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Title:Design, Synthesis and Applications of Complementary Quadruply Hydrogen Bonding Modules: A. Redox Responsive Naphthyridine and Application in Polymers. B. Probing the Polymeric Environmental Effect on the Complexation of Strong Hydrogen Bonding Species
Author(s):Quansah, Jennifer Efua Kwansima
Doctoral Committee Chair(s):Zimmerman, Steven C.
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Organic
Chemistry, Polymer
Abstract:As an approach to counter certain drawbacks that exist in the use of DNA as a building material for nanotechnology, simpler DNA inspired modules have been designed. These are units that have the desired property of forming multiple hydrogen bonds. The compounds can be prepared conveniently from inexpensive starting materials and thus are available in large quantities. By their design, exhibit high stability in self-association or hetero-complexation, enabling a high fidelity assembly.
This dissertation reports on the optimization of reproducible reaction conditions for the synthesis of the two previously reported quadruply hydrogen bonded modules, ureido guanosine (UG), and 2,7-diamido-1,8-naphthyridine (DAN), and various analogues. In particular, we report on efforts towards the generation of multi-gram quantities of these units. Efforts towards the synthesis of the newly designed quadruply hydrogen bonding module, ureido-7-deazaguanine (DeUG), is also presented.
To illustrate the utility of DAN and UG in supramolecular chemistry, DAN and DeUG functionalized monomers were synthesized and copolymerized with styrene and butyl methacrylate. The DAN and UG incorporated polymers presented here demonstrate the ability of these functionalized polymers to exhibit enhanced properties that are unavailable to traditional unfunctionalized polymers. Blends of polystyrene (PS) and poly(butyl methacrylate) (PBMA) are formed where miscibility is driven by the high affinity exhibited by the DAN and UG recognition units. In addition, these units are utilized in the surface functionalization of silica particles.
There is a growing interest in "smart" materials that display specific responses to stimuli. We report the design, synthesis and application of an oxygen and redox responsive hydrogen bonding module, N-(2-(4-hydroxyphenylamino)-1,8-naphthyridin-7-yl)heptanamide, (eDAN). The reduction-oxidation of eDAN is pseudo-reversible over multiple cycles without any signs of decomposition. Further, by taking advantage of the changes in binding affinity of the eDAN:UG complex on oxidation-reduction, eDAN is incorporated into polymers that gel and liquefy on redox stimulation.
To better understand the effect of larger macromolecules and polymeric environment on hydrogen bonding, polymers were synthesized with the quadruply hydrogen bonding module, DAN situated at the middle of the linear backbone. Using polymers with different backbone polarities (polystyrene and poly (butyl methacrylate)) and varying molecular weight, a guanosine analogue, G was used as a sensitive probe of the nature of the polymeric environment created around the host situated at the core of the polymer. We attempt to answer the question of how changes in polarity and molecular weight of the polymer backbone affect the final properties of the supramolecular material.
Issue Date:2009
Description:190 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2009.
Other Identifier(s):(UMI)AAI3392439
Date Available in IDEALS:2014-12-17
Date Deposited:2009

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