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The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry
Flex‐activated mechanophores can be used for small‐molecule release in polymers under tension by rupture of covalent bonds that are orthogonal to the polymer main chain. Using static and dynamic quantum chemical methods, we here juxtapose three different mechanical deformation modes in flex‐activate...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7702058/ https://www.ncbi.nlm.nih.gov/pubmed/32964598 http://dx.doi.org/10.1002/cphc.202000739 |
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author | Mier, Lennart J. Adam, Gheorghe Kumar, Sourabh Stauch, Tim |
author_facet | Mier, Lennart J. Adam, Gheorghe Kumar, Sourabh Stauch, Tim |
author_sort | Mier, Lennart J. |
collection | PubMed |
description | Flex‐activated mechanophores can be used for small‐molecule release in polymers under tension by rupture of covalent bonds that are orthogonal to the polymer main chain. Using static and dynamic quantum chemical methods, we here juxtapose three different mechanical deformation modes in flex‐activated mechanophores (end‐to‐end stretching, direct pulling of the scissile bonds, bond angle bendings) with the aim of proposing ways to optimize the efficiency of flex‐activation in experiments. It is found that end‐to‐end stretching, which is a traditional approach to activate mechanophores in polymers, does not trigger flex‐activation, whereas direct pulling of the scissile bonds or displacement of adjacent bond angles are efficient methods to achieve this goal. Based on the structural, energetic and electronic effects responsible for these observations, we propose ways of weakening the scissile bonds experimentally to increase the efficiency of flex‐activation. |
format | Online Article Text |
id | pubmed-7702058 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-77020582020-12-14 The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry Mier, Lennart J. Adam, Gheorghe Kumar, Sourabh Stauch, Tim Chemphyschem Communications Flex‐activated mechanophores can be used for small‐molecule release in polymers under tension by rupture of covalent bonds that are orthogonal to the polymer main chain. Using static and dynamic quantum chemical methods, we here juxtapose three different mechanical deformation modes in flex‐activated mechanophores (end‐to‐end stretching, direct pulling of the scissile bonds, bond angle bendings) with the aim of proposing ways to optimize the efficiency of flex‐activation in experiments. It is found that end‐to‐end stretching, which is a traditional approach to activate mechanophores in polymers, does not trigger flex‐activation, whereas direct pulling of the scissile bonds or displacement of adjacent bond angles are efficient methods to achieve this goal. Based on the structural, energetic and electronic effects responsible for these observations, we propose ways of weakening the scissile bonds experimentally to increase the efficiency of flex‐activation. John Wiley and Sons Inc. 2020-10-07 2020-11-03 /pmc/articles/PMC7702058/ /pubmed/32964598 http://dx.doi.org/10.1002/cphc.202000739 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Mier, Lennart J. Adam, Gheorghe Kumar, Sourabh Stauch, Tim The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry |
title | The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry |
title_full | The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry |
title_fullStr | The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry |
title_full_unstemmed | The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry |
title_short | The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry |
title_sort | mechanism of flex‐activation in mechanophores revealed by quantum chemistry |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7702058/ https://www.ncbi.nlm.nih.gov/pubmed/32964598 http://dx.doi.org/10.1002/cphc.202000739 |
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