Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 3, 2024

Abstract Over the last two decades ratchet mechanisms have transformed understanding and design of stochastic molecular systems—biological, chemical physical—in a move away from mechanical macroscopic analogies that dominated thinking regarding dynamics in 1990s early 2000s (e.g. pistons, springs, etc), to more scale‐relevant concepts underpin out‐of‐equilibrium research sciences today. Ratcheting has established nanotechnology as frontier for energy transduction metabolism, enabled reverse engineering biomolecular machinery, delivering insights into how molecules ‘walk’ track‐based synthesisers operate, acceleration reactions enables be transduced by catalysts (both motor proteins synthetic catalysts), dynamic systems can driven equilibrium through catalysis. The recognition biology, their invention systems, is proving significant areas diverse supramolecular chemistry, covalent DNA nanotechnology, polymer materials science, heterogeneous catalysis, endergonic synthesis, origin life, many other branches science. Put simply, give chemistry direction. Kinetic asymmetry, key feature ratcheting, counterpart structural asymmetry (i.e. chirality). Given ubiquity processes significance behaviour function it surely just fundamentally important. This Review charts recognition, development ratchets, focussing particularly on role which they were originally envisaged elements machinery. Different kinetically asymmetric are compared, consequences discussed. These archetypal examples demonstrate inexorably equilibrium, rather than relax towards it.

Language: Английский

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Self-assembly of stabilized droplets from liquid–liquid phase separation for higher-order structures and functions

Communications Chemistry, Journal Year: 2024, Volume and Issue: 7(1)

Published: April 9, 2024

Dynamic microscale droplets produced by liquid-liquid phase separation (LLPS) have emerged as appealing biomaterials due to their remarkable features. However, the instability of limits construction population-level structures with collective behaviors. Here we first provide a brief background in context materials properties. Subsequently, discuss current strategies for stabilizing including physical and chemical modulation. We also recent development LLPS various applications such synthetic cells biomedical materials. Finally, give insights on how stabilized can self-assemble into higher-order displaying coordinated functions fully exploit potentials bottom-up biology applications.

Language: Английский

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Controlled Supramolecular Polymerization via Bioinspired, Liquid–Liquid Phase Separation of Monomers

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12577 - 12586

Published: April 29, 2024

Dynamic supramolecular assemblies, driven by noncovalent interactions, pervade the biological realm. In synthetic domain, their counterparts, polymers, endowed with remarkable self-repair and adaptive traits, are often realized through bioinspired designs. Recently, controlled polymerization strategies have emerged, drawing inspiration from protein self-assembly. A burgeoning area of research involves mimicking liquid–liquid phase separation (LLPS) observed in proteins to create coacervate droplets recognizing significance cellular organization diverse functions. Herein, we introduce a novel perspective on coacervates, extending beyond established role biology as dynamic, membraneless phases enable structural control polymers. Drawing parallels cooperative growth amyloid fibrils LLPS, present metastable dormant monomer for polymerization. This is achieved via π-conjugated design that combines characteristics both coacervation its terminal ionic groups one-dimensional core. leads unique temporal resulting phase, which subsequently undergoes nucleation within droplets. In-depth spectroscopic microscopic characterization provides insights into evolution disordered ordered phases. Furthermore, modulate kinetics liquid-to-solid transformation achieve precise over invoke seeding droplets, showcasing living characteristics. Our work thus opens up new avenues exciting field polymerization, offering general principles synthesis precision self-assembled structures confined environments.

Language: Английский

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Droplet Physics and Intracellular Phase Separation

Annual Review of Condensed Matter Physics, Journal Year: 2023, Volume and Issue: 15(1), P. 237 - 261

Published: Dec. 7, 2023

Living cells are spatially organized by compartments that can nucleate, grow, and dissolve. Compartmentalization emerge phase separation, leading to the formation of droplets in cell's nucleo- or cytoplasm, also called biomolecular condensates. Such organize biochemistry cell providing specific chemical environments space time. These provide transient environments, suggesting relevance nonequilibrium physics as a key unraveling underlying physicochemical principles biological functions living cells. In this review, we highlight coarse-grained approaches capture chemically active emulsions model for condensates orchestrating processes. We discuss dynamics single molecules material properties their cell. Finally, propose wetting, prewetting, surface transitions possibility intracellular surfaces control condensates, membranes, exert mechanical forces.

