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

Pumping between phases with a pulsed-fuel molecular ratchet DOI
Dean Thomas, Daniel J. Tetlow, Yansong Ren

et al.

Nature Nanotechnology, Journal Year: 2022, Volume and Issue: 17(7), P. 701 - 707

Published: April 4, 2022

Language: Английский

Citations

63
Using Catalysis to Drive Chemistry Away from Equilibrium: Relating Kinetic Asymmetry, Power Strokes, and the Curtin–Hammett Principle in Brownian Ratchets DOI Creative Commons
Shuntaro Amano, Massimiliano Esposito, Elisabeth Kreidt

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20153 - 20164

Published: Oct. 26, 2022

Chemically fueled autonomous molecular machines are catalysis-driven systems governed by Brownian information ratchet mechanisms. One fundamental principle behind their operation is kinetic asymmetry, which quantifies the directionality of motors. However, it difficult for synthetic chemists to apply this concept design because asymmetry usually introduced in abstract mathematical terms involving experimentally inaccessible parameters. Furthermore, two seemingly contradictory mechanisms have been proposed chemically driven machines: and power stroke This Perspective addresses both these issues, providing accessible useful principles machinery. We relate Curtin–Hammett using a rotary motor kinesin walker as illustrative examples. Our approach describes motors mechanism but pinpoints chemical gating strokes tunable elements that can affect asymmetry. explain why consistent with previous ones outline conditions where be elements. Finally, we discuss role information, used different meanings literature. hope will broad range chemists, clarifying parameters usefully controlled synthesis related systems. It may also aid more comprehensive interdisciplinary understanding biomolecular

Language: Английский

Citations

54
Out‐of‐Equilibrium Self‐Replication Allows Selection for Dynamic Kinetic Stability in a System of Competing Replicators DOI Creative Commons
Bin Liu, Juntian Wu, Marc Geerts

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(18)

Published: Feb. 18, 2022

Abstract Among the key characteristics of living systems are their ability to self‐replicate and fact that they exist in an open system away from equilibrium. Herein, we show how outcome competition between two self‐replicators, differing size building block composition, is different depending on whether experiments conducted a closed vial or out‐of‐equilibrium replication–destruction regime. In system, slower replicator eventually prevails over faster competitor. replication‐destruction regime, implemented through flow reversed dominates. The interpretation experimental observations supported by mass‐action‐kinetics model. These results represent one few manifestations selection among competing self‐replicators based dynamic kinetic stability pave way towards Darwinian evolution abiotic systems.

Language: Английский

Citations

51
The role of kinetic asymmetry and power strokes in an information ratchet DOI Creative Commons

Lorna Binks,

Stefan Borsley, Todd R. Gingrich

et al.

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

Citations

37
pH-feedback systems to program autonomous self-assembly and material lifecycles DOI
Charu Sharma, Indrajit Maity, Andreas Walther

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(9), P. 1125 - 1144

Published: Jan. 1, 2023

We highlight the development of pH-feedback systems which can be coupled to diverse pH-switchable building blocks achieve transient self-assemblies and materials with programmable temporal behavior autonomous lifecycles.

Language: Английский

Citations

34
Kinetic Asymmetry versus Dissipation in the Evolution of Chemical Systems as Exemplified by Single Enzyme Chemotaxis DOI
Niladri Sekhar Mandal, Ayusman Sen, R. Dean Astumian

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(10), P. 5730 - 5738

Published: March 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.

Language: Английский

Citations

32
Artificial Molecular Ratchets: Tools Enabling Endergonic Processes DOI Creative Commons
Thitiporn Sangchai, Shaymaa Al Shehimy, Emanuele Penocchio

et al.

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

Citations

32
Kinetic Barrier Diagrams to Visualize and Engineer Molecular Nonequilibrium Systems DOI Creative Commons
Emanuele Penocchio, Giulio Ragazzon

Small, Journal Year: 2023, Volume and Issue: 19(14)

Published: Jan. 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.

Language: Английский

Citations

30
Light‐Fueled Nonequilibrium and Adaptable Hydrogels for Highly Tunable Autonomous Self‐Oscillating Functions DOI

Xuehan Yang,

Wencheng Shi,

Zhe Chen

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(24)

Published: March 6, 2023

Abstract Nonequilibrium oscillation fueled by dissipating chemical energy is ubiquitous in living systems for realizing a broad range of complex functions. The design synthetic materials that can mimic their biological counterparts the production dissipative structures and autonomous oscillations great interest but remains challenging. Here, series environmentally adaptable hydrogels functionalized with photoswitchable spiropyran derivatives display tunable equilibrium‐shifting capability, thus endowing those high degree freedom flexibility reported. Such nonequilibrium are able to responsively adapt shapes under constant light illumination due asymmetric deswelling, which turn generates self‐shadowing consequently creates self‐oscillating behaviors through negative feedback process. Diverse modes including bending, twisting, snap‐through buckling frequency amplitude widely observed three different molecular systems. Density functional theory calculations finite element simulations further demonstrated robustness such photoadaptable self‐oscillation mechanism. This study provides useful strategy construction highly potential applications self‐sustained soft robots devices.

Language: Английский

Citations

30
Ratcheting synthesis DOI
Stefan Borsley, James Gallagher, David A. Leigh

et al.

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

Published: Dec. 15, 2023

Language: Английский

Citations

30