Design and synthesis of self-assembling peptides for fabrication of functional nanomaterials

Abstract

Self-assembling peptides are a class of supramolecular polymers, which exploit noncovalent interactions such as hydrogen bonding, hydrophobic, electrostatic, charge-transfer complex, π-π, and van der Waals interactions to generate well-defined supramolecular nanostructures including nanospheres, nanosheets, nanotubes, and nanofibers. These versatile peptide-based supramolecular nanomaterials have been utilized in variety of applications including catalysis, sensing, light harvesting, optoelectronic, bioelectronic and tissue engineering. In this thesis, use of supramolecular peptide nanofibers formed by specially designed short peptide sequences that can form sheet-like hydrogen bonded structures for controlled synthesis of nanometer scale functional materials were explored. Specifically, n-type and p-type β-sheet forming short peptide sequences were synthesized, which assemble separately into well-ordered nanofibers in aqueous media. These p-type and n-type nanofibers coassemble via hydrogen bonding and electrostatic interactions to generate highly uniform supramolecular n/p-coassembled 1D nanowires. This smart molecular design ensures alternating arrangement of D and A chromophores within n/p-coassembled supramolecular nanowires. Supramolecular n/p- coassembled nanowires were found to be formed by alternating A-D-A unit cells having an association constant of (KA) of 5 x 105 M-1. Moreover, I designed and synthesized β-sheet forming peptide nanofibers to fabricate different metal and metal oxide nanostructures in highly controlled manner using wet chemistry and atomic layer deposition techniques. These hybrid organic-inorganic nanostructures were employed in model Suzuki coupling, alkyne-azide cycloaddition and hydrolysis of ammonia borane reactions.