Spectroscopic and theoretical studies of mononuclear non-heme iron enzymes : insight into the role of the facial triad and substrate effects on reactivity
Abstract/Contents
- Abstract
- Mononuclear non-heme iron enzymes are an important class with a wide range of medical, pharmaceutical and environmental applications. Within this class, the oxygen activating enzymes use Fe(II) to activate O2 for reaction with the substrate. The focus of this thesis is on understanding two major themes of the oxygen activating enzymes - the role of the (2His/1 carboxylate) facial triad and the initial O2 reaction steps of alpha-keto acid-dependent dioxygenases - using a combination of spectroscopic techniques and DFT calculations. For ferrous systems, abs/CD/MCD/VTVH MCD studies define the geometric and electronic structure of the ferrous site. In combination with DFT calculations, a structure/function picture of the ferrous sites is developed. To extend these studies to the initial steps of O2 binding, studies with NO as an O2 analogue ({FeNO}7/{FeO2}8) utilize EPR/abs/CD/MCD/VTVH MCD spectroscopy with DFT calculations to elucidate important effects of the substrate on the {FeNO}7 bond. These effects are used in the computational extension to the experimentally inaccessible O2 bound complexes giving insight into the initial steps of O2 binding and activation. Taken together, these studies shed light on the rational for facial triad ligation at the Fe(II) site in the oxygen activating enzymes and how the Fe(II) ligand set tunes the specific reactivity of these enzymes.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2011 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Diebold, Adrienne Renee |
|---|---|
| Associated with | Stanford University, Department of Chemistry |
| Primary advisor | Solomon, Edward I |
| Thesis advisor | Solomon, Edward I |
| Thesis advisor | Boxer, Steven G. (Steven George), 1947- |
| Thesis advisor | Cegelski, Lynette |
| Advisor | Boxer, Steven G. (Steven George), 1947- |
| Advisor | Cegelski, Lynette |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Adrienne Renee Diebold. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Ph.D. Stanford University 2011 |
| Location | electronic resource |
Access conditions
- Copyright
- © 2011 by Adrienne Renee Diebold
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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