Supramolecular construction of optoelectronic biomaterials

Peptide self-assembly is a powerful method to create functional nanoscale materials such as optoelectronically relevant organic nanostructures. The enormous potential that may come from bringing π-conjugated electronic function into biological environments is poised to impact cell and tissue engineering, biosensors, and related biomedical applications. However, very little synthetic guidance is available with respect to uniting these two different materials sets in a generally applicable manner. In this Account, I describe my group's work to synthesize and assemble peptidic nanostructures built around organic electronic elements. The Account begins with a very brief background to the area of supramolecular electronics, followed by a description of areas where these nanomaterials could be useful in biology. I then discuss the synthetic approaches that we utilized to embed a variety of π-electron units directly within peptide backbones. A key supramolecular challenge with respect to subsequent self-assembly of these new molecules is balancing electrostatic contributions within the resulting nanomaterials, because the suitable geometries for stabilizing peptide assemblies may not necessarily correspond to those suitable for maximizing intermolecular π-electron interactions. Regardless of the respective magnitudes of these two major influences, the assembly paradigm is fairly robust. Variation of the π-electron units and the peptide sequences that make up the "peptide-π-peptide" triblock molecules consistently leads to fairly uniform tape-like nanostructures that maintain strong electronic coupling among the component π-electron units. We explored a diverse range of π-electron units spanning fluorescent oligo(phenylene vinylene)s, electron-accepting rylene diimides, and hole-transporting oligothiophenes. I then describe the characterization of the nanomaterials that form after molecular self-assembly in order to understand their internal structures, electronic interactions, and morphologies as existing within self-supporting hydrogel matrices. I also describe how a facile shearing process provided globally aligned macroscopic collections of one-dimensional electronic fibrils in hydrogel matrices. These general assembly processes influence intermolecular π-stacking among the embedded chromophores, and the assemblies themselves can facilitate the covalent cross-linking and polymerization (for example, of reactive diyne units). The latter offers an exciting possibility to create peptidic nanostructures comprised of single polymer chains. Finally, I discuss electronic properties as manifested in the interactions of transition dipoles within the nanomaterials and electrical properties resulting from field-effect gating. The ability to tune the observable electrical properties of the nanostructures externally will allow for their transition to in vitro or in vivo platforms as a powerful new approach to regulating biological interactions at the nanoscale.