PART I: CARBOXYLATE BASED PRECURSORS FOR THE SYNTHESIS OF HEXAKIS(ISONITRILE) TECHNETIUM(I) SALTS. PART II: ELECTROCHEMICALLY MODULATED LIQUID CHROMATOGRAPHY
Abstract
The incessant commerce between technetium chemistry and the particular needs within nuclear medicine has provided the basis for this work. Formate, acetate, and pivalate based complexes of technetium have been examined by subtractively normalized interfacial Fourier transform, electron spin resonance, and electronic spectroscopy, electrochemistry, electrophoresis, and chromatography. Both electrochemical and chemical synthetic routes to the Tc-carboxylate complexes have been explored. These complexes have been proposed to be metal-metal bonded dioxo bridged ditechnetium(IV) species with axial and bridged carboxylate ligands. The Tc-carboxylate complexes show promise as practical starting materials for the synthesis of technetium-99m compounds of known organ imaging ability. Towards this end, hexakis (isonitrile) $\sp{99}$Tc(I) cations have been prepared from carboxylate based starting materials. The following ligands have been employed: tert -butyl, n -butyl, cyclohexyl, and benzyl isonitrile. The products have been characterized by UV-visible and infrared spectroscopy, cyclic voltammetry, fast atom bombardment mass spectrometry, and electrophoresis. The second portion of this work introduces electrochemically modulated liquid chromatography. In this form of chromatography, tunable selectivity control is derived through the electrochemical modulation of a carbon packing material which has been chemically modified with an electroactive molecule. Thus, an electrochemical potential is employed on-column to effect separability in a manner analogous to column switching as well as to solvent or temperature programming. An electrochemically modulated aminoanthraquinone modified carbon packing material is employed to separate phenylalkanols, methylbenzenes, and aromatic hydrocarbons at various applied potentials.
Degree
Ph.D.
Subject Area
Analytical chemistry
Off-Campus Purdue Users:
To access this dissertation, please log in to our
proxy server.