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Construction Of An X-Band Electron Nuclear Double Resonance Spectrometer And Partial Characterization Of An Iron Nitrosyl Complex Of Transferrin, Pamela Marie Proulx-Curry

Doctoral Dissertations

An X-band Electron Nuclear Double Resonance (ENDOR) spectrometer was constructed, tested at both room and liquid helium temperatures, and characterized at liquid helium temperature using a vanadyl-imidazole standard.

An iron nitrosyl complex of transferrin was studied. Three methods of generating nitric oxide gas were tested and resulted in no differences in product formation. The g-factors for the rhombic complex--prepared with and without carbonate addition to the buffer--were determined. For the complex prepared with carbonate g$\sb{\rm x}$ = 2.052, g$\sb{\rm y}$ = 2.028, and g$\sb{\rm z}$ = 2.013. For the complex prepared without addition of carbonate g$\sb{\rm x}$ = 2.051, g$\sb{\rm …

Absorption And Fluorescence Spectra Of Sodium In An Argon Matrix, Alan Bruce Tutein

Doctoral Dissertations

A computer simulation of the formation of trapping sites for sodium atoms trapped in a solid argon matrix has been performed, using experimentally determined argon-argon and sodium-argon potentials available in the literature. The simulation method is a greatly simplified version of the more time-consuming molecular dynamics approach. Optical absorption and emission spectra corresponding to the matrix-perturbed 3s-3p sodium transition were calculated for each simulated trapping site, using first-order perturbation theory and the available sodium-argon dimer potentials. Two of the three requisite sodium-argon dimer potentials, the X$\sp2\Sigma$ and the A$\sp2\Pi,$ have been determined experimentally, but for the B$\sp2\Sigma$ potential, only a …

Novel Pericyclic Routes To Strained Organic Molecules: Theoretical And Experimental Studies, Alexander Zak Bradley

Doctoral Dissertations

The chemistry of cyclobutyne (20) and 1,2-cyclobutadiene (21) has been investigated. Research efforts were focused on attempting to independently generate and trap these highly reactive species. The trapping experiments were inconclusive in each case.

Calculations using MCSCF theory indicate that perfluorination of cyclobutyne will have a profound effect that stabilizes the cyclobutyne relative to rearrangement. However, experiments designed to generate and trap perfluorocyclobutyne (73) did not provide evidence for this compound.

The development of new routes to strained organic compounds through the extension of known pericyclic reactions is described. These novel pericyclic reactions have been investigated by ab initio calculations …

Novel Rearrangements Of Oxonium Ylides And Chain Extension Of Beta-Ketoesters, John Bucknam Brogan

Doctoral Dissertations

A series of ketal-containing diazocarbonyl substrates was prepared. Exposure of these substrates to catalytic Rh(II) and Cu(II) resulted in intramolecular oxonium ylide formation followed by selective rearrangements. The isolated products suggested that bicyclic oxonium ylide rearrangement is controlled by ring strain and ketal substituents. Ylides prepared from larger ring size ketals efficiently generated ring fused products by 1,2-shift of the ketal carbon. Ylides which were prepared from dioxolanes underwent $\beta$-elimination reactions competitively with 1,2-shift of the ketal carbon. When stabilizing groups were present at dioxolane 4 and 5 positions, a 1,2-shift of the exocyclic, stabilized carbon was observed. This novel …