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 (∼1 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.

Cyclic bottlebrush polymers are macrocycles that contain pendent side-chain polymers on nearly every repeat unit. We leveraged a method to generate cyclic bottlebrush polymers utilizing ring-expansion polymerization (REP) followed by subsequent grafting-from via atom-transfer radical polymerization (ATRP) to produce core−shell cyclic bottlebrush polymers and investigated their self-assembly behavior in water. The bottlebrush polymers were comprised of a cyclic backbone with side chains composed of a hydrophobic polystyrene block and a hydrophilic poly(acrylic acid) block. A two-step morphological transformation from spheres to porous spheres to nanobowls (spheres with a single large pore) was observed with solvent exchange from tetrahydrofuran to water. In contrast, under identical experimental conditions, an analogous linear bottlebrush polymer with a similar backbone and side chain degrees of polymerizations did not aggregate into nanobowls but rather exhibited a porous sphere morphology. These unusual morphologies and their propensities to transform can be attributed to changes in the internal viscosity of the aggregates during the solvent exchange process. Additionally, the rate of solvent exchange was found to influence the propensity for shape transformation to occur.

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.