Metal Coordination Induces Phase Segregation in Amphipolar Arborescent Copolymers with a Core−Shell−Corona Architectureстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 25 ноября 2020 г.
Аннотация:Arborescent copolymers with a core−shell−corona(CSC) architecture were synthesized and the topology of themolecules was challenged (constrained) through intramolecularinteractions, resulting in phase separation breaking the symmetry of radial density. The inner poly(2-vinylpyridine) shell of thesearborescent polystyrene-g-[poly(2-vinylpyridine)-b-polystyrene]molecules can self-assemble by binding metallic salts and acids inapolar and intermediate-polarity solvents. Upon loading withHAuCl4, the characteristics of the polymer templates govern the“loading sites” of the metal within the molecules. Uniquemorphologies were observed for the metal-loaded G0−G4 arborescent copolymers investigated, namely, spherical, toroidal,raspberry-like, spherical nanocage, and a new worm-in-sphere morphology. The reason for the emergence of such morphologies isthe interplay among intramolecular interactions of unlike polymer segments, solvent selectivity, the entropic elasticity of thearborescent substrate, and phase segregation induced by coordination with the charged metallic species. Meanwhile, the stability ofthe arborescent molecules against aggregation provides intramolecular phase segregation with imposed “confined” geometry andthus leads to nonconventional morphologies. Furthermore, the size of the arborescent molecules is much smaller than that of otherknown particles (droplets) serving as confined geometries. Computer simulations were used to model the mesostructure of thearborescent copolymers, to demonstrate the influence of solvent selectivity, together with HAuCl4 loading, on the evolution of themorphology of the macromolecules.