Details

Autor(en) / Beteiligte

• Gothard, Chris M

Titel

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

Erscheinungsjahr

2007

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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 (Abc < super > R < /er > ) and ends with the development of a water-soluble Abc analog, Abc < super > 2K < /er > . Chapter 1 focuses on the development and transition from molecular rods containing aliphatic side chains [Boc-(Abc < super > R < /er > )(n)-OR, n =1-4] that can be solublized in organic solvents to molecular rods containing charged moieties [H-(Abc < super > K < /er > )( n)-NH(2), n =1-5 and H-(Abc < super > 2K < /er > )(n)-NH( 2), n =1-10] that can be solublized in water. Chapter 1 introduces Abc < super > 2K < /er > 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 Abc < super > 2K < /er > 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 Abc < super > 2K < /er > 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 Abc < super > 2K < /er > oligomers are then described and will show that Abc < super > 2K < /er > 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 Abc < super > 2K < /er > oligomers. Chapter 3 describes how variants of the Abc < super > 2K < /er > building block, m-Abc < super > 2K < /er > and o-Abc < super > 2K < /er > , 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.