Progressive Endergonic Synthesis of Diels–Alder Adducts Driven by Chemical Energy DOI Creative Commons
Shaymaa Al Shehimy,

Hai‐Dang Le,

Shuntaro Amano

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)

Published: July 17, 2024

Abstract The overwhelming majority of artificial chemical reaction networks respond to stimuli by relaxing towards an equilibrium state. opposite response—moving away from equilibrium—can afford the endergonic synthesis molecules, which only rare examples have been reported. Here, we report six Diels–Alder adducts formed in process and use this strategy realize their stepwise accumulation. Indeed, systems repeated occurrences same stimulus increasing amount adduct formed, with final network distribution depending on number received. Our findings indicate how processes can contribute transition responsive adaptive systems.

Language: Английский

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
Endergonic synthesis driven by chemical fuelling DOI Creative Commons
Enzo Olivieri, James Gallagher, Alexander Betts

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(6), P. 707 - 714

Published: March 11, 2024

Abstract 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 deracemizations 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 yield (15% after two fuelling cycles) with high levels regio- (>99%) stereoselectivity (92:8 exo : endo ). Kinetic asymmetry cycle ratchets away equilibrium distribution Diels–Alder:retro-Diels–Alder products. The driving endergonic occurs through ratchet mechanism (an information ratchet, depending synthetic protocol), reminiscent how molecular machines directionally bias motion. Ratcheting synthesis potential expand chemistry toolbox terms reactivity, complexity control.

Language: Английский

Citations

13
Dynamic Promotion of the Oxygen Evolution Reaction via Programmable Metal Oxides DOI
Sallye R. Gathmann, Christopher J. Bartel, Lars C. Grabow

et al.

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(5), P. 2013 - 2023

Published: April 8, 2024

Hydrogen gas is a promising renewable energy storage medium when produced via water electrolysis, but this process limited by the sluggish kinetics of anodic oxygen evolution reaction (OER). Herein, we used microkinetic model to investigate promoting OER using programmable oxide catalysts (i.e., forced catalyst dynamics). We found that could increase current density at fixed overpotential (100–600× over static rates) or reduce required reach 10 mA cm–2 (45–140% reduction vs static). In our kinetic parametrization, key parameters controlling quality catalytic ratchet were O*-to-OOH* and O*-to-OH* activation barriers. Our findings indicate may be viable strategy for accelerating enabling lower-overpotential operation, more accurate parametrization precise predictions performance, quality, resulting efficiency.

Language: Английский

Citations

11
Photoswitchable Imines Drive Dynamic Covalent Systems to Nonequilibrium Steady States DOI Creative Commons
Jiarong Wu, Jake L. Greenfield

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 20720 - 20727

Published: July 18, 2024

Coupling a photochemical reaction to thermal exchange process can drive the latter nonequilibrium steady state (NESS) under photoirradiation. Typically, systems use separate motifs for photoresponse and equilibrium-related processes. Here, we show that photoswitchable imines fulfill both roles simultaneously, autonomously driving dynamic covalent system into NESS continuous light irradiation. We demonstrate this using transimination reactions, where

Language: Английский

Citations

11
Artificial molecular pumps DOI
Long Zhang, Huang Wu, Xuesong Li

et al.

Nature Reviews Methods Primers, Journal Year: 2024, Volume and Issue: 4(1)

Published: Feb. 22, 2024

Language: Английский

Citations

7
A Minimalistic Covalent Bond‐Forming Chemical Reaction Cycle that Consumes Adenosine Diphosphate DOI Creative Commons
Tommaso Marchetti, Benjamin M. W. Roberts, Diego Frezzato

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 27, 2024

Abstract The development of synthetic active matter requires the ability to design materials capable harnessing energy from a source carry out work. Nature achieves this using chemical reaction cycles in which released an exergonic is used drive biochemical processes. Although many chemically fuelled that control transient responses, such as self‐assembly, have been reported, generally high complexity reported systems hampers full understanding how available actually exploited by these systems. This lack limiting factor matter. Here, we report minimalistic responsive cycle adenosine diphosphate (ADP) triggers formation catalyst for its own hydrolysis. establishes interdependence between concentrations network components resulting catalyst. sufficiently simple all kinetic and thermodynamic parameters governing behaviour can be characterised, allowing models built simulate progress reactions within network. While current does not enable ADP‐hydrolysis populate non‐equilibrium composition, provide insight into way dissipates energy. Furthermore, essential principles are revealed constructing driven systems, composition away equilibrium through consumption

Language: Английский

Citations

7
Analysis of kinetic asymmetry in a multi-cycle reaction network establishes the principles for autonomous compartmentalized molecular ratchets DOI Creative Commons
Emanuele Penocchio,

Ahmad Bachir,

Alberto Credi

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(12), P. 3644 - 3655

Published: Sept. 13, 2024

Language: Английский

Citations

7
Progressive Endergonic Synthesis of Diels–Alder Adducts Driven by Chemical Energy DOI Creative Commons
Shaymaa Al Shehimy,

Hai‐Dang Le,

Shuntaro Amano

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 17, 2024

The overwhelming majority of artificial chemical reaction networks respond to stimuli by relaxing towards an equilibrium state. opposite response-moving away from equilibrium-can afford the endergonic synthesis molecules, which only rare examples have been reported. Here, we report six Diels-Alder adducts formed in process and use this strategy realize their stepwise accumulation. Indeed, systems repeated occurrences same stimulus increasing amount adduct formed, with final network distribution depending on number received. Our findings indicate how processes can contribute transition responsive adaptive systems.

Language: Английский

Citations

5
The sugar cube: Network control and emergence in stereoediting reactions DOI
Hayden M. Carder, Gino Occhialini, Giovanni Bistoni

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6707), P. 456 - 463

Published: July 25, 2024

Stereochemical editing strategies have recently enabled the transformation of readily accessible substrates into rare and valuable products. Typically, site selectivity is achieved by minimizing kinetic complexity using protecting groups to suppress reactivity at undesired sites (substrate control) or catalysts with tailored shapes drive desired (catalyst control). We propose "network control," a contrasting paradigm that exploits hidden interactions between rate constants greatly amplify modest intrinsic biases enable precise multisite editing. When network control applied photochemical isomerization hexoses, six eight possible diastereomers can be selectively obtained. The amplification effect viewed as mesoscale phenomenon limiting regimes in simple chemical systems metabolic regulation complex biological systems.

Language: Английский

Citations

5
Endergonic synthesis of Diels-Alder adducts enables non-equilibrium adaptive behaviors in chemical reaction networks DOI Creative Commons
Shaymaa Al Shehimy,

Hai-Dang Le,

Simone Di Noja

et al.

Published: Jan. 29, 2024

The overwhelming majority of artificial chemical reaction networks respond to stimuli relaxing towards an equilibrium state. opposite response – moving away from can afford the endergonic synthesis molecules, which only rare examples have been reported. Here, we report six Diels-Alder adducts accumulated in process and use this strategy realize adaptive phenomena. Indeed, systems repeated occurrences same stimulus by increasing amount adduct formed, with final network distribution depending on number frequency received. Our findings indicate how processes contribute transition responsive systems.

Language: Английский

Citations

4