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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(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

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

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(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

Процитировано

6
Switched “On” Transient Fluorescence Output from a Pulsed-Fuel Molecular Ratchet DOI Creative Commons
Andrei S. Baluna, Marcel Dommaschk,

Burkhard Groh

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 27113 - 27119

Опубликована: Дек. 4, 2023

We report the synthesis and operation of a molecular energy ratchet that transports crown ether from solution onto thread, along axle, over fluorophore, off other end thread back into bulk solution, all in response to single pulse chemical fuel (CCl3CO2H). The fluorophore is pyrene residue whose fluorescence normally prevented by photoinduced electron transfer (PET) nearby N-methyltriazolium group. However, binding site inhibits PET, switching on under UV irradiation. Each results cycle transient (encompassing threading, transport site, then dethreading), with onset fluorescent time period determined amount each end-point concentration reagents for disulfide exchange reaction. system provides potential alternative signaling approach artificial machines read symbols sequence-encoded tapes.

Язык: Английский

Процитировано

5
Cyclodextrin-Catalyzed Diels–Alder Reaction for the Syntheses of Cyclodextrin Polyrotaxanes, Molecular Tubes, and Molecular Shuttles DOI
Ying Sun, Yongmin Zhang,

Mengke Liang

и другие.

Macromolecules, Год журнала: 2024, Номер 57(11), С. 5208 - 5217

Опубликована: Май 31, 2024

The existing synthesis methods of cyclodextrin (CD) polyrotaxanes (PRs) are generally tedious and low-yield. Herein, we report an efficient strategy for α-, β-, γ-CD PRs. A Diels–Alder (DA) reaction between 9-anthracenemethanol maleimide was used as the capping since adduct large enough to lock α- β-CDs could be catalyzed by CDs, achieving high yields in aqueous medium under mild conditions. For PRs, introduced maleimide-modified second-generation polylysine dendrons at both ends polymer axle slow dethreading during increase number end-capping groups. Through microwave-assistant retro-DA reaction, synthesized molecular tubes with desirable yields. We further expanded β-CD rotaxane-based shuttles achieved fluorescence modulation using light-driven shuttle movement CD ring along axle.

Язык: Английский

Процитировано

1
Endergonic synthesis driven by chemical fuelling DOI Creative Commons

Enzo Olivieri,

James Gallagher, Alexander Betts

и другие.

Опубликована: Ноя. 8, 2023

Spontaneous chemical reactions proceed energetically downhill to either a local or global minimum, limiting possible transformations those that are exergonic. Endergonic do not spontaneously and require an input of energy. Light has been used drive number deracemisations thermodynamically unfavourable bond-forming reactions, but is restricted substrates can absorb, directly indirectly, energy provided by photons. In contrast, anabolism involves uphill powered fuels. Here we report on the transduction from artificial fuel Diels–Alder reaction. Carboxylic acid catalysed carbodiimide-to-urea formation chemically orthogonal reaction diene dienophile, transiently brings functional groups into close proximity, causing otherwise prohibited cycloaddition in modest (12%) yield with high levels regio- (>99%) stereoselectivity (92:8 exo:endo). At fuelled steady state, kinetic asymmetry fuelling cycle ratchets away equilibrium distribution Diels–Alder:retro-Diels–Alder products. The driving endergonic occurs through ratchet mechanism, reminiscent how molecular machines directionally bias motion. Ratcheting synthesis potential expand synthetic chemistry toolbox, offering new paradigms reactivity, complexity control.

Язык: Английский

Процитировано

2
Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction DOI Creative Commons
Stefan Borsley, David A. Leigh, Benjamin M. W. Roberts

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(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

Процитировано

0