Chemistry and Chemical Biology ETDs

Publication Date

Summer 7-15-2024

Abstract

Molybdenum and tungsten chemistry in biology is dominated by bonding interactions with sulfur and the other chalcogens. The highly-conserved structures of these enzymes’ active sites suggest an early evolution in the history of life, with molybdenum and/or tungsten enzymes likely expressed by the last universal common ancestor. Despite their active site similarities, molybdenum and tungsten enzymes catalyze a diverse array of reactions via equally diverse mechanisms. A deep understanding of the electronic structures of these enzyme active sites and their catalytic intermediates is key to understanding this remarkable chemistry.

The work presented here aims to deepen the understanding of molybdenum and tungsten chemistries in sulfur-rich coordination environments. Structural and electronic data obtained via x-ray crystallography, x-ray absorption and emission spectroscopies, and electronic absorption spectroscopy are analyzed and interpreted by the major theories of chemical bonding, including Valence Bond, Molecular Orbital, Natural Bonding Orbital, Density Functional, and Group Theories.

Language

English

Keywords

Molybdoenzyme RIXS FDH Tungstoenzyme NBO DFT

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Martin L. Kirk

Second Committee Member

Jeff Rack

Third Committee Member

Mark Walker

Fourth Committee Member

Abhaya Datye

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