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| Title: | DESIGNING MOLECULAR RECOGNITION IN THE CONTEXT OF HYDROGEN BONDING AND MOLECULAR DYNAMICS |
| Authors: | Willis, Peter G. |
| Keywords: | Intramolecular hydrogen bond
Conformational design
Benzimidazole
Oligomers |
| Date Created: | 2001 |
| Publisher: | University of Kentucky |
| Abstract: | The effect of hydrogen bonding on the conformation of organic molecules
unifies two projects in this thesis. In one project, the stability of the intramolecular
hydrogen bond in derivatives of 2-guanidinobenzimidazole was studied by
dynamic 1H NMR spectrometry. The impact that this intramolecular hydrogen
bond had on the bond order of the neutral guanidino group and on the dynamic
conformation of these aromatic structures was related to the concept of hydrogen
bond-assisted resonance. In another project, an oligomer possessing repetitive
conformation and capable of much inter- and intramolecular hydrogen bonding
was designed and synthesized. The sensitivity of this oligomer to changes in
anion concentration, as well as its own propensity to self-aggregate were
measured.
Hydrogen bonds found in many biological oligomers are connected though
a system of conjugated bonds. Guanidinobenzimidazole is a conjugated system
of carbon and nitrogen, connected by an intramolecular hydrogen bond. Several
derivatives of guanidinobenzimidazole were synthesized, and the effect of
several simple alkyl for hydrogen substitutions were studied.
Guanidinobenzimidazole was used as a model to study what effect the
conjugation and the intramolecular hydrogen bond have on each other.
The formation of redundant low energy hydrogen bonds is universal in
biological oligomers. In DNA and RNA multiple hydrogen bonds are formed with
a typical energy contribution of only 1-2 kcal/mol. Individually, these interactions
do not give the biological oligomers their conformational stability, but together
they are very stable. The urea and amide based oligomers designed in the work
and discussed in the thesis should form multiple hydrogen bonds with
themselves and/or with anionic guests. Chiral oligoureas were designed to
possess this characteristic of cooperative conformation that so many biological
oligomers and polymers share. |
| URI: | http://hdl.handle.net/10225/153 |
| Appears in Collections: | Electronic Theses and Dissertations
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| Willis.pdf | | 2663Kb | Adobe PDF | View/Open |
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