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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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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Ratcheting synthesis

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 8(1), P. 8 - 29

Published: Dec. 15, 2023

Language: Английский

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Waste-Free Fully Electrically Fueled Dissipative Self-Assembly System

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(6), P. 3727 - 3735

Published: Feb. 6, 2023

The importance and prevalence of energy-fueled active materials in living systems have inspired the design synthetic using various fuels. However, several major limitations current designs remain to be addressed, such as accumulation chemical wastes during process, unsustainable behavior, lack precise spatiotemporal control. Here, we demonstrate a fully electrically fueled (e-fueled) self-assembly material that can overcome aforementioned limitations. Using an electrochemical setup with dual electrocatalysts, anodic oxidation one electrocatalyst (ferrocyanide, [Fe(CN)6]4-) creates positive fuel activate self-assembly, while simultaneously, cathodic reduction other (methyl viologen, [MV]2+) generates negative triggering fiber disassembly. Due catalytic nature for reaction networks, this e-fueled system does not generate any waste, sustain behavior extended period when electrical potential is maintained, provides

Language: Английский

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Supramolecular dissipative self‐assembly systems: Approaches and applications

Deleted Journal, Journal Year: 2023, Volume and Issue: 1(2)

Published: Oct. 18, 2023

Abstract Dissipative self‐assembly (DSA) system requires a continuous supply of fuels to maintain the far‐from‐equilibrium assembled state. Living organisms exist and operate far from thermodynamic equilibrium by consumption energy taken surroundings, so how realize construction artificial DSA has attracted much attention researchers all over world. Owing dynamic controllable noncovalent interactions, supramolecular systems have achieved higher functions fueled various types energy, such as chemical fuels, light, electric acoustic mechanical energy. Upon input external nonactive precursors can be activated form building blocks at levels then self‐assemble into transient structures. As proceeding deactivation reaction, with level dissipate back initial precursors, resulting in disassembly process, complete full cycle. In this review, we summarize recent advances on its strategies energy‐fueled regulation approaches. The applications luminescence modulating, information encryption, self‐regulating gels, drug delivery, catalysis are also discussed. We hope that review article will facilitate further understanding development systems.

Language: Английский

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A Chemical Reaction Network Drives Complex Population Dynamics in Oscillating Self-Reproducing Vesicles

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(27), P. 18262 - 18269

Published: June 25, 2024

We report chemically fueled oscillations of vesicles. The population cycling vesicles is driven by their self-reproduction and collapse within a biphasic reaction network involving the interplay molecular supramolecular events. studied on scales tracked vesicle populations in time interferometric scattering microscopy dynamic light scattering. Complex events were observed during oscillations─including reproduction, growth, decomposition─and differences number, size, mass aggregates can often be between pulses. This system's behavior reminiscent reproductive cycle living cells.

Language: Английский

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Analysis of kinetic asymmetry in a multi-cycle reaction network establishes the principles for autonomous compartmentalized molecular ratchets

Chem, Journal Year: 2024, Volume and Issue: 10(12), P. 3644 - 3655

Published: Sept. 13, 2024

Language: Английский

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Autonomous Non‐Equilibrium Self‐Assembly and Molecular Movements Powered by Electrical Energy**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(5)

Published: Nov. 24, 2022

The ability to exploit energy autonomously is one of the hallmarks life. Mastering such processes in artificial nanosystems can open technological opportunities. In last decades, light- and chemically driven autonomous systems have been developed relation conformational motion self-assembly, mostly molecular motors. contrast, despite electrical being an attractive source power nanosystems, its harnessing has received little attention. Herein we consider operation mode that allows exploitation by a self-assembling system. Threading dethreading motions pseudorotaxane take place solution, powered current flowing between electrodes scanning electrochemical microscope. underlying ratchet mechanism drives self-assembly steps away from equilibrium with higher efficiency compared other systems. strategy general might be extended redox-driven

Language: Английский

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