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Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude

The reaction kinetics between like-charged compounds in water is extremely slow due to Coulomb repulsions. Here, we demonstrate that by screening these interactions and, in consequence, increasing the local concentration of reactants, we boost the reactions by many orders of magnitude. The reaction...

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Autores principales: Kowalski, Adam, Bielec, Krzysztof, Bubak, Grzegorz, Żuk, Pawel J., Czajkowski, Maciej, Sashuk, Volodymyr, Huck, Wilhelm T. S., Antosiewicz, Jan M., Holyst, Robert
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9616817/
https://www.ncbi.nlm.nih.gov/pubmed/36307412
http://dx.doi.org/10.1038/s41467-022-34182-z
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author Kowalski, Adam
Bielec, Krzysztof
Bubak, Grzegorz
Żuk, Pawel J.
Czajkowski, Maciej
Sashuk, Volodymyr
Huck, Wilhelm T. S.
Antosiewicz, Jan M.
Holyst, Robert
author_facet Kowalski, Adam
Bielec, Krzysztof
Bubak, Grzegorz
Żuk, Pawel J.
Czajkowski, Maciej
Sashuk, Volodymyr
Huck, Wilhelm T. S.
Antosiewicz, Jan M.
Holyst, Robert
author_sort Kowalski, Adam
collection PubMed
description The reaction kinetics between like-charged compounds in water is extremely slow due to Coulomb repulsions. Here, we demonstrate that by screening these interactions and, in consequence, increasing the local concentration of reactants, we boost the reactions by many orders of magnitude. The reaction between negatively charged Coenzyme A molecules accelerates ~5 million-fold using cationic micelles. That is ~10(4) faster kinetics than in 0.5 M NaCl, although the salt is ~10(6) more concentrated. Rate enhancements are not limited to micelles, as evidenced by significant catalytic effects (10(4)–10(5)-fold) of other highly charged species such as oligomers and polymers. We generalize the observed phenomenon by analogously speeding up a non-covalent complex formation—DNA hybridization. A theoretical analysis shows that the acceleration is correlated to the catalysts’ surface charge density in both experimental systems and enables predicting and controlling reaction rates of like-charged compounds with counter-charged species.
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spelling pubmed-96168172022-10-30 Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude Kowalski, Adam Bielec, Krzysztof Bubak, Grzegorz Żuk, Pawel J. Czajkowski, Maciej Sashuk, Volodymyr Huck, Wilhelm T. S. Antosiewicz, Jan M. Holyst, Robert Nat Commun Article The reaction kinetics between like-charged compounds in water is extremely slow due to Coulomb repulsions. Here, we demonstrate that by screening these interactions and, in consequence, increasing the local concentration of reactants, we boost the reactions by many orders of magnitude. The reaction between negatively charged Coenzyme A molecules accelerates ~5 million-fold using cationic micelles. That is ~10(4) faster kinetics than in 0.5 M NaCl, although the salt is ~10(6) more concentrated. Rate enhancements are not limited to micelles, as evidenced by significant catalytic effects (10(4)–10(5)-fold) of other highly charged species such as oligomers and polymers. We generalize the observed phenomenon by analogously speeding up a non-covalent complex formation—DNA hybridization. A theoretical analysis shows that the acceleration is correlated to the catalysts’ surface charge density in both experimental systems and enables predicting and controlling reaction rates of like-charged compounds with counter-charged species. Nature Publishing Group UK 2022-10-28 /pmc/articles/PMC9616817/ /pubmed/36307412 http://dx.doi.org/10.1038/s41467-022-34182-z Text en © The Author(s) 2022, corrected publication 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Kowalski, Adam
Bielec, Krzysztof
Bubak, Grzegorz
Żuk, Pawel J.
Czajkowski, Maciej
Sashuk, Volodymyr
Huck, Wilhelm T. S.
Antosiewicz, Jan M.
Holyst, Robert
Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude
title Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude
title_full Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude
title_fullStr Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude
title_full_unstemmed Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude
title_short Effective screening of Coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude
title_sort effective screening of coulomb repulsions in water accelerates reactions of like-charged compounds by orders of magnitude
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9616817/
https://www.ncbi.nlm.nih.gov/pubmed/36307412
http://dx.doi.org/10.1038/s41467-022-34182-z
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