Spectroscopic Studies of Rhodium(ii) Perfluorobutyrate and Synthesis of Metallo-Hapten Complexes

138 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.In part I, the bonding interactions between rhodium(II) perfluorobutyrate (Rh(,2)(pfb)(,4)) and several Lewis bases was investigated using electron paramagnetic resonance (EPR) and infrared (IR) spectroscopy. The shift of the g-value in the EPR spectra of the spin label complex 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) and the shift of the infrared stretching frequency of carbon monoxide (CO) were measured as various Lewis bases bound to the second rhodium center.When Lewis bases with only sigma binding capabilities bound to the Rh(,2)(pfb)(,4)-TEMPO adduct, a linear relationship was found between the g-shift and the predicted enthalpy of adduct formation. Those bases which were capable of both sigma and pi bonding interactions deviated from this correlation thus demonstrating the importance of pi interactions between Lewis bases and Rh(,2)(pfb)(,4).From the infrared stretching frequencies of the base-Rh(,2)(pfb)(,4)-CO adducts a trend toward increasing sigma bonding ability at the first rhodium center was observed as pi bonding interactions increased at the second rhodium center. This demonstrated the synergistic interaction between the two rhodium centers.In part II, several paramagnetic transition and lanthanide metal complexes were synthesized to be used as haptens to study the normal immune response in rabbits. The metallo-hapten complexes were bound to a carrier protein, injected into albino rabbits then the antibodies specific toward the metallo-hapten separated from the serum.Nuclear magnetic resonance spectra of the antibody populations were obtained before and after addition of the paramagnetic metal complexes to try to identify amino acid residues at the antibodies' active sites. The identification was hampered by the low levels of metallo-hapten specific antibodies. Suggestions were made as to the design of a superior metallo-hapten complex to elicit a greater immune response.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD