Issue 12, 2020

Effects of topological constraints on linked ring polymers in solvents of varying quality

Abstract

We investigate the effects of topological constraints in catenanes composed of interlinked ring polymers on their size in a good solvent as well as on the location of their θ-point when the solvent quality is worsened. We mainly focus on poly[n]catenanes consisting of n ring polymers each of length m interlocked in a linear fashion. Using molecular dynamics simulations, we study the scaling of the poly[n]catenane's radius of gyration in a good solvent, assuming in general that Rgmμnν and we find that μ = 0.65 ± 0.02 and ν = 0.60 ± 0.01 for the range of n and m considered. These findings are further rationalized with the help of a mean-field Flory-like theory yielding the values of μ = 16/25 and ν = 3/5, consistent with the numerical results. We show that individual rings within catenanes feature a surplus swelling due to the presence of NL topological links. Furthermore, we consider poly[n]catenanes in solvents of varying quality and we demonstrate that the presence of topological links leads to an increase of its θ-temperature in comparison to isolated linear and ring chains with the following ordering: Tθcatenane > Tθlinear > Tθring. Finally, we show that the presence of links similarly raises the θ-temperature of a single linked ring in comparison to an unlinked one, bringing its θ-temperature close to the one of a poly[n]catenane.

Graphical abstract: Effects of topological constraints on linked ring polymers in solvents of varying quality

Article information

Article type
Paper
Submitted
02 Dec 2019
Accepted
20 Feb 2020
First published
04 Mar 2020

Soft Matter, 2020,16, 3029-3038

Effects of topological constraints on linked ring polymers in solvents of varying quality

Z. Ahmadian Dehaghani, I. Chubak, C. N. Likos and M. R. Ejtehadi, Soft Matter, 2020, 16, 3029 DOI: 10.1039/C9SM02374G

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