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Multivalency in a Dendritic Host–Guest System
[Image: see text] Multivalency is an important instrument in the supramolecular chemistry toolkit for the creation of strong specific interactions. In this paper we investigate the multivalency effect in a dendritic host–guest system using molecular dynamics simulations. Specifically, we consider ur...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6458993/ https://www.ncbi.nlm.nih.gov/pubmed/30983632 http://dx.doi.org/10.1021/acs.macromol.8b02357 |
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author | Smeijers, A. F. Pieterse, Koen Hilbers, Peter A. J. Markvoort, Albert J. |
author_facet | Smeijers, A. F. Pieterse, Koen Hilbers, Peter A. J. Markvoort, Albert J. |
author_sort | Smeijers, A. F. |
collection | PubMed |
description | [Image: see text] Multivalency is an important instrument in the supramolecular chemistry toolkit for the creation of strong specific interactions. In this paper we investigate the multivalency effect in a dendritic host–guest system using molecular dynamics simulations. Specifically, we consider urea–adamantyl decorated poly(propyleneimine) dendrimers that together with compatible mono-, bi-, and tetravalent ureidoacetic acid guests can form dynamic patchy nanoparticles. First, we simulate the self-assembly of these particles into macromolecular nanostructures, showing guest-controlled reduction of dendrimer aggregation. Subsequently, we systematically study guest concentration dependent multivalent binding. At low guest concentrations multivalency of the guests clearly increases relative binding as tethered headgroups bind more often than free guests’ headgroups. We find that despite an abundance of binding sites, most of the tethered headgroups bind in close proximity, irrespective of the spacer length; nevertheless, longer spacers do increase binding. At high guest concentrations the dendrimer becomes saturated with bound headgroups, independent of guest valency. However, in direct competition the tetravalent guests prevail over the monovalent ones. This demonstrates the benefit of multivalency at high as well as low concentrations. |
format | Online Article Text |
id | pubmed-6458993 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-64589932019-04-12 Multivalency in a Dendritic Host–Guest System Smeijers, A. F. Pieterse, Koen Hilbers, Peter A. J. Markvoort, Albert J. Macromolecules [Image: see text] Multivalency is an important instrument in the supramolecular chemistry toolkit for the creation of strong specific interactions. In this paper we investigate the multivalency effect in a dendritic host–guest system using molecular dynamics simulations. Specifically, we consider urea–adamantyl decorated poly(propyleneimine) dendrimers that together with compatible mono-, bi-, and tetravalent ureidoacetic acid guests can form dynamic patchy nanoparticles. First, we simulate the self-assembly of these particles into macromolecular nanostructures, showing guest-controlled reduction of dendrimer aggregation. Subsequently, we systematically study guest concentration dependent multivalent binding. At low guest concentrations multivalency of the guests clearly increases relative binding as tethered headgroups bind more often than free guests’ headgroups. We find that despite an abundance of binding sites, most of the tethered headgroups bind in close proximity, irrespective of the spacer length; nevertheless, longer spacers do increase binding. At high guest concentrations the dendrimer becomes saturated with bound headgroups, independent of guest valency. However, in direct competition the tetravalent guests prevail over the monovalent ones. This demonstrates the benefit of multivalency at high as well as low concentrations. American Chemical Society 2019-03-21 2019-04-09 /pmc/articles/PMC6458993/ /pubmed/30983632 http://dx.doi.org/10.1021/acs.macromol.8b02357 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. |
spellingShingle | Smeijers, A. F. Pieterse, Koen Hilbers, Peter A. J. Markvoort, Albert J. Multivalency in a Dendritic Host–Guest System |
title | Multivalency in a Dendritic Host–Guest System |
title_full | Multivalency in a Dendritic Host–Guest System |
title_fullStr | Multivalency in a Dendritic Host–Guest System |
title_full_unstemmed | Multivalency in a Dendritic Host–Guest System |
title_short | Multivalency in a Dendritic Host–Guest System |
title_sort | multivalency in a dendritic host–guest system |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6458993/ https://www.ncbi.nlm.nih.gov/pubmed/30983632 http://dx.doi.org/10.1021/acs.macromol.8b02357 |
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