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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Dynamic Promotion of the Oxygen Evolution Reaction via Programmable Metal Oxides

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(5), P. 2013 - 2023

Published: April 8, 2024

Hydrogen gas is a promising renewable energy storage medium when produced via water electrolysis, but this process limited by the sluggish kinetics of anodic oxygen evolution reaction (OER). Herein, we used microkinetic model to investigate promoting OER using programmable oxide catalysts (i.e., forced catalyst dynamics). We found that could increase current density at fixed overpotential (100–600× over static rates) or reduce required reach 10 mA cm–2 (45–140% reduction vs static). In our kinetic parametrization, key parameters controlling quality catalytic ratchet were O*-to-OOH* and O*-to-OH* activation barriers. Our findings indicate may be viable strategy for accelerating enabling lower-overpotential operation, more accurate parametrization precise predictions performance, quality, resulting efficiency.

Language: Английский

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Non-equilibrium self-assembly for living matter-like properties

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(10), P. 723 - 740

Published: Aug. 23, 2024

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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Computational Analysis of the Kinetic Requirements for Coupled Reaction Systems

Molecules, Journal Year: 2025, Volume and Issue: 30(4), P. 911 - 911

Published: Feb. 15, 2025

The art of designing coupling systems to drive reactions for endergonic synthesis is a subject great interest in the scientific community, but it still presents major challenges. aim this kinetic study was run simulations COPASI 4.39 test behavior hypothetical models system that couples two independent reactions, one exergonic and other endergonic. In our computational study, we unraveled qualitative quantitative conditions allow benefit coupling, considering all possible reaction pathways within network. Optimal were reached by assigning favorable directionalities low activation energies six steps network featured twenty steps. Moreover, different designed tested order investigate availability with

Language: Английский

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Abiotic Acyl Transfer Cascades Driven by Aminoacyl Phosphate Esters and Self-Assembly

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29621 - 29629

Published: Oct. 17, 2024

Biochemical acyl transfer cascades, such as those initiated by the adenylation of carboxylic acids, are central to various biological processes, including protein synthesis and fatty acid metabolism. Designing cascade reactions in aqueous media remains challenging due need control multiple, sequential a single pot manage stability reactive intermediates. Herein, we developed abiotic cascades using aminoacyl phosphate esters, synthetic counterparts adenylates, drive chemical self-assembly pot. We demonstrated that structural elements amino side chains (aromatic versus aliphatic) significantly influence reactivity half-lives ranging from hours days. This behavior, turn, affects number couplings can achieve network propensity activated intermediate structures. The constructed bifunctional peptide substrates featuring chain nucleophiles. Specifically, aromatic acids facilitate formation transient thioesters, which preorganized into spherical aggregates further couple chimeric assemblies composed esters thioesters. In contrast, aliphatic lack ability form structures, predominantly undergo hydrolysis, bypassing transformations after thioester formation. Additionally, mixtures containing multiple substrates, achieved selective product following distinct pathway favors subsequent through changes self-assembly. By coupling with molecules varying time scales, reaction clocks lifetimes dynamics, facilitating precise temporal regulation.

Language: Английский

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Synthesis goes uphill

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(6), P. 673 - 674

Published: March 27, 2024

Language: Английский

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The role of Kinetic Asymmetry in Chemical and Thermodynamic Coupling

ChemSystemsChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract The input of energy can shift an isomerization reaction A⇌B away from equilibrium, but which way, in favor A or B? answer to this question lies understanding kinetic asymmetry, a concept first discussed the context how oscillating fluctuating perturbation act concert with catalyst drive equilibrium. key theoretical result is non‐equilibrium pumping equality that generalizes idea equilibrium constant steady‐state.

Language: Английский

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Cascading Macrocycle and Helix Motions in a Foldarotaxane Molecular Shuttle

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 9, 2024

Abstract The design of a dynamically assembled foldarotaxane was envisioned with the aim operating as two cascading trigger‐based molecular shuttle. Under acidic conditions, both macrocycle and helix were localized around their respective best stations because they are far enough from each other not to alter stability complexes. pH‐dependent localization along encircled axle allowed us modulate association between helical foldamer its sites interaction on axle. kinetic control—at low concentration room temperature—when supramolecular architecture is kinetically stable, pH‐responsive translation thread triggered gliding away initial station. At higher concentration—when assembly/disassembly process accelerated—the system reached equilibrium state. A new isomer then appeared through change relative position thread. In this isomer, segregated fine control thermodynamic processes, combined pH, reciprocal segregation or ring interaction.

Language: Английский

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Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(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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