Supramolecular copolymers predominated by alternating order: Theory and application

Abstract

We investigate the copolymerization behavior of a two-component system into quasilinear self-assemblies under conditions that interspecies binding is favored over identical species binding. The theoretical framework is based on a coarse-grained self-assembled Ising model with nearest neighbor interactions. In Ising language, such conditions correspond to the antiferromagnetic case giving rise to copolymers with predominantly alternating configurations. In the strong coupling limit, we show that the maximum fraction of polymerized material and the average length of strictly alternating copolymers depend on the stoichiometric ratio and the activation free energy of the more abundant species. They are substantially reduced when the stoichiometric ratio noticeably differs from unity. Moreover, for stoichiometric ratios close to unity, the copolymerization critical concentration is remarkably lower than the homopolymerization critical concentration of either species. We further analyze the polymerization behavior for a finite and negative coupling constant and characterize the composition of supramolecular copolymers. Our theoretical insights rationalize experimental results of supramolecular polymerization of oppositely charged monomeric species in aqueous solutions.

Autoren

Reinier van Buel
Daniel Spitzer
Christian Marijan Berac
Paul van der Schoot
Pol Besenius
Sara Jabbari-Farouji

DOI

10.1063/1.5097577

eISSN

1089-7690

ISSN

0021-9606

Ausgabe der Veröffentlichung

1

Zeitschrift

The Journal of Chemical Physics

Sprache

en

Online publication date

2019

Datum der Veröffentlichung

2019

Status

Published

Herausgeber

AIP Publishing

Herausgeber URL

http://dx.doi.org/10.1063/1.5097577

Datum der Datenerfassung

2023

Titel

Supramolecular copolymers predominated by alternating order: Theory and application

Ausgabe der Zeitschrift

151

Datenquelle: Crossref

Abstract

We investigate the copolymerization behavior of a two-component system into quasilinear self-assemblies under conditions that interspecies binding is favored over identical species binding. The theoretical framework is based on a coarse-grained self-assembled Ising model with nearest neighbor interactions. In Ising language, such conditions correspond to the antiferromagnetic case giving rise to copolymers with predominantly alternating configurations. In the strong coupling limit, we show that the maximum fraction of polymerized material and the average length of strictly alternating copolymers depend on the stoichiometric ratio and the activation free energy of the more abundant species. They are substantially reduced when the stoichiometric ratio noticeably differs from unity. Moreover, for stoichiometric ratios close to unity, the copolymerization critical concentration is remarkably lower than the homopolymerization critical concentration of either species. We further analyze the polymerization behavior for a finite and negative coupling constant and characterize the composition of supramolecular copolymers. Our theoretical insights rationalize experimental results of supramolecular polymerization of oppositely charged monomeric species in aqueous solutions.

Addresses

Institute of Physics, Johannes Gutenberg-University, Staudingerweg 7-9, 55128 Mainz, Germany.

Autoren

Reinier van Buel
Daniel Spitzer
Christian Marijan Berac
Paul van der Schoot
Pol Besenius
Sara Jabbari-Farouji

DOI

10.1063/1.5097577

eISSN

1089-7690

Externe Identifier

PubMed Identifier: 31272178

Funding acknowledgements

Deutsche Forschungsgemeinschaft: 233630050 - TRR 146

Open access

false

ISSN

0021-9606

Ausgabe der Veröffentlichung

1

Zeitschrift

The Journal of chemical physics

Sprache

eng

Medium

Print

Paginierung

014902

Datum der Veröffentlichung

2019

Status

Published

Datum der Datenerfassung

2019

Titel

Supramolecular copolymers predominated by alternating order: Theory and application.

Sub types

Journal Article

Ausgabe der Zeitschrift

151

Datenquelle: Europe PubMed Central

Abstract

We investigate the copolymerization behavior of a two-component system into quasilinear self-assemblies under conditions that interspecies binding is favored over identical species binding. The theoretical framework is based on a coarse-grained self-assembled Ising model with nearest neighbor interactions. In Ising language, such conditions correspond to the antiferromagnetic case giving rise to copolymers with predominantly alternating configurations. In the strong coupling limit, we show that the maximum fraction of polymerized material and the average length of strictly alternating copolymers depend on the stoichiometric ratio and the activation free energy of the more abundant species. They are substantially reduced when the stoichiometric ratio noticeably differs from unity. Moreover, for stoichiometric ratios close to unity, the copolymerization critical concentration is remarkably lower than the homopolymerization critical concentration of either species. We further analyze the polymerization behavior for a finite and negative coupling constant and characterize the composition of supramolecular copolymers. Our theoretical insights rationalize experimental results of supramolecular polymerization of oppositely charged monomeric species in aqueous solutions.

Autoren

Reinier van Buel
Daniel Spitzer
Christian Marijan Berac
Paul van der Schoot
Pol Besenius
Sara Jabbari-Farouji

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/31272178

DOI

10.1063/1.5097577

eISSN

1089-7690

Ausgabe der Veröffentlichung

1

Zeitschrift

J Chem Phys

Sprache

eng

Country

United States

Paginierung

014902

Datum der Veröffentlichung

2019

Status

Published

Titel

Supramolecular copolymers predominated by alternating order: Theory and application.

Sub types

Journal Article

Ausgabe der Zeitschrift

151

Datenquelle: PubMed

Supramolecular copolymers predominated by alternating order: Theory and application

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