challenging due generation mixtures with responses that are difficult predict, characterize, diversify. Here, we navigate between self-assembled architectures using light by operating an intrinsic photoswitchable building block governs state system. When complementary units present, photoswitch determines predominant architecture, reversibly adapting cage macrocycles, including (otherwise inaccessible) higher-energy assemblies. Our study showcases this concept seven different transformations, offering unprecedented degree control, diversification, adaptation self-selecting units. These findings could enable applications on-demand dissipative macrocycles based on bonds. We also envision transient nanostructures, e.g., reticular polymeric materials, being explored fine-tuning nature unit.

Language: Английский

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Cell-size space effects on phase separation of binary polymer blends

Biophysical Reviews, Journal Year: 2022, Volume and Issue: 14(5), P. 1093 - 1103

Published: Oct. 1, 2022

Abstract Within living cells, a diverse array of biomolecules is present at high concentrations. To better understand how molecular behavior differs under such conditions (collectively described as macromolecular crowding), the crowding environment has been reproduced inside artificial cells. We have previously shown that combination and microscale geometries imposed by cells can alter behaviors induced in bulk solutions. named effect makes difference cell-size space (CSE). Here, we review underlying biophysics CSE for phase separation binary polymer blends. discuss initiate separation, unlike nano-sized spaces, which are known to hinder nucleation separation. Additionally, dimensions cell its membrane characteristics significantly impact dynamics equilibrium composition. Although these findings are, themselves, very interesting, their real significance may lie helping clarify functions size regulation intracellular

Language: Английский

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Temporal (Dis)Assembly of Peptide Nanostructures Dictated by Native Multistep Catalytic Transformations

Nano Letters, Journal Year: 2024, Volume and Issue: 24(7), P. 2250 - 2256

Published: Feb. 8, 2024

Emergence of complex catalytic machinery via simple building blocks under non-equilibrium conditions can contribute toward the system level understanding extant biocatalytic reaction network that fuels metabolism. Herein, we report temporal (dis)assembly peptide nanostructures in presence a cofactor dictated by native multistep cascade transformations. The short form dynamic covalent bond with thermodynamically activated substrate and recruit hemin to access (positive feedback). neighboring imidazole moieties assembled state rapidly converted product(s) two-step (hydrolase-peroxidase like) subsequently triggered disassembly (negative feedback coupled cycle involving intrinsic prowess peptides realize advanced trait two-stage degradation foreshadows protometabolic networks might have preceded chemical emergence life.

Language: Английский

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Binding of Precursors to Replicator Assemblies Can Improve Replication Fidelity and Mediate Error Correction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 21, 2024

Abstract Copying information is vital for life‘s propagation. Current life forms maintain a low error rate in replication, using complex machinery to prevent and correct errors. However, primitive had deal with higher rates, limiting its ability evolve. Discovering mechanisms reduce errors would alleviate this constraint. Here, we introduce new mechanism that decreases rates corrects synthetic self‐replicating systems driven by self‐assembly. Previous work showed macrocycle replication occurs through the accumulation of precursor material on sides fibrous replicator assemblies. Stochastic simulations now reveal selective binding fiber surface enhances fidelity correction. Centrifugation experiments show fibers can exhibit necessary selectivity binding. Our results suggest are more evolvable than previously thought, encouraging further evolution‐focused experiments.

Language: Английский

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Spontaneous Curvature Induction in an Artificial Bilayer Membrane

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 9, 2024

Abstract Maintaining lipid asymmetry across membrane leaflets is critical for functions like vesicular traffic and organelle homeostasis. However, a lack of molecular‐level understanding the mechanisms underlying fission fusion processes in synthetic systems precludes their development as artificial analogs. Here, we report induction bilayer formed by an extended π‐conjugated molecule with oxyalkylene side chains bearing terminal tertiary amine moieties ( BA1 ) water. Autogenous protonation amines periphery water induces anisotropic curvature, resulting to form vesicles can be monitored using time‐dependent spectroscopy microscopy. Interestingly, upon loss induced extensive organic acid restored membrane. The mechanism leading compositional leaflet curvature validated density functional theory (DFT) calculations. Studies control molecules having changes hydrophilic BA2 hydrophobic BA3 segments provide insight into delicate nature molecular scale interactions dynamic transformation supramolecular structures. synergic effect interaction hydrated state aggregates dynamicity unusual stability. Our study unveils mechanistic membranes vesicles.

Language: Английский

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Bistable Functions and Signaling Motifs in Systems Chemistry: Taking the Next Step Toward Synthetic Cells

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

ConspectusA key challenge in modern chemistry research is to mimic life-like functions using simple molecular networks and the integration of such into first functional artificial cell. Central this endeavor development signaling elements that can regulate cell function time space by producing entities code with specific information induce downstream activity. Such motifs emerge nonequilibrium systems, exhibiting complex dynamic behavior like bistability, multistability, oscillations, chaos. However, de novo, bottom-up design systems remains challenging, primarily because kinetic characteristics energy aspects yielding bifurcation have not yet been globally defined. We herein review our recent work focuses on analysis peptide-based networks, propelled replication reactions bistable behavior. Furthermore, we rationalize discuss their exploitation implementation as variable homogeneous heterogeneous environments.The constitute reversible second-order autocatalysis positive feedback generate two distinct product distributions at steady state (SS), low-SS high-SS. Quantitative analyses reveal a phase transition from equilibration dynamics bistability takes place when system continuously fueled, reducing agent, keep it far equilibrium. In addition, an extensive set experimental, theoretical, simulation studies highlight defined parameter where operates.Analogous arrangement protein-based intracellular pathways, sequential concatenation synthetic used for signal processing media. The cascaded network output signals are switched erased or transduced manipulating order addition components, allowing reach "on demand" either pre-encoded also useful programming tool regulation nanoscale materials properties, bridging together Systems Chemistry Nanotechnology fields. cascade outputs serve input consecutive nanoparticle formation reaction growth processes, which–depending applied conditions–regulate various features (Au) shape assembly.Our enables production apparatus feature higher complexity than previously observed chemical networks. Future studies, briefly discussed end Account, will be directed more elaborate functionality, under flow conditions, oscillations. propose profound understanding principles facilitating replication-based related bear implications exploring origin protein functionality prior highly evolved replication–translation–transcription machinery. within future cells seems straightforward alternating states memory switch controlling division even communication among different cells. furthermore suggest introduced living biotechnology applications, switches temporal spatial manipulations.

Language: Английский

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Solvent-mediated subcomponent self-assembly of covalent metallacycles for hierarchical porous materials synthesis

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A solvent-mediated subcomponent self-assembly strategy was developed for synthesizing covalent metallacycles with different shapes.

Language: Английский

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