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Supramolecular Polymer Brushes: Influence of Molecular Weight and Cross-Linking on Linear Viscoelastic Behavior.

ABSTRACT: The origin of unique rheological response in supramolecular brush polymers is investigated using different polymer chemistries (poly(methyl acrylate) (PmA) and poly(ethylene glycol) (PEG)), topologies (linear or star), and molecular weights. A recently developed hydrogen-bonding moiety (1-(6-isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)-urea) (ODIN) was coupled to PmAs and PEGs to form supramolecular brush polymers, the backbone of which is formed by the associated moieties. At low molecular weights of monofunctionalized polymers (both PmA and PEG), the formed brushes are mostly composed of a thick backbone (with very short arms) and are surrounded by other similar brush polymers, which prevent them from diffusing and relaxing. Therefore, the monofunctionalized PmA with a low M n does not show terminal flow even at the highest experimentally studied temperature (or at longest time scales). By increasing the length of the chains, supramolecular brushes with longer arms are obtained. Due to their lower density of thick backbones, these last ones have more space to move and their relaxation is therefore enhanced. In this work, we show that despite similarities between covalent and transient brush polymers, the elastic response in the latter does not originate from the brush entanglements with a large M e (entanglement molecular weight), but it rather stems from the impenetrable rigid backbone and caging effect similar to the one described for hyperstars.

SUBMITTER: Golkaram M

PROVIDER: S-EPMC7315638 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Supramolecular Polymer Brushes: Influence of Molecular Weight and Cross-Linking on Linear Viscoelastic Behavior.

Golkaram Milad M van Ruymbeke Evelyne E Portale Giuseppe G Loos Katja K

Macromolecules 20200604 12

The origin of unique rheological response in supramolecular brush polymers is investigated using different polymer chemistries (poly(methyl acrylate) (PmA) and poly(ethylene glycol) (PEG)), topologies (linear or star), and molecular weights. A recently developed hydrogen-bonding moiety (1-(6-isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)-urea) (ODIN) was coupled to PmAs and PEGs to form supramolecular brush polymers, the backbone of which is formed by the associated moieties. At lo ...[more]

PMID: 32595235

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Project description:Anfinsen's famous experiment showed that the restoration of catalytic activity of a completely unfolded ribonuclease A is only possible when the correct order of events is followed during the refolding process. Inspired by this work, the effect of structural constraints induced by covalent cross-links on the folding of a synthetic polymer chain via hydrogen-bonding interactions is investigated. Hereto, methacrylate-based monomers comprising either benzene-1,3,5-tricarboxamide (BTA)-based or coumarin-based pendants are copolymerized with n-butyl methacrylate in various ratios via reversible addition-fragmentation chain-transfer (RAFT) polymerization. To assess whether the folding and single-chain polymeric nanoparticle (SCPN) formation depend on the order of events, we compare two folding pathways. In the one case, we first covalently cross-link the coumarin pendants within the polymers in a solvent that prevents hydrogen bonding, after which hydrogen bonding is activated, inducing folding of the polymer. In the other case, we induce hydrogen-bonding interactions between tethered BTAs prior to covalent cross-linking of the coumarin pendants. A combination of circular dichroism (CD) spectroscopy, UV-vis spectroscopy, size-exclusion chromatography (SEC), and dynamic light scattering (DLS) is employed to understand the effect of the structural constraints on the folding behavior of these synthetic polymers. The results show that like in ribonuclease A, the order of events matters greatly and determines the outcome. Importantly, a hydrogen-bond-promoting solvent prevents the formation of SCPNs upon covalent cross-linking and results in multichain aggregates. In contrast, covalently cross-linking the polymer when no hydrogen bonds are present followed by inducing hydrogen bonding favors the formation of SCPNs above the UCST of the methacrylate-based polymer. To our surprise, the two systems show a fundamentally different response to changes in temperature, indicating that also in synthetic polymers differences in the folding pathway induce differences in the properties of the resultant nanostructures.

Dataset Information

Supramolecular Polymer Brushes: Influence of Molecular Weight and Cross-Linking on Linear Viscoelastic Behavior.

Publications

Supramolecular Polymer Brushes: Influence of Molecular Weight and Cross-Linking on Linear Viscoelastic Behavior.

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