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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...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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Nature Publishing Group UK
2022
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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. |
format | Online Article Text |
id | pubmed-9616817 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
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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