How to assemble in water without really bonding : aromatic-donor acceptor interactions in foldamers, DNA intercalation and "pi-stacking"
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Non-covalent interactions are of great interest to chemists and biologists who study the molecular structure and function of biological systems, as well as those who seek to control, undo, or improve upon the efficiency of these systems with man-made chemical tools. The Iverson group has specifically applied noncovalent aromatic donor-acceptor interactions to biotic and abiotic aqueous systems through the use of the electron-rich 1,5-dialkoxynaphthalene (DAN) and electron-deficient 1,4,5,8-naphthalenetetracarboxylic diimide (NDI) moieties. Chapter 1 introduces and reviews the current state of self-assembly research, especially work conducted in aqueous media. Chapter 2 delineates the design and synthesis of a molecule that can self-assemble and form disulfide bonds, with the goal of creating higher-order structure. Chapter 3 comprises the design and synthesis of a series of pendant-NDI bisintercalators of DNA that are distinct from the backbone-incorporated intercalators previously employed in our laboratory. Chapter 4 contextualizes the term of art “pi-stacking,” reviewing the current state of knowledge of specific contributions to this effect and commenting on the putative uniqueness of the interaction. Theoretical and experimental work in the field is summarized. The work discussed in this dissertation serves to expand the scope of programmability of our DNA intercalators, to probe the higher-order assembly behavior of our donor-acceptor pair, and to clarify the term “pi-stacking,” lately overused, that imperfectly describes the interaction that gives both these systems their compelling binding properties.