Date of Award

2017

Document Type

Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

Committee Chair

Anusree Mukherjee

Committee Member

Bernhard Vogler

Committee Member

Carmen Scholz

Subject(s)

Ligands, Coordination compounds, Active oxygen, Superoxide dismutase

Abstract

Reactive oxygen species (ROS) naturally occur as side products of oxidation reactions in aerobic organisms, however high concentrations of ROS can cause tissue damage and even cell death. Thus, aerobic organisms have developed several mechanisms of defense against ROS that include catalase (CAT), glutathione peroxidase (GPx), and superoxide dismutase (SOD) enzymes. This thesis details the design and synthesis of novel nickel superoxide dismutase (NiSOD) and copper zinc superoxide dismutase (CuZnSOD) biomimics which were probed for reactivity with superoxide and hydrogen peroxide. The metal complexes are supported by nitrogen rich, macrocyclic ligands that were designed to alter the electronic environment of the metal center in order to support superoxide dismutation. Experiments with KO2 and H2O2 monitored by absorption spectroscopy suggest the formation of a M-O2 adduct which is a key intermediate in the SOD enzyme mechanism. Both the nickel and copper complexes demonstrated superoxide reduction.

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