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Type of Document Dissertation Author Forbes, Christopher C. Author's Email Address cforbes@nd.edu URN etd-07202005-184654 Title Supramolecular Chemistry of Amide Containing Molecules Degree Doctor of Philosophy Department Chemistry and Biochemistry Advisory Committee
Advisor Name Title Marvin J. Miller Committee Member Paul Helquist Committee Member Seth N. Brown Committee Member Keywords
- squaraine
- Rotaxane
- phospholipid flip flop
Date of Defense 2005-06-29 Availability restricted Abstract Amide-based synthetic molecules have been prepared and examined in four separate research projects which investigate conformational isomerization, anion binding, phospholipid translocation and rotaxane formation. It was found that N-(pyrimidin-2-yl)pentafluorobenzamide adopts a cis conformation in the solid state with a nitrogen of the pyrimidine ring pointing toward the center of the perfluorinated ring. In solution the compound is a mixture of cis and trans isomers. The conformational equilibrium is strongly solvent dependent, and the cis conformation is entropically favored. A disulfide macrocyclic compound possessing an isophthalamide moiety, which is a known hydrogen bond donor, was shown to bind chloride, acetate and dihydrogen phosphate anions with binding constants of 30, 137, and 151 M-1 respectively. The binding ability of the isophthalamide moiety was also used to construct rotaxane architectures around fumaramide and squaraine bearing thread molecules. The investigation into squaraine-based rotaxanes shows significant enhancement in chemical stability of the parent squaraine dye molecule with only minimal changes in quantum yield of fluorescence. These results represent a new method of protecting squaraine dyes from harsh chemical environments. Bolaamphiphilic fumaramide-based rotaxanes and amide-based bolaamphiphilic thread molecules that are long enough to span a phospholipid bilayer membrane were shown to induce the translocation of phospholipid probes across vesicle membranes. The mechanism of translocase activity is theorized to be a “slip-pop” mechanism involving local perturbations of the membrane headgroup region.Files
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