Synthesis And Characterization Of Nickel Complexes With Relevance To Nickel Acireductone Dioxygenase And Nickel Superoxide Dismutase

<p>This research presents an investigation of synthetic model complexes with relevance to the active site of Ni(II) acireductone dioxygenase (Ni-ARD) and Ni(II) superoxide dismutase (Ni-SOD). Acireductone dioxygenases (ARDs) are a unique set of enzymes found in the methionine salvage pathway that catalyze the oxidation reaction of acireductone (1, 2-dihydroxy-3-oxo-5-(methylthio)pent-1-ene). These enzymes share a compolypeptide sequence but bind different metal ions, Ni2+ or Fe2+, at the active site. The Ni-ARD enzyme is responsible for the off pathway shunt in the pathway. Using the tridentate nitrogen donor ligands hydrotris(3,5-dimethyl-1-pyrazolyl)borate (Tp*) and the newly developed tris(1, 2-dimethyl-4-imadozyl)carbinol, (4-TICMe, Me) several reactions involving the acireductone analog 2-hydroxy-1, 3-diphenylpropan-1, 3-dione and O2 were investigated for similarities to the Ni-ARD active site. Superoxide dismutases (SODs) play a key role in protecting cells against oxidative damage by regulating the cellular concentration of the superoxide radical (O2.-) which is an unwanted byproduct of cellular metabolism. This process is accomplished by converting the superoxide radicals to hydrogen peroxide and molecular oxygen. Several small-molecule complexes were synthesized and characterized in an effort to model the reduced state of the Ni-SOD using the Tp* ligand. The structures for these complexes have been determined using X-Ray Crystallography.</p>

Name thesis:degree_name

Ph.D. in Chemistry

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry and Biochemistry

Year dc:date.available

2012

Author dc:creator

• Montgomery, Margo Nicole

Contributors dc:contributor

• Walter E. Cleland
• Donald Cole
• Daniell L. Mattern

• Chemistry

Repository record dc:identifier

https://egrove.olemiss.edu/etd/417

OAI identifier oai:identifier

oai:egrove.olemiss.edu:etd-1416