Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 2778-2788 |
| Number of pages | 11 |
| Journal | Macromolecules |
| Volume | 52 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - 9 Apr 2019 |
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Keywords
- molecular dynamics simulations
- dendrimers
- Host-guest chemistry
- multivalency
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Multivalency in a dendritic host-guest system. / Smeijers, A.F.; Pieterse, Koen; Hilbers, Peter A.J.; Markvoort, Albert J. (Corresponding author).
In: Macromolecules, Vol. 52, No. 7, 09.04.2019, p. 2778-2788.Research output: Contribution to journal › Article › Academic › peer-review
TY - JOUR
T1 - Multivalency in a dendritic host-guest system
AU - Smeijers, A.F.
AU - Pieterse, Koen
AU - Hilbers, Peter A.J.
AU - Markvoort, Albert J.
PY - 2019/4/9
Y1 - 2019/4/9
N2 - 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.
AB - 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.
KW - molecular dynamics simulations
KW - dendrimers
KW - Host-guest chemistry
KW - multivalency
UR - http://www.scopus.com/inward/record.url?scp=85063408446&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.8b02357
DO - 10.1021/acs.macromol.8b02357
M3 - Article
C2 - 30983632
AN - SCOPUS:85063408446
VL - 52
SP - 2778
EP - 2788
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 7
ER -