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Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains
Chains of hydrogen bonds such as those found in water and proteins are often presumed to be more stable than the sum of the individual H bonds. However, the energetics of cooperativity are complicated by solvent effects and the dynamics of intermolecular interactions, meaning that information on coo...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2017
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5488241/ https://www.ncbi.nlm.nih.gov/pubmed/28493462 http://dx.doi.org/10.1002/anie.201703757 |
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author | Dominelli‐Whiteley, Nicholas Brown, James J. Muchowska, Kamila B. Mati, Ioulia K. Adam, Catherine Hubbard, Thomas A. Elmi, Alex Brown, Alisdair J. Bell, Ian A. W. Cockroft, Scott L. |
author_facet | Dominelli‐Whiteley, Nicholas Brown, James J. Muchowska, Kamila B. Mati, Ioulia K. Adam, Catherine Hubbard, Thomas A. Elmi, Alex Brown, Alisdair J. Bell, Ian A. W. Cockroft, Scott L. |
author_sort | Dominelli‐Whiteley, Nicholas |
collection | PubMed |
description | Chains of hydrogen bonds such as those found in water and proteins are often presumed to be more stable than the sum of the individual H bonds. However, the energetics of cooperativity are complicated by solvent effects and the dynamics of intermolecular interactions, meaning that information on cooperativity typically is derived from theory or indirect structural data. Herein, we present direct measurements of energetic cooperativity in an experimental system in which the geometry and the number of H bonds in a chain were systematically controlled. Strikingly, we found that adding a second H‐bond donor to form a chain can almost double the strength of the terminal H bond, while further extensions have little effect. The experimental observations add weight to computations which have suggested that strong, but short‐range cooperative effects may occur in H‐bond chains. |
format | Online Article Text |
id | pubmed-5488241 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-54882412017-07-13 Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains Dominelli‐Whiteley, Nicholas Brown, James J. Muchowska, Kamila B. Mati, Ioulia K. Adam, Catherine Hubbard, Thomas A. Elmi, Alex Brown, Alisdair J. Bell, Ian A. W. Cockroft, Scott L. Angew Chem Int Ed Engl Communications Chains of hydrogen bonds such as those found in water and proteins are often presumed to be more stable than the sum of the individual H bonds. However, the energetics of cooperativity are complicated by solvent effects and the dynamics of intermolecular interactions, meaning that information on cooperativity typically is derived from theory or indirect structural data. Herein, we present direct measurements of energetic cooperativity in an experimental system in which the geometry and the number of H bonds in a chain were systematically controlled. Strikingly, we found that adding a second H‐bond donor to form a chain can almost double the strength of the terminal H bond, while further extensions have little effect. The experimental observations add weight to computations which have suggested that strong, but short‐range cooperative effects may occur in H‐bond chains. John Wiley and Sons Inc. 2017-06-01 2017-06-19 /pmc/articles/PMC5488241/ /pubmed/28493462 http://dx.doi.org/10.1002/anie.201703757 Text en © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution (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 Dominelli‐Whiteley, Nicholas Brown, James J. Muchowska, Kamila B. Mati, Ioulia K. Adam, Catherine Hubbard, Thomas A. Elmi, Alex Brown, Alisdair J. Bell, Ian A. W. Cockroft, Scott L. Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains |
title | Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains |
title_full | Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains |
title_fullStr | Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains |
title_full_unstemmed | Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains |
title_short | Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains |
title_sort | strong short‐range cooperativity in hydrogen‐bond chains |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5488241/ https://www.ncbi.nlm.nih.gov/pubmed/28493462 http://dx.doi.org/10.1002/anie.201703757 |
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