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Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question

[Image: see text] Micrometer-sized objects are widely known to exhibit chemically driven motility in systems away from equilibrium. Experimental observation of reaction-induced motility or enhancement in diffusivity at the much shorter length scale of small molecules is, however, still a matter of d...

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Autores principales: Rezaei-Ghaleh, Nasrollah, Agudo-Canalejo, Jaime, Griesinger, Christian, Golestanian, Ramin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8796239/
https://www.ncbi.nlm.nih.gov/pubmed/35078321
http://dx.doi.org/10.1021/jacs.1c11754
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author Rezaei-Ghaleh, Nasrollah
Agudo-Canalejo, Jaime
Griesinger, Christian
Golestanian, Ramin
author_facet Rezaei-Ghaleh, Nasrollah
Agudo-Canalejo, Jaime
Griesinger, Christian
Golestanian, Ramin
author_sort Rezaei-Ghaleh, Nasrollah
collection PubMed
description [Image: see text] Micrometer-sized objects are widely known to exhibit chemically driven motility in systems away from equilibrium. Experimental observation of reaction-induced motility or enhancement in diffusivity at the much shorter length scale of small molecules is, however, still a matter of debate. Here, we investigate the molecular diffusivity of reactants, catalyst, and product of a model reaction, the copper-catalyzed azide–alkyne cycloaddition click reaction, and develop new NMR diffusion approaches that allow the probing of reaction-induced diffusion enhancement in nanosized molecular systems with higher accuracy than the state of the art. Following two different approaches that enable the accounting of time-dependent concentration changes during NMR experiments, we closely monitored the diffusion coefficient of reaction components during the reaction. The reaction components showed distinct changes in the diffusivity: while the two reactants underwent a time-dependent decrease in their diffusivity, the diffusion coefficient of the product gradually increased and the catalyst showed only slight diffusion enhancement within the range expected for reaction-induced sample heating. The decrease in diffusion coefficient of the alkyne, one of the two reactants of click reaction, was not reproduced during its copper coordination when the second reactant, azide, was absent. Our results do not support the catalysis-induced diffusion enhancement of the components of the click reaction and, instead, point to the role of a relatively large intermediate species within the reaction cycle with diffusivity lower than that of both the reactants and product molecule.
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spelling pubmed-87962392022-01-28 Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question Rezaei-Ghaleh, Nasrollah Agudo-Canalejo, Jaime Griesinger, Christian Golestanian, Ramin J Am Chem Soc [Image: see text] Micrometer-sized objects are widely known to exhibit chemically driven motility in systems away from equilibrium. Experimental observation of reaction-induced motility or enhancement in diffusivity at the much shorter length scale of small molecules is, however, still a matter of debate. Here, we investigate the molecular diffusivity of reactants, catalyst, and product of a model reaction, the copper-catalyzed azide–alkyne cycloaddition click reaction, and develop new NMR diffusion approaches that allow the probing of reaction-induced diffusion enhancement in nanosized molecular systems with higher accuracy than the state of the art. Following two different approaches that enable the accounting of time-dependent concentration changes during NMR experiments, we closely monitored the diffusion coefficient of reaction components during the reaction. The reaction components showed distinct changes in the diffusivity: while the two reactants underwent a time-dependent decrease in their diffusivity, the diffusion coefficient of the product gradually increased and the catalyst showed only slight diffusion enhancement within the range expected for reaction-induced sample heating. The decrease in diffusion coefficient of the alkyne, one of the two reactants of click reaction, was not reproduced during its copper coordination when the second reactant, azide, was absent. Our results do not support the catalysis-induced diffusion enhancement of the components of the click reaction and, instead, point to the role of a relatively large intermediate species within the reaction cycle with diffusivity lower than that of both the reactants and product molecule. American Chemical Society 2022-01-14 2022-01-26 /pmc/articles/PMC8796239/ /pubmed/35078321 http://dx.doi.org/10.1021/jacs.1c11754 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Rezaei-Ghaleh, Nasrollah
Agudo-Canalejo, Jaime
Griesinger, Christian
Golestanian, Ramin
Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question
title Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question
title_full Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question
title_fullStr Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question
title_full_unstemmed Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question
title_short Molecular Diffusivity of Click Reaction Components: The Diffusion Enhancement Question
title_sort molecular diffusivity of click reaction components: the diffusion enhancement question
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8796239/
https://www.ncbi.nlm.nih.gov/pubmed/35078321
http://dx.doi.org/10.1021/jacs.1c11754
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