Non-equilibrium Steady States in Catalysis, Molecular Motors, and Supramolecular Materials: Why Networks and Language Matter

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(26), С. 14169 - 14183

Опубликована: Июнь 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.

Язык: Английский

---

Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 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.

Язык: Английский

---

Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(9)

Опубликована: Янв. 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.

Язык: Английский

---

Transducing chemical energy through catalysis by an artificial molecular motor

Nature, Год журнала: 2025, Номер 637(8046), С. 594 - 600

Опубликована: Янв. 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.

Язык: Английский

---

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

Chem, Год журнала: 2023, Номер 9(10), С. 2902 - 2917

Опубликована: Июнь 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

Язык: Английский

---

Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(47)

Опубликована: Авг. 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.

Язык: Английский

---

Kinetic Asymmetry versus Dissipation in the Evolution of Chemical Systems as Exemplified by Single Enzyme Chemotaxis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(10), С. 5730 - 5738

Опубликована: Март 3, 2023

Single enzyme chemotaxis is a phenomenon by which nonequilibrium spatial distribution of an created and maintained concentration gradients the substrate product catalyzed reaction. These can arise either naturally through metabolism or experimentally, e.g., flow materials microfluidic channels use diffusion chambers with semipermeable membranes. Numerous hypotheses regarding mechanism this have been proposed. Here, we discuss based solely on chemical reaction show that kinetic asymmetry, difference in transition state energies for dissociation/association product, diffusivities bound free forms enzyme, are determinates direction result positive negative chemotaxis, both demonstrated experimentally. Exploration these fundamental symmetries govern behavior helps to distinguish between possible mechanisms evolution system from initial steady whether principle determines shifts when exposed external energy source thermodynamics kinetics latter being supported results present paper. Our that, while dissipation ineluctably accompanies phenomena, including systems do not evolve maximize minimize but rather attain greater stability accumulate regions where their effective coefficient as small possible. The chemotactic response formed other enzymes participating catalytic cascade provides forming loose associations known metabolons. Significantly, force due depends asymmetry so be nonreciprocal, one attracted another repelled one, seeming contradiction Newtons third law. This nonreciprocity important ingredient active matter.

Язык: Английский

---

Kinetic Barrier Diagrams to Visualize and Engineer Molecular Nonequilibrium Systems

Small, Год журнала: 2023, Номер 19(14)

Опубликована: Янв. 26, 2023

Molecular nonequilibrium systems hold great promises for the nanotechnology of future. Yet, their development is slowed by absence an informative representation. Indeed, while potential energy surfaces comprise in principle all information, they hide dynamic interplay multiple reaction pathways underlying systems, i.e., degree kinetic asymmetry. To offer insightful visual representation asymmetry, we extended approach pertaining to catalytic networks, span model, focusing on system dynamics - rather than thermodynamics. Our encompasses both chemically and photochemically driven ranging from unimolecular motors simple self-assembly schemes. The obtained diagrams give immediate access information needed guide experiments, such as states' population, rate machine operation, maximum work output, effects design changes. proposed barrier a unifying graphical tool disparate phenomena.

Язык: Английский

---

Ratcheting synthesis

Nature Reviews Chemistry, Год журнала: 2023, Номер 8(1), С. 8 - 29

Опубликована: Дек. 15, 2023

Язык: Английский

---

A molecular information ratchet using a cone-shaped macrocycle

Chem, Год журнала: 2023, Номер 9(5), С. 1147 - 1163

Опубликована: Янв. 19, 2023

Язык: Английский

---