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Modeling Complexity: Development and Characterization of a Carbon Monoxide Dehydrogenase Mimic to Identify Key Factors for Reactivity

Schneider, Camille Rae
http://rave.ohiolink.edu/etdc/view?acc_num=osu1563525837991322

Abstract Details

2019, Doctor of Philosophy, Ohio State University, Biochemistry Program, Ohio State.
Due to anthropogenic combustion of fossil fuels, atmospheric carbon dioxide levels have surpassed 400 ppm. This increase has resulted in a multitude of global changes, such as increased global temperature, rising sea levels, and ocean acidification. Carbon dioxide can be utilized as a C1 feedstock through conversion to many value-added products. A native system for carbon dioxide reduction is the nickel- and iron-containing carbon monoxide dehydrogenase (CODH). This system selectively catalyzes the reversible reduction of CO2 to carbon monoxide; however, it suffers from oxygen sensitivity and requires complex cofactors, complicating its largescale utilization. Synthetic models have been developed to circumvent the aforementioned issues and one catalyst of interest is [Ni(cyclam)] (cyclam = 1,4,8,11-tetraazacyclotetradecane) due to its reported selectivity for carbon monoxide production in water. This thesis aims to identify important factors for controlling reactivity and focuses on the development and characterization of an artificial enzyme system to functionally model CODH. [Ni(cyclam)] has been incorporated into azurin to examine the catalytic reduction of carbon dioxide to carbon monoxide. These semisynthetic enzymes display an increase in selectivity and the presence of a redox active metal exhibits heightened activity, demonstrating the importance of intramolecular electron transfer. Covalent attachment of a ruthenium-based phototrigger results in a completely selective catalyst for carbon dioxide reduction. [Ni(cyclam)] reactivity can be altered simply by changing the reaction medium and axial coordination to a cationic buffer enhances activity. However, these effects are mitigated in the semisynthetic azurin platform, further supporting the intricate interplay of factors required to govern catalysis.
Hannah Shafaat (Advisor)
Claudia Turro (Committee Member)
Anne Co (Committee Member)
James Cowan (Committee Member)
315 p.
Biochemistry

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Citations

  • Schneider, C. R. (2019). Modeling Complexity: Development and Characterization of a Carbon Monoxide Dehydrogenase Mimic to Identify Key Factors for Reactivity [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1563525837991322

    APA Style (7th edition)

  • Schneider, Camille. Modeling Complexity: Development and Characterization of a Carbon Monoxide Dehydrogenase Mimic to Identify Key Factors for Reactivity. 2019. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1563525837991322.

    MLA Style (8th edition)

  • Schneider, Camille. "Modeling Complexity: Development and Characterization of a Carbon Monoxide Dehydrogenase Mimic to Identify Key Factors for Reactivity." Doctoral dissertation, Ohio State University, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=osu1563525837991322

    Chicago Manual of Style (17th edition)

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This open access ETD is published by The Ohio State University and OhioLINK.
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