Non-equilibrium Steady States in Catalysis, Molecular Motors, and Supramolecular Materials: Why Networks and Language Matter

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14169 - 14183

Published: June 21, 2023

All chemists are familiar with the idea that, at equilibrium steady state, relative concentrations of species present in a system predicted by corresponding constants, which related to free energy differences between components. There is also no net flux species, matter how complicated reaction network. Achieving and harnessing non-equilibrium states, coupling network second spontaneous chemical process, has been subject work several disciplines, including operation molecular motors, assembly supramolecular materials, strategies enantioselective catalysis. We juxtapose these linked fields highlight their common features challenges as well some misconceptions that may be serving stymie progress.

Language: Английский

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Active Colloids as Models, Materials, and Machines

Annual Review of Chemical and Biomolecular Engineering, Journal Year: 2023, Volume and Issue: 14(1), P. 1 - 30

Published: March 17, 2023

Active colloids use energy input at the particle level to propel persistent motion and direct dynamic assemblies. We consider three types of animated by chemical reactions, time-varying magnetic fields, electric currents. For each type, we review basic propulsion mechanisms discuss their consequences for collective behaviors in ensembles. These microscopic systems provide useful experimental models nonequilibrium many-body physics which dissipative currents break time-reversal symmetry. Freed from constraints thermodynamic equilibrium, active assemble form materials that move, reconfigure, heal, adapt. Colloidal machines based on engineered particles assemblies a basis mobile robots with increasing levels autonomy. This provides conceptual framework understanding applying create material mimic functions living matter. highlight opportunities engineers contribute this growing field.

Language: Английский

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Liquid spherical shells are a non-equilibrium steady state of active droplets

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 17, 2023

Liquid-liquid phase separation yields spherical droplets that eventually coarsen to one large, stable droplet governed by the principle of minimal free energy. In chemically fueled separation, formation phase-separating molecules is coupled a fuel-driven, non-equilibrium reaction cycle. It thus dissipative structures sustained continuous fuel conversion. Such are ubiquitous in biology but poorly understood as they thermodynamics. Here, we bridge gap between passive, close-to-equilibrium, and active, with separation. We observe spherical, active can undergo morphological transition into liquid, shell. demonstrate mechanism related gradients short-lived material. characterize how far out equilibrium shell state chemical power necessary sustain it. Our work suggests alternative avenues for assembling complex morphologies, which might already be exploited form membraneless organelles cells.

Language: Английский

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Supramolecular gels – a panorama of low-molecular-weight gelators from ancient origins to next-generation technologies

Soft Matter, Journal Year: 2023, Volume and Issue: 20(1), P. 10 - 70

Published: Dec. 11, 2023

Supramolecular gels, self-assembled from low-molecular-weight gelators (LMWGs), have a long history and bright future.

Language: Английский

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Chemically Fueled Supramolecular Materials

Accounts of Materials Research, Journal Year: 2023, Volume and Issue: 4(5), P. 416 - 426

Published: April 14, 2023

In biology, the function of many molecules is regulated through nonequilibrium chemical reaction cycles. The prototypical example phosphorylation an amino acid in enzyme which induces a functional change, e.g., it folds or unfolds, assembles disassembles, binds substrate. Such does not occur spontaneously but requires phosphorylating agent with high potential (for example, adenosine triphosphate (ATP)) to be converted into molecule lower (adenosine diphosphate (ADP)). When this energy used regulate assembly, we speak chemically fueled assemblies; i.e., potential, fuel, self-assembly process. For binding guanosine (GTP) tubulin self-assembly. bound GTP hydrolyzed (GDP) upon disassembly. result dynamic assembly endowed unique characteristics, such as time-dependent behavior and ability self-heal. These intriguing, properties have inspired supramolecular chemists create similar molecular assemblies from bottom up. While examples been designed, they remain scarce partly because cycles are rare often complex. Thus, recently developed carbodiimide-driven cycle that versatile easy use, quantitatively understood, suffer side reactions. cycle, carboxylate precursor reacts carbodiimide form activated species like anhydride ester. state water thereby reverts its state; deactivated. Effectively, catalyzes carbodiimides' conversion waste forms transient state. We designed building blocks range materials at expense fuel. simplicity versatility democratized popularized field assemblies. Account, describe what "learned" on our way. introduce exemplified by biological design cycle. Using group others, offer rules for block's structure strategies desired morphology materials. discussed morphologies include fibers, colloids, crystals, oil- coacervate-based droplets. then demonstrate how these material Besides, discuss concept reciprocal coupling exerts feedback also mechanisms. Finally, close Account discussion outlook field. This aims provide fundamental understanding facilitate further progress toward conceptually new

