RESUMEN
Covalent adaptable networks (CANs) combine the mechanical and chemical stability of thermosets with the reprocessability of thermoplastics through the incorporation of stimuli-responsive dynamic crosslinks. To allow for processing through induction heating, we have created associative CANs that include fillers in the polymer matrix for efficient heat transfer. While the inclusion of inorganic fillers often decreases flow rate in CANs and complicates reprocessing of the material, the presence of Fe3O4 nanoparticles had no detrimental effect on flow behavior in a vinylogous urethane vitrimer, an observation we attribute to the catalytic nature of nanoparticles on the dynamic exchange chemistry. We employed two methods of nanoparticle incorporation: blending bare nanoparticles and crosslinking chemically modified nanoparticles. The vitrimers with covalently crosslinked nanoparticles exhibited a decreased relaxation time compared to those with blended nanoparticles. The magnetic character of the Fe3O4 nanoparticles enabled self-healing of the vitrimer composite materials upon exposure to an alternating electromagnetic field during induction heating.
RESUMEN
Poly(ethylene oxide43- b-lysine62- b-leucine72) (wherein subscripts denote the degree of polymerization) was synthesized via ring-opening polymerization of N-carboxyanhydrides using an amine-terminated poly(ethylene oxide) macroinitiator, with polypeptide blocks produced by sequential monomer addition. Infrared and circular dichroism spectroscopy indicated that the peptide blocks in this polymer formed α-helices in the solid and solution states, respectively. In the aqueous solution, this polymer self-assembled into spherical micelles with a hydrodynamic radius of approximately 90 nm at concentrations between 0.05 and 0.20% w/w and pH values between 2 and 6.5. Upon preparation of transmission electron microscopy (TEM) grids, the micelles at pH 2 underwent hierarchical assembly to produce fractal assemblies, whereas small clusters were observed for micellar solutions at pH 6.5. Cryogenic-TEM of solutions showed spherical micelles, and dynamic light scattering showed no large (â¼1 µm) aggregates in the solution, which suggests that fractal formation was a result of the drying process, and that fractals were not present in the solution. This system provides a facile route to nanostructured surfaces, which can be used for applications such as modulating cell adhesion or promoting the growth of neurons.
