Structural Influence of the Chemical Fueling System on a Catalysis-Driven Rotary Molecular Motor DOI Creative Commons

Hua‐Kui Liu,

Toufic W. Mrad, Axel Troncossi

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Continuous directionally biased 360° rotation about a covalent single bond was recently realized in the form of chemically fueled 1-phenylpyrrole 2,2′-dicarboxylic acid rotary molecular motor. However, original fueling system and reaction conditions resulted motor directionality only ∼3:1 (i.e., on average backward for every three forward rotations), along with catalytic efficiency operation 97% fuel 14%. Here, we report efficacy series chiral carbodiimide fuels hydrolysis promoters (pyridine pyridine N-oxide derivatives) driving improved directional this motor-molecule. We outline complete network operation, composed directional, futile, slip cycles. Using derivatives where final conformational step is either very slow or completely blocked, phenylpyrrole diacid becomes enantiomerically enriched, allowing kinetic gating individual steps cycle to be measured. The that produces highest gives 13% enantiomeric excess (e.e.) anhydride-forming kinetically gated step, while most effective promoter generates 90% e.e. step. Combining best-performing into results 92% e.e.. Under dilute chemostated regime (to avoid N-acyl urea formation at high concentrations promoters), continuously rotates ∼24:1 24 rotations) >99% 51%.

Language: Английский

Dissipative DNA nanotechnology DOI
Erica Del Grosso, Elisa Franco, Leonard J. Prins

et al.

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(6), P. 600 - 613

Published: June 1, 2022

Language: Английский

Citations

129
Autonomous fuelled directional rotation about a covalent single bond DOI
Stefan Borsley, Elisabeth Kreidt, David A. Leigh

et al.

Nature, Journal Year: 2022, Volume and Issue: 604(7904), P. 80 - 85

Published: April 6, 2022

Language: Английский

Citations

113
Chemical fuels for molecular machinery DOI
Stefan Borsley, David A. Leigh, Benjamin M. W. Roberts

et al.

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(7), P. 728 - 738

Published: July 1, 2022

Language: Английский

Citations

111
Insights into Chemically Fueled Supramolecular Polymers DOI

Anastasiia Sharko,

Dimitri Livitz, Serena De Piccoli

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(13), P. 11759 - 11777

Published: June 8, 2022

Supramolecular polymerization can be controlled in space and time by chemical fuels. A nonassembled monomer is activated the fuel subsequently self-assembles into a polymer. Deactivation of molecule either solution or inside polymer leads to disassembly. Whereas biology has already mastered this approach, fully artificial examples have only appeared past decade. Here, we map available literature four distinct regimes depending on their activation/deactivation rates equivalents deactivating fuel. We present increasingly complex mathematical models, first considering (i.e., transient activation) later including full details isodesmic cooperative supramolecular processes self-assembly). finish showing that sustained oscillations are possible chemically fueled provide mechanistic insights. hope our models encourage quantification activation, deactivation, assembly, disassembly kinetics future studies.

Language: Английский

Citations

94
An electric molecular motor DOI Creative Commons
Long Zhang, Yunyan Qiu,

Wei-Guang Liu

et al.

Nature, Journal Year: 2023, Volume and Issue: 613(7943), P. 280 - 286

Published: Jan. 11, 2023

Macroscopic electric motors continue to have a large impact on almost every aspect of modern society. Consequently, the effort towards developing molecular

Language: Английский

Citations

89
Insights from an information thermodynamics analysis of a synthetic molecular motor DOI
Shuntaro Amano, Massimiliano Esposito, Elisabeth Kreidt

et al.

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(5), P. 530 - 537

Published: March 17, 2022

Language: Английский

Citations

80
Non-equilibrium Steady States in Catalysis, Molecular Motors, and Supramolecular Materials: Why Networks and Language Matter DOI Creative Commons
Ivan Aprahamian, Stephen M. Goldup

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

Citations

79
Thermodynamics of Ionic Thermoelectrics for Low-Grade Heat Harvesting DOI Creative Commons
Xin Qian, Zhihao Ma, Qiangqiang Huang

et al.

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(2), P. 679 - 706

Published: Jan. 31, 2024

More than half of the waste heat rejected into environment has temperatures lower 100 °C, which accounts for nearly 85 PWh/year worldwide. Efficiently harvesting low-grade could be a promising step toward carbon neutrality. Recent developments ionic thermoelectrics (i-TE) with giant thermopower have provoked intensive interest in using ions as energy and charge carriers efficient thermal harvesting. However, current literature primarily focuses on improving only, while ion transport thermodynamics affecting efficiencies been largely neglected. This Review clarifies fundamentals electrochemistry developing highly i-TE devices. Two major types devices, thermo-ionic capacitors (TICs) thermogalvanic cells (TGCs), are discussed detail. The analyzes methods enhancing by taking an entropic point view. We also derived modified thermoelectric factor Z both TICs TGCs that fully incorporate dynamics electrochemical reactions. hybrid devices showing improved efficiencies, power density, multifunctionality reviewed. Finally, we comment remaining challenges provide outlook future directions.

Language: Английский

Citations

35
Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction DOI Creative Commons
Stefan Borsley, David A. Leigh, Benjamin M. W. Roberts

et al.

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

Citations

35
Transducing chemical energy through catalysis by an artificial molecular motor DOI Creative Commons
Peng-Lai Wang, Stefan Borsley, M. Power

et al.

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

Citations

3