Endergonic synthesis driven by chemical fuelling DOI Creative Commons

Enzo Olivieri,

James Gallagher, Alexander Betts

et al.

Published: Jan. 17, 2024

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 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, offering new paradigms reactivity, complexity control.

Language: Английский

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
Endergonic synthesis driven by chemical fuelling DOI Creative Commons

Enzo Olivieri,

James Gallagher, Alexander Betts

et al.

Published: Jan. 17, 2024

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 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, offering new paradigms reactivity, complexity control.

Language: Английский

Citations

2