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Nanomaterials 2018, 8(12), 1029;

Supramolecular Modification of ABC Triblock Terpolymers in Confinement Assembly

Physical Chemistry, University of Duisburg-Essen, 47057 Duisburg, Germany
Organic Chemistry, University of Duisburg-Essen, 41125 Essen, Germany
Center for Nanointegration Duisburg Essen (CENIDE), University of Duisburg-Essen, 47057 Duisburg, Germany
Authors to whom correspondence should be addressed.
Received: 22 November 2018 / Revised: 5 December 2018 / Accepted: 6 December 2018 / Published: 10 December 2018
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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The self-assembly of AB diblock copolymers in three-dimensional (3D) soft confinement of nanoemulsions has recently become an attractive bottom up route to prepare colloids with controlled inner morphologies. In that regard, ABC triblock terpolymers show a more complex morphological behavior and could thus give access to extensive libraries of multicompartment microparticles. However, knowledge about their self-assembly in confinement is very limited thus far. Here, we investigated the confinement assembly of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or SVT) triblock terpolymers in nanoemulsion droplets. Depending on the block weight fractions, we found spherical microparticles with concentric lamella–sphere (ls) morphology, i.e., PS/PT lamella intercalated with P4VP spheres, or unusual conic microparticles with concentric lamella–cylinder (lc) morphology. We further described how these morphologies can be modified through supramolecular additives, such as hydrogen bond (HB) and halogen bond (XB) donors. We bound donors to the 4VP units and analyzed changes in the morphology depending on the binding strength and the length of the alkyl tail. The interaction with the weaker donors resulted in an increase in volume of the P4VP domains, which depends upon the molar fraction of the added donor. For donors with a high tendency of intermolecular packing, a visible change in the morphology was observed. This ultimately caused a shape change in the microparticle. Knowledge about how to control inner morphologies of multicompartment microparticles could lead to novel carbon supports for catalysis, nanoparticles with unprecedented topologies, and potentially, reversible shape changes by light actuation. View Full-Text
Keywords: 3D confinement assembly; block copolymers; halogen bond; microparticles; multicompartment; nanoemulsions; supramolecular chemistry 3D confinement assembly; block copolymers; halogen bond; microparticles; multicompartment; nanoemulsions; supramolecular chemistry

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Quintieri, G.; Saccone, M.; Spengler, M.; Giese, M.; Gröschel, A.H. Supramolecular Modification of ABC Triblock Terpolymers in Confinement Assembly. Nanomaterials 2018, 8, 1029.

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