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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...

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Autores principales: Smeijers, A. F., Pieterse, Koen, Hilbers, Peter A. J., Markvoort, Albert J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
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.
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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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