The influence of directed hydrogen bonds on the self-assembly of amphiphilic polymers in water.

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ID: 50253
2019
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Abstract
Molecules forming directed intermolecular hydrogen bonds, such as the well-known benzene-1,3,5-tricarboxamides (BTA) motif, are known to self-assemble into long fibrous structures. However, only a few of these systems have so far demonstrated the ability to form such anisotropic nanostructures, if they are combined with hydrophilic polymers to create an amphiphilic material. Here, we designed BTA-polymer conjugates to investigate whether the directionality of the hydrogen bonds or the ratio of hydrophobic to hydrophilic parts of the molecule, and thus the packing parameter, is decisive for obtaining anisotropic supramolecular structures in water.Poly(ethylene glycol) was conjugated to BTA moieties with varying lengths of hydrophobic alkyl spacers ranging from two to twelve methylene units. The resulting amphiphilic materials were characterized in aqueous solution by light and small-angle neutron scattering, analytical ultracentrifugation, and cryo-transmission electron microscopy.While spherical micelles were observed for C and C alkyl spacers, anisotropic structures were only present in case of the C spacer. The comparison to an analogous material, which lacks the directed hydrogen bonds, revealed that the BTA motif cannot provide a sufficient driving force to induce anisotropic structures, but increases the packing density in the hydrophobic part. Therefore, the packing parameter governs the appearance of anisotropic aggregates.
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Authors Klein, Tobias;Gruschwitz, Franka V;Rogers, Sarah;Hoeppener, Stephanie;Nischang, Ivo;Brendel, Johannes C;
Journal Journal of colloid and interface science
Year 2019
DOI
S0021-9797(19)31079-3
URL
Keywords
supramolecular self-assembly block copolymers amphiphilic materials analytical ultracentrifugation benzenetrisamides hydrogen bonds packing parameter

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