This thesis begins with a brief overview of supramolecular chemistry and selfassembly
and simple examples derived from Nature that provide the motivation for the
work presented here. The concept of a synthetic noncovalent toolbox is then introduced.
The discussion then focuses more explicitly on side-chain and main-chain functionalized
motifs and the methodologies employed in supramolecular polymer functionalization.
The primary hypothesis of the thesis is that the combination of supramolecular strategies,
ring-opening metathesis polymerization, and a well-understood toolbox of functionalities
capable of noncovalent interactions, comprises a method for generating bioinspired
materials. This hypothesis was tested by synthesizing unique functionalized
supramolecular polymers that allowed for a detailed understanding of the orthogonality
of noncovalent interactions and how such interactions can begin to mimic the complexity
of functional biomaterials. The strategies and methods discussed in the synthesis of these
bioinspired materials are divided into three chapters: (1) an exploration of the self-sorting
phenomena between two non-complementary pairs of hydrogen bonds along polymer
side-chains, (2) the extension of the self-sorting concept to include a metal coordination
moiety, and (3) the side-chain functionalization strategies of chapters 2 and 3 in
combination with the main-chain ROMP methodologies discussed in chapter 1 to form
orthogonally self-assembled multifunctional block copolymers. The main results of this
thesis include the results that multifunctional block copolymers can be fashioned via
ROMP, functionalized in both the main- and side-chains, and self-assembled in an
orthogonal fashion. In addition, these studies have found that self-sorting between pairs of non-complementary hydrogen bonding motifs can occur in supramolecular synthetic
systems, that the interactions are extremely solvent dependent and that these interactions
can result in unexpected phenomena. These results demonstrate the importance of a fully
understood toolbox for the rapid development of supramolecular materials. The
knowledge derived from this toolbox and presented in chapters 2, 3, and 4, allows for the
careful selection of compounds for cleverly designed self-assembly materials inspired by
Nature. Finally, conclusions are drawn to the success of the synthetic toolbox and the
various strategies presented herein, and potential future directions are discussed.
| Identifer | oai:union.ndltd.org:GATECH/oai:smartech.gatech.edu:1853/24627 |
| Date | 08 July 2008 |
| Creators | Burd, Caroline Glenn |
| Publisher | Georgia Institute of Technology |
| Source Sets | Georgia Tech Electronic Thesis and Dissertation Archive |
| Detected Language | English |
| Type | Dissertation |
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