Language: Английский

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Tuning interfacial fluidity and colloidal stability of membranized coacervate protocells

Communications Chemistry, Journal Year: 2024, Volume and Issue: 7(1)

Published: June 3, 2024

Abstract The cell membrane not only serves as the boundary between cell’s interior and external environment but also plays a crucial role in regulating fundamental cellular behaviours. Interfacial membranization of membraneless coacervates, formed through liquid-liquid phase separation (LLPS), represents reliable approach to constructing hierarchical cell-like entities known protocells. In this study, we demonstrate capability modulate interfacial fluidity thickness dextran-bound coacervate protocells by adjusting molecular weight dextran or utilizing dextranase-catalyzed hydrolysis. This modulation allows for rational control over colloidal stability, transport cell-protocell interactions. Our work opens new avenue surface engineering protocells, enabling establishment cell-mimicking structures

Language: Английский

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Reaction-Driven Diffusiophoresis of Liquid Condensates: Potential Mechanisms for Intracellular Organization

ACS Nano, Journal Year: 2024, Volume and Issue: 18(26), P. 16530 - 16544

Published: June 14, 2024

The cellular environment, characterized by its intricate composition and spatial organization, hosts a variety of organelles, ranging from membrane-bound ones to membraneless structures that are formed through liquid–liquid phase separation. Cells show precise control over the position such condensates. We demonstrate organelle movement in external concentration gradients, diffusiophoresis, is distinct one colloids because fluxes can remain finite inside liquid-phase droplets latter arises incompressibility. Within domains diffusiophoresis naturally biochemical reactions driven chemical fuel produce waste. Simulations analytical arguments within minimal model reaction-driven separation reveal directed stems two contributions: Fuel waste refilled or extracted at boundary, resulting which (i) induce product via incompressibility (ii) result an asymmetric forward reaction droplet's surroundings (as well as backward droplet), thereby shifting position. former contribution dominates sets direction movement, toward away source sink, depending on molecules' affinity waste, respectively. mechanism thus provides simple means organize condensates with different composition. Particle-based simulations systems more complex cycles corroborate robustness universality this mechanism.

Language: Английский

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Progressive Endergonic Synthesis of Diels–Alder Adducts Driven by Chemical Energy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 17, 2024

The overwhelming majority of artificial chemical reaction networks respond to stimuli by relaxing towards an equilibrium state. opposite response-moving away from equilibrium-can afford the endergonic synthesis molecules, which only rare examples have been reported. Here, we report six Diels-Alder adducts formed in process and use this strategy realize their stepwise accumulation. Indeed, systems repeated occurrences same stimulus increasing amount adduct formed, with final network distribution depending on number received. Our findings indicate how processes can contribute transition responsive adaptive systems.

Language: Английский

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Charge separation at liquid interfaces

Physical Review Research, Journal Year: 2024, Volume and Issue: 6(3)

Published: Aug. 5, 2024

We present a theory for phase-separated liquid coacervates with salt, taking into account spatial heterogeneities and interfacial profiles. find that charged layers of alternating sign can form around the interface while bulk phases remain approximately charge neutral. show salt concentration regulates number amplitude layer's density electrostatic potential. Such either repel or attract single-charged molecules diffusing across interface. Our could be relevant artificial systems biomolecular condensates in cells. work suggests interfaces mediate charge-specific transport similar to membrane-bound compartments. Published by American Physical Society 2024

Language: Английский

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Pumping Small Molecules Selectively through an Energy-Assisted Assembling Process at Nonequilibrium States

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3323 - 3330

Published: Jan. 26, 2024

In living organisms, precise control over the spatial and temporal distribution of molecules, including pheromones, is crucial. This level equally important for development artificial active materials. this study, we successfully controlled small molecules in system at nonequilibrium states by actively transporting them, even against apparent concentration gradient, with high selectivity. As a demonstration, aqueous solution acid orange (AO7) TMC

Language: Английский

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Bursting of condensates

Communications Physics, Journal Year: 2024, Volume and Issue: 7(1)

Published: May 17, 2024

Abstract Numerous biomolecular shell-forming condensates are reported in cells and bioengineered vitro. The relationship between the molecular structure of their biophysical properties remains largely unexplored. To fill this gap, we characterize spider silk proteins based on Araneus diadematus major ampulla gland fibroin 3 (ADF3) using micropipette aspiration. We observe that can burst during aspiration like soap bubbles or polymersomes, demonstrating formation a dense protein layer (shell) at condensate interface. tendency to is more pronounced for formed from with weakly dimerizing terminal blocks. develop model analyse bursting condensates, obtain surface bulk viscosity, estimate shell thickness viscosity. Understanding controlling will open avenues use materials, as compartments reactions drug delivery systems.

Language: Английский

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