Justin D. Fox

A self-repairing, supramolecular polymer system: healability as a consequence of donor–acceptor π–π stacking interactions

A novel supramolecular polymer system, in which the terminal pyrenyl groups of a polyamide intercalate into the chain-folds of a polyimide via electronically-complementary pi-pi stacking, shows both enhanced mechanical properties relative to those of its individual components and facile healing characteristics as a result of the thermoreversibility of non-covalent interactions.

High-strength, healable, supramolecular polymer nanocomposites

A supramolecular polymer blend, formed via π-π interactions between a π-electron rich pyrenyl end-capped oligomer and a chain-folding oligomer containing pairs of π-electron poor naphthalene-diimide (NDI) units, has been reinforced with cellulose nanocrystals (CNCs) to afford a healable nanocomposite material. Nanocomposites with varying weight percentage of CNCs (from 1.25 to 20.0 wt %) within the healable supramolecular polymeric matrix have been prepared via solvent casting followed by compression molding, and their mechanical properties and healing behavior have been evaluated. It is found that homogeneously dispersed films can be formed with CNCs at less than 10 wt %. Above 10 wt % CNC heterogeneous nanocomposites were obtained. All the nanocomposites formed could be rehealed upon exposure to elevated temperatures although, for the homogeneous films, it was found that the healing rate was reduced with increasing CNC content. The best combination of healing efficiency and mechanical properties was obtained with the 7.5 wt % CNC nanocomposite which exhibited a tensile modulus enhanced by as much as a factor of 20 over the matrix material alone and could be fully rehealed at 85 °C within 30 min. Thus it is demonstrated that supramolecular nanocomposites can afford greatly enhanced mechanical properties relative to the unreinforced polymer, while still allowing efficient thermal healing.

Effect of monomer structure and solvent on the growth of supramolecular nanoassemblies on a graphite surface

The self-assembly of high aspect ratio hierarchical surface assemblies, as observed by fluid tapping mode AFM, can be achieved through careful design of the supramolecular interactions between low-molecular-weight adsorbates. Needlelike assemblies of monotopic guanine end-capped alkanes grow on a graphite surface when deposited from a water/DMSO solution. The growth of these assemblies can be monitored by AFM in real time, and the growth rate along the two different axes can be understood (through molecular modeling) in terms of the specific adsorbate-adsorbate interactions along those axes. Additionally, through judicious solvent selection (e.g., use of non-H-bonding solvents such as o-dichlorobenzene), which allows the formation of hydrogen-bonding aggregates in solution and influences the surface-adsorbate interactions, dramatically different surface assemblies of these guanine derivatives are obtained.