Nuclear resonance vibrational spectroscopic studies of the biferric and high-valent states of binuclear non-heme iron enzymes
Abstract/Contents
- Abstract
- Binuclear non-heme iron (NH2Fe) enzymes play significant roles in all realms of life including human health, drug discovery, and antibiotic biosynthesis. These enzymes reductively activate dioxygen to form reactive intermediates that go on catalyze a wide variety of chemical reactions including hydroxylation, N-oxygenation, and electrophilic aromatic substitution. Defining the geometric and electronic structure of these enzymes in their resting biferric and intermediate states is critical in understanding their reaction mechanisms. Nuclear resonance vibrational spectroscopy (NRVS) probes the vibrational quanta of the 57Fe Mössbauer transition and is thus well-suited for selectively probing the NH2Fe center of this enzyme class. NRVS does not possess an optical selection rule, and the partial vibrational density of states (PVDOS) spectrum obtained from NRVS exhibits intensity for all modes containing 57Fe iron motion, yielding rich vibrational data. Calculation of the NRVS PVDOS spectra for candidate structural models using quantum mechanical methods permits modeling and assignment of the NRVS data, leading to elucidation of the geometric structure of a target molecule. In this thesis, NRVS is applied to the biferric states of class Ia ribonucleotide reductase (RnR) and soluble methane monooxygenase (sMMO), as well as the methane-reactive intermediate Q in sMMO, to define their geometric structures and understand how these structures influence their function.
Description
| Type of resource | text |
|---|---|
| Form | electronic resource; remote; computer; online resource |
| Extent | 1 online resource. |
| Place | California |
| Place | [Stanford, California] |
| Publisher | [Stanford University] |
| Copyright date | 2021; ©2021 |
| Publication date | 2021; 2021 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Jacobs, Ariel Benjamin |
|---|---|
| Degree supervisor | Solomon, Edward I |
| Thesis advisor | Solomon, Edward I |
| Thesis advisor | Karunadasa, Hemamala |
| Thesis advisor | Stack, T. (T. Daniel P.), 1959- |
| Degree committee member | Karunadasa, Hemamala |
| Degree committee member | Stack, T. (T. Daniel P.), 1959- |
| Associated with | Stanford University, Department of Chemistry |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Ariel Benjamin Jacobs. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis Ph.D. Stanford University 2021. |
| Location | https://purl.stanford.edu/kj320pg9830 |
Access conditions
- Copyright
- © 2021 by Ariel Benjamin Jacobs
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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