Dataset Information

A Critical Approach to Polymer Dynamics in Supramolecular Polymers.

ABSTRACT: Over the past few years, the concurrent (1) development of polymer synthesis and (2) introduction of new mathematical models for polymer dynamics have evolved the classical framework for polymer dynamics once established by Doi-Edwards/de Gennes. Although the analysis of supramolecular polymer dynamics based on linear rheology has improved a lot recently, there are a large number of insecurities behind the conclusions, which originate from the complexity of these novel systems. The interdependent effect of supramolecular entities (stickers) and chain dynamics can be overwhelming depending on the type and location of stickers as well as the architecture and chemistry of polymers. This Perspective illustrates these parameters and strives to determine what is still missing and has to be improved in the future works.

SUBMITTER: Golkaram M

PROVIDER: S-EPMC6933822 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

A Critical Approach to Polymer Dynamics in Supramolecular Polymers.

Golkaram Milad M Loos Katja K

Macromolecules 20191216 24

Over the past few years, the concurrent (1) development of polymer synthesis and (2) introduction of new mathematical models for polymer dynamics have evolved the classical framework for polymer dynamics once established by Doi-Edwards/de Gennes. Although the analysis of supramolecular polymer dynamics based on linear rheology has improved a lot recently, there are a large number of insecurities behind the conclusions, which originate from the complexity of these novel systems. The interdependen ...[more]

PMID: 31894159

Similar Datasets

Project description:Polar cosolvents are commonly used to guide the self-assembly of amphiphiles in water. Here we investigate the influence of the cosolvent acetonitrile (ACN) on the structure and dynamics of a supramolecular polymer in water, which is based on the well-known benzene-1,3,5-tricarboxamide motif. Hydrogen/deuterium exchange mass spectroscopy measurements show that a gradual increase in the amount of ACN results in a gradual increase in the exchange dynamics of the monomers. In contrast, the morphology of the supramolecular polymers remains unchanged up to 15% of ACN, but then an abrupt change occurs and spherical aggregates are formed. Remarkably, this abrupt change coincides with the formation of micro-heterogeneity in the water-ACN mixtures. The results illustrate that in order to completely characterize supramolecular polymers it is important to add time-resolved measurements that probe their dynamic behavior, to the conventional techniques that are used to assess the morphology of the polymers. Subsequently we have used time-resolved measurements to investigate the influence of the concentration of ACN on the polymerization and depolymerization rates of the supramolecular polymers. Polymerization occurs within minutes when molecularly dissolved monomers are injected from ACN into water and is independent of the fraction of ACN up to 15%. In the depolymerization experiments-initiated by mixing equilibrated supramolecular polymers with dissolved monomers-the equilibration of the system takes multiple hours and does depend on the fraction of ACN. Interestingly, the longest equilibration time of the polymers is observed at a critical solvent composition of around 15% ACN. The differences in the timescales detected in the polymerization and depolymerization experiments are likely correlated to the non-covalent interactions involved, namely the hydrophobic effect and hydrogen-bonding interactions. We attribute the observed fast kinetics in the polymerization reactions to the hydrophobic effect, whereas the formation of intermolecular hydrogen bonds is the retarding factor in the equilibration of the polymers in the depolymerization experiments. Molecular dynamics simulations show that the latter is a likely explanation because ACN interferes with the hydrogen bonds and loosens the internal structure of the polymers. Our results highlight the importance of the solution conditions during the non-covalent synthesis of supramolecular polymers, as well as after equilibration of the polymers.

Dataset Information

A Critical Approach to Polymer Dynamics in Supramolecular Polymers.

Publications

A Critical Approach to Polymer Dynamics in Supramolecular Polymers.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets