Journal
SOFT MATTER
Volume 7, Issue 16, Pages 7395-7403Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1sm05636k
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Funding
- Agence Nationale de la Recherche [ANR-08-BLAN-0209-01]
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The morphological control of polymer micellar aggregates is a very important issue in applications such as drug delivery and material science. We report the temperature-controlled formation of nanotubes, nanofibers, ellipsoidal and faceted vesicles, and spherical aggregates by nanoprecipitation of amphiphilic diblock copolymers in dioxane/water mixture. The copolymers used are composed of a cholesterol-based smectic liquid crystal core-forming block and a PEG hydrophilic block. The morphology of the micellar self-assemblies was studied by transmission electron microscopy (TEM), cryo-electron microscopy (cryo-TEM) and atomic force microscopy (AFM). In all these aggregates smectic organization is clearly present in the hydrophobic cores. We propose a smectic liquid crystallization-driven self-assembly process for the formation of nanofibers and nanotubes on the basis of small angle X-ray scattering (SAXS) studies during the nanoprecipitation. The temperature dependence of the morphology (from T = 5-55 degrees C) is explained by the free energy consideration. The different aggregates finally dispersed in water after the removal of dioxane are thermally stable at temperature <= 55 degrees C and can be preserved for years at room temperature without structural change.
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