Self-assembled supramolecular peptidic materials are of great interest due to their applications as biocompatible nanoelectronics. Introducing π-functionalities within peptidic domain gives rise to intricate assembly characteristics as well as new avenues for application. Detailed understanding of molecular parameters to modulate the formation of hierarchical structures can inform design principles for materials with engineered optical and electronic properties. In this work, we combine molecular level characterization techniques with all-atom molecular simulations to understand the relationship between supramolecular chirality with molecular level variation in peptide-π-peptide networks. We found out that incorporation of alkyl spacer within peptidic and π-functionalities provide a handle to control supramolecular chirality: even no. of spacer (0,2) showing M-type helical character whereas odd no. of spacer (1,3) induces P-type helical character. Variation of chirality of consituent amino acids also showed how subtle variation of chemical structures may impact supramolecular outcome.<br/>We also investigated the 1D nanostructures and charge transport properties of these peptide-π-peptide networks. In presence of KOH, that was used to dissolve the peptidic materials in aqueous systems prior to formation of self-assembly by exposing it to HCl vapor, we found unexpected biomineralization of KCl templated by glutamic acid residues in the peptidic backbone forming dendritic structures. Electrical characterisation suggested that when well-interconnected, these inorganic-organic hybrid materials maintain conductivities in the metallic range.<br/>Our results presented a molecular-level design rule to engineer supramolecular outcomes of optically and electronically active nanoaggregates along with development of highly conductive dendritic nanostructures formed from these peptide-π conjugated systems.

Self-assembly and application of peptide-driven organic electronic nanostructures in aqueous media

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.