Language: Английский

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Dynamic Near‐Infrared Circularly Polarized Luminescence Encoded by Transient Supramolecular Chiral Assemblies

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 13, 2024

Abstract Circularly polarized luminescence (CPL) is promising for applications in many fields. However, most systems involving CPL are within the visible range; near‐infrared (NIR) CPL‐active materials, especially those that exhibit high g lum values and can be controlled spatially temporally, rare. Herein, dynamic NIR‐CPL with a value of 2.5×10 −2 was achieved through supramolecular coassembly energy‐transfer strategies. The chiral assemblies formed by between adenosine triphosphate (ATP) pyrene derivative exhibited red signal ( 10 −3 ). further introduction sulfo‐cyanine5 resulted process, which not only led to NIR but also increased . Temporal control these realized introducing alkaline phosphatase fabricate biomimetic enzyme‐catalyzed network, allowing turned on. Based on enzyme‐regulated temporally controllable assemblies, multilevel information encryption system developed. This study provides pioneering example construction materials ability perform temporal via assembly strategy, expected aid design complex more closely resemble natural biological systems.

Language: Английский

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pH-feedback systems to program autonomous self-assembly and material lifecycles

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(9), P. 1125 - 1144

Published: Jan. 1, 2023

We highlight the development of pH-feedback systems which can be coupled to diverse pH-switchable building blocks achieve transient self-assemblies and materials with programmable temporal behavior autonomous lifecycles.

Language: Английский

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Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Aug. 7, 2023

Abstract Non‐equilibrium chemical systems underpin multiple domains of contemporary interest, including supramolecular chemistry, molecular machines, prebiotic and energy transduction. Experimental chemists are now pioneering the realization artificial that can harvest away from equilibrium. In this tutorial Review, we provide an overview ratchets: mechanisms enabling absorption environment. By focusing on mechanism type—rather than application domain or source—we offer a unifying picture seemingly disparate phenomena, which hope will foster progress in fascinating science.

Language: Английский

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Dynamic covalent synthesis

Chemical Science, Journal Year: 2023, Volume and Issue: 15(3), P. 879 - 895

Published: Dec. 11, 2023

Dynamic covalent synthesis aims to precisely control the assembly of simple building blocks linked by reversible bonds generate a single, structurally complex, product. In recent years, considerable progress in programmability dynamic systems has enabled easy access broad range assemblies, including macrocycles, shape-persistent cages, unconventional foldamers and mechanically-interlocked species (catenanes, knots,

Language: Английский

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Pillararene-Based Supramolecular Polymers for Cancer Therapy

Molecules, Journal Year: 2023, Volume and Issue: 28(3), P. 1470 - 1470

Published: Feb. 3, 2023

Supramolecular polymers have attracted considerable interest due to their intriguing features and functions. The dynamic reversibility of noncovalent interactions endows supramolecular with tunable physicochemical properties, self-healing, externally stimulated responses. Among them, pillararene-based show great potential for biomedical applications fascinating host–guest easy modification. Herein, we summarize the state art cancer therapy illustrate its developmental trend future perspective.

Language: Английский

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