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Title page for ETD etd-03222009-164627


Type of Document Dissertation
Author Boone, Marcus Alexander
Author's Email Address mboone@chem.fsu.edu
URN etd-03222009-164627
Title Determining the Solution Conformational Entropy of Oligosaccharides: Isolating the Effects of Anomeric Configuration, Glycosidic Linkage, Degree of Polymerization, Linearity versus Cyclicity, and Hydrogen Bonding
Degree Doctor of Philosophy
Department Chemistry and Biochemistry, Department of
Advisory Committee
Advisor Name Title
Andre Striegel Committee Chair
Hugh Nymeyer Committee Member
John Dorsey Committee Member
Emmanuel Collins Outside Committee Member
Keywords
  • Size-exclusion Chromatography
  • Conformational Entropy
  • Oligosaccharides
Date of Defense 2009-02-27
Availability restricted
Abstract
Oligosaccharides have various fundamental roles, ranging from providing nutritional and flavoring support to being involved in fertilization and parasite infection processes. Maltooligosaccharides are used heavily in the food and pharmaceutical industries, cellooligosaccharides have shown promise as prebiotic candidates, and cyclodextrins are potential candidates for drug delivery. Factors such as degree of polymerization and hydrogen bonding play key roles in the aforementioned processes and phenomena. Other factors such as anomeric configuration have been shown to influence bacterial binding and docking, while the glycosidic linkage is known to be a factor in binding processes such as those related to the interspecies spreading of avian influenza virus.

Our group has pioneered the use of size-exclusion chromatography (SEC) in investigating solution conformational entropy (∆S) of select O-linked disaccharides and their monosaccharide constituents. I recently expanded the scope of these investigations to quantitate the ∆S of several homologous series of oligosaccharides, malto- and cellooligosaccharides and cyclodextrins. By using SEC and appropriate selection of hydrogen-bond accepting or non hydrogen-bond accepting solvents, I was able to isolate and quantitate the individual contributions of degree of polymerization, anomeric configuration, linearity versus cyclicity, and hydrogen bonding to the solution conformational entropy of the oligosaccharides. Due to the importance of oligosaccharides in biomolecular recognition phenomena, the next step was to study oligosaccharides at quasi-physiological conditions, i.e., in an aqueous solvent, at 37 C, and at a pH of 7.39.

In the final step of the research I isolated the effects of glycosidic linkage on solution conformational entropy. To this effect, I compared homologous series of -(16) and -(1 3) oligomers, individually, to their -(1 4) and -(14) counterparts, respectively. The -(16) oligomers were the isomaltosides with DP 2-7, which were compared to the maltooligosaccharides. The -(1 3) series examined were the laminarbiosides with DP 2-7, compared to the previously studied cellooligosaccharides.

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