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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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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Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 18, 2024

Abstract Scientists have long been fascinated by the biomolecular machines in living systems that process energy and information to sustain life. The first synthetic molecular rotor capable of performing repeated 360° rotations due a combination photo‐ thermally activated processes was reported 1999. progress designing different intervening years has remarkable, with several outstanding examples appearing last few years. Despite accomplishments, there remains confusion regarding fundamental design principles which motions molecules can be controlled, significant intellectual tension between mechanical chemical ways thinking about describing machines. A thermodynamically consistent analysis kinetics rotors pumps shows while light driven operate power‐stroke mechanism, kinetic asymmetry—the relative heights barriers—is sole determinant directionality catalysis Power‐strokes—the depths wells—play no role whatsoever determining sign directionality. These results, elaborated using trajectory thermodynamics nonequilibrium pump equality, show asymmetry governs response many non‐equilibrium phenomena.

Language: Английский

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Transducing chemical energy through catalysis by an artificial molecular motor

Nature, Journal Year: 2025, Volume and Issue: 637(8046), P. 594 - 600

Published: Jan. 15, 2025

Abstract Cells display a range of mechanical activities generated by motor proteins powered through catalysis 1 . This raises the fundamental question how acceleration chemical reaction can enable energy released from that to be transduced (and, consequently, work done) molecular catalyst 2–7 Here we demonstrate molecular-level transduction force 8 in form contraction and re-expansion cross-linked polymer gel driven directional rotation artificial catalysis-driven 9 motors. Continuous 360° rotor about stator motor-molecules incorporated polymeric framework twists chains network around one another. progressively increases writhe tightens entanglements, causing macroscopic approximately 70% its original volume. The subsequent addition opposite enantiomer fuelling system powers reverse direction, unwinding entanglements re-expand. Continued twisting strands new direction causes re-contract. In actuation, motor-molecule produces other physical outcomes, including changes Young modulus storage modulus—the latter is proportional increase strand crossings resulting rotation. experimental demonstration against load synthetic organocatalyst, mechanism 6 , informs both debate 3,5,7 surrounding generation biological motors design principles 6,10–14 for nanotechnology.

Language: Английский

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Using Catalysis to Drive Chemistry Away from Equilibrium: Relating Kinetic Asymmetry, Power Strokes, and the Curtin–Hammett Principle in Brownian Ratchets

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20153 - 20164

Published: Oct. 26, 2022

Chemically fueled autonomous molecular machines are catalysis-driven systems governed by Brownian information ratchet mechanisms. One fundamental principle behind their operation is kinetic asymmetry, which quantifies the directionality of motors. However, it difficult for synthetic chemists to apply this concept design because asymmetry usually introduced in abstract mathematical terms involving experimentally inaccessible parameters. Furthermore, two seemingly contradictory mechanisms have been proposed chemically driven machines: and power stroke This Perspective addresses both these issues, providing accessible useful principles machinery. We relate Curtin–Hammett using a rotary motor kinesin walker as illustrative examples. Our approach describes motors mechanism but pinpoints chemical gating strokes tunable elements that can affect asymmetry. explain why consistent with previous ones outline conditions where be elements. Finally, we discuss role information, used different meanings literature. hope will broad range chemists, clarifying parameters usefully controlled synthesis related systems. It may also aid more comprehensive interdisciplinary understanding biomolecular

Language: Английский

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A tape-reading molecular ratchet

Nature, Journal Year: 2022, Volume and Issue: 612(7938), P. 78 - 82

Published: Oct. 19, 2022

Language: Английский

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Polyrotaxanes and the pump paradigm

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(20), P. 8450 - 8475

Published: Jan. 1, 2022

The year 2022 marks the 30th anniversary of first reports polyrotaxanes in scientific literature. During past three decades, many combinations molecular rings and polymer chains have been synthesised characterised. Until recently, however, permutations available to researchers were limited by synthetic methods which typically relied on an innate affinity between chains. With advent oligorotaxane-forming pumps 2015, it has now become possible pump multiple against their will onto oligomer little or no for rings. These pumps, can recruit actively from solution form precise polyrotaxanes, represent a major breakthrough field. This Tutorial Review highlights key milestones synthesis investigation along with recent developments theory relating pumps. Polyrotaxane properties, arising topologies, allowed them steal march traditional polymers wide range applications materials, electronic biological science, slide-ring gels robust coatings cell phones, wires flexible binders battery anodes, efficient multivalent protein bio-cleavable polyplexes cellular DNA delivery. Molecular potential blaze contemporary trail mechanically interlocked especially those dependent non-equilibrium chemistry related energy storage nanomedicine.

Language: Английский

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Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(7), P. 889 - 899

Published: March 14, 2023

ConspectusThe achievement of artificial systems capable being maintained in out-of-equilibrium states featuring functional properties is a main goal current chemical research. Absorption electromagnetic radiation or consumption species (a "chemical fuel") are the two strategies typically employed to reach such states, which have persist as long one above stimuli present. For this reason often referred "dissipative systems". In simplest scheme, dissipative system initially found resting, equilibrium state. The addition fuel causes shift an When exhausted, reverts initial, Thus, from mechanistic standpoint, turns out be catalyst for consumption. It has noted that, although very simple, scheme implies chance temporally control system. principle, modulating nature and/or amount added, can full time spent by state.In 2016, we that 2-cyano-2-phenylpropanoic acid (1a), whose decarboxylation proceeds smoothly under mild basic conditions, could used drive back and forth motion catenane-based molecular switch. donates proton catenane passes neutral state A transient protonated B. Decarboxylation resulting carboxylate (1acb), generates carbanion, which, strong base, retakes consequently, returns initial A. larger added fuel, longer transient, Since then, 1a other activated carboxylic acids (ACAs) been operation large number based on acid-base reaction, machines host-guest systems, catalysts smart materials, so on. This Account illustrates with purpose show wide applicability ACAs fuels. generality due simplicity idea underlying principle ACAs, always translates into simple experimental requirements.

Language: Английский

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The role of kinetic asymmetry and power strokes in an information ratchet

Chem, Journal Year: 2023, Volume and Issue: 9(10), P. 2902 - 2917

Published: June 19, 2023

Biomolecular machines are driven by information ratchet mechanisms, where kinetic asymmetry in the machine's chemomechanical cycle of fuel-to-waste catalysis induces net directional dynamics. A large-scale energetically downhill conformational change, termed a "power stroke," has often been erroneously implicated as mechanistic driving feature such machines. We investigated roles and power strokes series rotaxane-based ratchets found that alone determines directionality all use same amount fuel to reach normalized steady state. However, can nonetheless influence performance, how fast state is reached. Moreover, nonequilibrium thermodynamic analysis revealed alter form (information [Shannon entropy] versus intercomponent binding energy) free energy stored ratchets. These findings have implications for both understanding biological design principles artificial (supra)molecular

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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