Date of Award
Doctor of Philosophy (PhD)
Chemistry | Physical Sciences and Mathematics
Chapter 2: Photocatalytic turnover of CO2 under visible light by Re(I) naphthalimide complexes in tandem with a sacrificial donor Increased levels of atmospheric, anthropogenic CO2 and rapid consumption of fossil fuels present major challenges for society and prompts the development of new potent catalysts that can absorb visible light to reduce greenhouse gasses1,2. The photocatalytic reduction of CO2 using rhenium(I) has been demonstrated but suffers from low turnover. Herein, we describe a [Re(CO)3(1-(1,10)phenanthroline-5-(4-nitro-naphthalimide))Cl] (Re5-PAN) photocatalyst, which when combined with the sacrificial donor 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole, results in selective production of formic acid and a high turnover number of 533 and turnover frequency of 356 h−1. Single-crystal X-ray diffraction and DFT studies are discussed as well as a preliminary look at a series of next-generation Re(I) catalysts with modified ligand conjugation. Chapter 3: Synthesis, Characterization, and Imaging of Fluoroplatin: a Pro-drug for Fluorescence Detection of Aquated Cisplatin Nausea and emesis are common side effects of cancer chemotherapy; however, their physiological origins and pathways are often unknown. Cisplatin has been used in chemotherapy since 1978 but the ability to track its localization and assay its transcriptional effects has been hampered by its lack of fluorescence. Herein, we synthesized and characterized a Pt (IV) pro-probe, 6,8-difluoro-7-hydroxy-4-methylcoumarin-cis-diamminehydroxyplatinum(IV)dichloro ester (1). In a reducing environment, 1 formed the aquated products of intracellular cisplatin, as evidenced by 1H and 195Pt NMR, IR, high resolution mass spectroscopy, and fluorescence spectroscopy. Live-cell imaging supported accumulation of the probe in the nucleus of HEK-293 cells at one hour. This pro-probe will allow for visual validation of cisplatin uptake in tissues, which can then be used for studies including single cell RNA sequencing transcriptomics to better understand the physiological pathways of cisplatin-induced side effects and/or function. Chapter 4: Rapid, green disulfide bond formation in water using the corrin dicyanocobinamide Peptide chemists seek rapid methods combined with facile purification when producing disulfide bonds post solid-phase synthesis. Current methods typically require long reaction times of up to two days, can result in side-products from over-oxidation and/or degradation, require organic solvents, and/or require challenging purification. Herein, we describe a rapid, green, and facile oxidation of a series of peptides with up to three disulfide bonds. The method was conducted in aqueous solution, in air, utilizing the biocompatible corrin ring-containing compound dicyanocobinamide, and offers reaction times under 1 hour with simple one step removal of the catalyst.
Spear, Alyssa, "Small molecule and peptide redox reactions using rare and earth abundant metal complexes" (2023). Dissertations - ALL. 1737.
Available for download on Friday, February 02, 2024