No abstract

A novel and facile strategy, combining anisotropic micellization of amphiphilic crystalline-coil copolymer in water and reassembly during single spinneret electrospinning, was developed for preparing nanofibers with very fine core-shell structure. Polyvinyl alcohol (PVA) and polyethylene glycol-block-poly(p-dioxanone) (PEG-b-PPDO) were used as the shell and the crystallizable core layer, respectively. The core-shell structure could be controllably produced by altering concentration of PEG-b-PPDO, and the chain length of the PPDO block. The morphology of the nanofibers was investigated by Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM). X-ray rocking curve measurements were performed to investigate the degree of ordered alignment of the PPDO crystalline lamellae in the nanofiber. The results suggested that the morphology of nanoparticles in spinning solution plays very important role in determining the phase separation of nanofibers. The amphiphilic PEG-b-PPDO copolymer self-assembled into star anise nanoaggregates in water solution induced by the crystallization of PPDO blocks. When incorporated with PVA, the interaction between PVA and PEG-b-PPDO caused a morphological transition of the nanoaggregates from star anise to small flake. For flake-like particles, their flat surface is in favor of compact stacking of PPDO crystalline lamellae and interfusion of amorphous PPDO in the core of nanofibers, leading to a relatively ordered alignment of PPDO crystalline lamellae and well-defined core-shell phase separation. However, for star anise-like nanoaggregates, their multibranched morphology may inevitably prohibit the compact interfusion of PPDO phase, resulting in a random microphase separation.

A novel and facile method was developed for morphological controlling of self-assemblies prepared by crystallization induced self-assembly of crystalline-coil copolymer depending on the combination effect of crystallization and micellization. The morphological evolution of the self-assemblies of alternating poly(p-dioxanone)-block-poly(ethylene glycol) (PPDO-PEG) multiblock copolymer prepared by different solvent mixing methods in aqueous solution were investigated. "Chrysanthemum"-like and "star anise"-like self-assemblies were obtained at different rates of solvent mixing. The results suggested gradually change in solvent quality (slowly dropping water into DMF solution) leaded to a hierarchical micellization-crystallization process of core-forming PPDO blocks, and flake-like particles were formed at the initial stage of crystallization. Meanwhile, crystallization induced micellization process occurred when solvent quality changed drastically. Shuttle-like particles, which have much smaller size than those of flake-like particles, were formed at the initial stage of crystallization when quickly injecting water into DMF solution of the copolymer. Therefore, owing to the different changing rate of solvent quality, which may result in different combination effect of crystallization and micellization during self-assembly of the copolymer, PPDO-PEG self-assemblies with different hierarchical morphology in nano scale could be obtained.

A novel and facile bottom-up strategy for preparing core-shell nanofibers with selectively localized carbon nanotubes is developed using hierarchical composite micelles of crystalline-coil copolymer and carbon nanotubes as the building blocks. An amphiphilic di-block copolymer of poly (p-dioxanone) (PPDO) and PEG (polyethylene glycol) functionalized with pyrene moieties at the chain ends of PPDO blocks (Py-PPDO-b-PEG) is designed for constructing composite micelles with multiwalled carbon nanotubes (MWCNTs). The self-assembly of Py-PPDO-b-PEG and MWCNTs is co-induced by the crystallization of PPDO blocks and the π-π stacking interactions between pyrene moieties and MWCNTs, resulting in composite micelles with "shish kebab"-like nanostructure. A mixture of composite micelles and polyvinyl alcohol (PVA) water solution is then used as the spinning solution for preparing electrospun nanofibers. The morphologies of the nanofibers with different composition are investigated by SEM and TEM. The results suggest that the MWCNTs selectively localized in the core of the nanofibers of MWCNTs/Py-PPDO-b-PEG/PVA. The alignment and interfusion of composite micelles during the formation of nanofibers may confine the carbon nanotubes in the hydrophobic core region. In contrast, the copolymer without pyrene moieties cannot form composite micelles, thus these nanofibers show selective localization of MWCNTs in the PVA shell region.

No abstract