Magnetic Nanoparticles Improve Flow Rate and Enable Self-Healing in Covalent Adaptable Networks.

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.

Hierarchical Fractal Assemblies from Poly(ethylene oxide- b-lysine- b-leucine).

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.

Evaluating the Impact of Fluorination on the Electro-optical Properties of Cross-Conjugated Benzobisoxazoles.

Six 2,4,6,8-tetrarylbenzo[1,2- d:4,5- d']bisoxazoles (BBOs) were synthesized: three bearing phenyl substituents at the 2- and 6-positions and three bearing perfluorophenyl groups at those positions. The influence of perfluoro-aryl group substitution on the physical, optical, and electronic properties of 2,4,6,8-tetrarylbenzo[1,2- d:4,5- d']bisoxazoles (BBO) was evaluated using both experimental and theoretical methods. The density functional theory (DFT) model was found to be well-matched to the experimental optical data, as evidenced by the UV-vis spectra. Both cyclic voltammetry (CV) and ultraviolet photoelectron spectroscopy (UPS) were used to determine the position of the HOMO with varying results. The values obtained by CV were deeper than those obtained via UPS and correlated well with the theoretical calculations. However, the UPS values were more consistent with the expected outcomes for a system with segregated frontier molecular orbitals (FMOs). The UPS results are also supported by the electrostatic potential maps, which indicate that the electron density within the LUMO and HOMO is nearly completely localized along the 2,6- or 4,8-axis, respectively. The summation of the results indicates that strongly electron-withdrawing groups can be used to selectively tune the LUMO level with minor perturbation of the HOMO, something that is challenging to accomplish in typical donor-acceptor systems.