Unusually Conductive Organic-Inorganic Hybrid Nanostructures Derived from Bio-Inspired Mineralization of Peptide/Pi-Electron Assemblies

Supramolecular materials derived from pi-conjugated peptidic macromolecules are well-established to self-assemble into 1D nanostructures. In the presence of KOH, which was used to more fully dissolve the peptide macromolecules prior to triggering the self-assembly by way of exposure to HCl vapor, we report here an unexpected mineralization of KCl as templated presumably by the glutamic acid residues that were present along the backbone of the peptide macromolecules. In order to decouple the peptidic side chains from the central pi-electron unit, three-carbon spacers were added between them on both sides. The assembled structures that resulted from the collective formation of beta-sheets, pi-orbital overlaps, and mineralization resulted in highly interconnected dendritic structures under suitable KOH concentrations. Electrical measurements indicated that when well-interconnected, these dendritic structures maintained conductivities comparable to those of metals at around 1800 S/cm. About 50 mA current was measured for 0.5 V/37.5 mu m. Varying the gate voltage in a transistor configuration had no effect on the current levels, indicating a conductive instead of a semiconducting pathway. Control experiments without the peptide, measurements of conductivity over time, and conductivity quenching by ammonia suggested the conductivity of these dendritic networks was derived from proton doping of the central pi-electron units in a strong acid environment and was facilitated by closely spaced chromophores, as suggested in the literature, leading to facile pi-electron transfer along the interconnected dendritic pathways. Our findings suggest that mineralization templated by appropriate amino acids combined with peptide/pi-electron self-assembly can lead to highly conductive dendritic macrostructures as well as control of nanowire growth in specific directions.