Aminobiphenylcarboxylic acid derivatives for the creation of nanometer-scale molecular rods and shape -persistent macrocycles

This dissertation contains three chapters involving the design and synthesis of nanometer-sized building blocks for the creation of nanometer-scaled architectures. Chapter 1 describes the development of aminobiphenylcarboxylic acid (Abc)-based amino acids and their use in synthesis of molecular rods. The chapter begins with Abc building blocks designed for solubility in lipophilic organic solvents (AbcR) and ends with the development of a water-soluble Abc analog, Abc2K. Chapter 1 focuses on the development and transition from molecular rods containing aliphatic side chains [Boc-(Abc R)n-OR, n =1-4] that can be solublized in organic solvents to molecular rods containing charged moieties [H-(AbcK) n-NH2, n =1-5 and H-(Abc2K)n-NH 2, n =1-10] that can be solublized in water. Chapter 1 introduces Abc 2K oligomers as a new class of water-soluble molecular rods that can be synthesized in precise and defined lengths up to at least 10 nm in 1-nm increments. The synthesis of the protected building blocks and compatibility of the building blocks with standard solid-phase peptide synthesis techniques will be demonstrated. The compatibility of the unprotected water-soluble oligomers with standard analytical purification and characterization techniques will also be demonstrated. Finally, the chapter ends in a discussion about the biological applications of Abc2K amino acids by showing how they can be combined with alpha-amino acids to serve as rigid linkers between various biologically relevant peptides.;Chapter 2 describes the rigidity studies used to support a model in which Abc2K oligomers are relatively straight and rigid. The question of rigidity is first addressed by way of molecular modeling studies. Fluorescence resonance energy transfer (FRET) experiments of Abc2K oligomers are then described and will show that Abc2K oligomers behave as rigid rods with a length of 1.0 nm per monomer unit. Finally, Chapter 2 describes my work involving TEM and AFM imaging of supramolecular assemblies that are formed from individual Abc2K oligomers.;Chapter 3 describes how variants of the Abc2K building block, m-Abc2K and o-Abc 2K, can be combined to create various types of molecular architectures, such as angled molecular rods and shape-persistent macrocycles of shapes that resemble triangles, parallelograms, and hexagons.