From Brownian to Deterministic Motor Movement in a DNA-Based Molecular Rotor

Nano Letters, Journal Year: 2024, Volume and Issue: 24(17), P. 5224 - 5230

Published: April 19, 2024

Molecular devices that have an anisotropic periodic potential landscape can be operated as Brownian motors. When the is cyclically switched with external force, such harness random fluctuations to generate a directed motion. Recently, motor-like rotatory movement was demonstrated electrically DNA origami rotor designed ratchet-like obstacles. Here, we demonstrate intrinsic anisotropy of rotors also sufficient result in motor movement. We show for low amplitudes switching field, operate motors, while at higher amplitudes, they behave deterministically overdamped electrical characterize amplitude and frequency dependence movements, showing after initial steep rise, angular speed peaks drops excessive driving frequencies. The well described by simple stochastic model system.

Language: Английский

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Catalytic resonance theory: the catalytic mechanics of programmable ratchets

Chemical Science, Journal Year: 2024, Volume and Issue: 15(34), P. 13872 - 13888

Published: Jan. 1, 2024

Catalytic reaction networks of multiple elementary steps operating under dynamic conditions

Language: Английский

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Supramolecular polymerization induced by the rotation of light-driven molecular motors

Published: Aug. 16, 2024

Molecular motors are capable of producing mechanical work on their environment by using unique capacity to generate non-reciprocal autonomous motions at the nanoscale. Although operating principles now well understood, artificial molecular have yet demonstrate general confer novel properties (supra)molecular systems and materials. Here we show that amphiphilic light-driven can adsorb onto air-water interface form Langmuir monolayers upon compression. Under irradiation, surface pressure isotherms these films reveal a drastic shift toward smaller areas as consequence motors’ activation. We explain this counterintuitive phenomenon rotation-induced supramolecular polymerization motors, limited maximal torque they deliver, leading formation highly organized patterns. This serendipitous discovery highlights opportunities offered control processes active nanostructures for design innovative

Language: Английский

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Power Strokes in Molecular Motors: Predictive, Irrelevant, or Somewhere in Between?

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

For several decades, molecular motor directionality has been rationalized in terms of the free energy conformations visited before and after takes a step, so-called power stroke mechanism with analogues macroscopic engines. Despite theoretical experimental demonstrations its flaws, language is quite ingrained, some communities still value intuition. By building catalysis-driven into simulated numerical experiments, we here systematically report on how responds when modified accordingly to We confirm that generally does not predict directionality. Nevertheless, simulations illustrate relative stability should be included as potential design element adjust directional bias. Though strokes are formally unimportant for determining directionality, show practical attempts alter have side effects can fact The change bias align what intuition would suggested, offering explanation why flawed retain apparent utility engineering specific systems.

Language: Английский

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Transducing chemical energy through catalysis by an artificial molecular motor

Published: May 24, 2024

Cells display a range of mechanical activities enabled by the cytoskeleton, viscoelastic hydrogel manipulated motor proteins powered through catalysis. This raises question how acceleration chemical reaction can enable energy released from that to be transduced, and thereby work done, molecular catalyst. Here we demonstrate molecular-level transduction force in form contraction re-expansion crosslinked polymer gel driven directional rotation embedded artificial catalysis-driven motors. Continuous 360° rotor about stator motor-molecules incorporated within polymeric framework gel, twists chains network around one another (either clockwise or anti-clockwise, depending on chirality fuelling system). progressively increases writhe tightens entanglements, causing macroscopic ~70% its original volume. The limit corresponds stall motor; point at which, despite catalysis continuing, untwisting exerted entwined strands balances conformation selection motor’s catalytic cycle. Subsequent addition opposite enantiomeric system powers contracted reverse direction, unwinding entanglements re-expand. Continued twisting new direction causes contract once again. experimental demonstration against load synthetic catalyst, mechanism catalyst kinetic asymmetry fuel-to-waste reaction, informs both debate surrounding generation biological motors design principles for nanotechnology.

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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Transient transition from stable to dissipative assemblies in response to the spatiotemporal availability of a chemical fuel

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

Published: Oct. 15, 2024

The transition from inactive to active matter implies a thermodynamically stable energy-dissipating structures. Here, we show how the spatiotemporal availability of chemical fuel causes self-assembled structure transiently pass an state. system relies on local injection weak affinity phosphodiester substrate into agarose hydrogel containing surfactant-based structures templated by ATP. Injection leads inclusion additional surfactant molecules in assemblies leading formation catalytic hotspots for conversion. After disappearance as result conversion and diffusion spontaneously return state, which can be reactivated upon new batch fuel. study illustrates dissipating cope with intermittent energy without compromising long-term structural stability.

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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Power strokes in molecular motors: Predictive, irrelevant, or somewhere in between?

Published: April 16, 2024

For several decades, molecular motor directionality has been rationalized in terms of the free energy conformations visited before and after takes a step, so-called power-stroke mechanism with analogues macroscopic engines. Despite theoretical experimental demonstrations its flaws, language is quite ingrained, some communities still value intuition. By building catalysis-driven into simulated numerical experiments, we here systematically report on how responds when modified accordingly to We confirm that power stroke does not generally predict directionality. Still, relative stability can nevertheless be useful design element helps one alter directional bias motor. The ostensible effectiveness intuition explained by recognition target conformation stability, must interactions between moieties motor, those altered do affect isolation. This lead apparent correlations might leverage engineering specific systems.

Language: Английский

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Life in Lab: Chemically Fueled Systems Chemistry for Emergent Properties

ChemSystemsChem, Journal Year: 2024, Volume and Issue: 6(6)

Published: July 9, 2024

Abstract Understanding the emergence of complex properties in dissipative non‐equilibrium systems is crucial for unraveling mysteries life processes. The review focuses on documented research chemically fueled autonomous systems, self‐sorting towards compartmentalization, self‐replication via autocatalysis, and rhythmic chemical oscillators. In addition to that, also discusses newly introduced reactions dynamic combinatorial libraries systems.

Language: Английский

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