Please use this identifier to cite or link to this item:
http://arks.princeton.edu/ark:/88435/dsp01r207ts71p
Title: | OXYGENATION OF SYNTHETICALLY AND ENVIRONMENTALLY RELEVANT SUBSTRATES BY A FUNGAL PEROXYGENASE |
Authors: | Davis , Dali Lee |
Advisors: | Groves, John T |
Contributors: | Chemistry Department |
Keywords: | enzymes fungal peroxygenase green chemistry organic substrates oxyfunctionalization |
Subjects: | Chemistry Organic chemistry |
Issue Date: | 2024 |
Publisher: | Princeton, NJ : Princeton University |
Abstract: | The selective oxidation of organic molecules is among the most impactful chemical processes due to its significance in both the synthesis of commercial and pharmaceutical products and implications in bioremediation. Over the years, several transition-metal catalysts have been developed to achieve this type of reactivity; however, the synthesis of these catalysts and their optimal reaction conditions can result in high-energy consumption and the production of hazardous waste. In contrast, biocatalysts, which have received growing attention as more people become aware of and better versed in “green” approaches in chemistry, are considered powerful alternatives. There are several biocatalysts which have an aptitude for performing selective reactions under mild conditions without the formation of harmful side products. One class of these catalysts is referred to as an unspecific peroxygenase (UPO). These heme-thiolate, fungal enzymes have displayed the ability to oxidize a host of organic substrates while tolerating different functional groups and functioning under unnatural conditions, and they are recognized as emerging biocatalysts. Additionally, they are considered environmentally benign and only require hydrogen peroxide (or an organic peroxide) as a co-substrate. The UPO of interest in this work, referred to as MroUPO since it is secreted from the ATCC 76395 variant of the fungus Marasmius rotula, was initially discovered, isolated, and characterized in the Groves lab. Although it shares over 95% sequence identity with other MroUPO strains, it has proven to have unique reactivity and selectivity; however, it has remained underexplored. To highlight some of its capabilities, in this dissertation, I detail its ability to oxygenate unactivated C–H bonds and nitrogen centers in a variety of substrates including halo(cyclo)alkanes, organic pollutants, anilines, and drug molecules. The reactivity of this MroUPO strain offers an efficient and safe method to access useful synthetic building blocks and to breakdown recalcitrant and toxic molecules. |
URI: | http://arks.princeton.edu/ark:/88435/dsp01r207ts71p |
Type of Material: | Academic dissertations (Ph.D.) |
Language: | en |
Appears in Collections: | Chemistry |
Files in This Item:
This content is embargoed until 2025-06-06. For questions about theses and dissertations, please contact the Mudd Manuscript Library. For questions about research datasets, as well as other inquiries, please contact the DataSpace curators.
Items in Dataspace are protected by copyright, with all rights reserved, unless otherwise indicated.