Advancing Waste Management: Biomass Ozonolysis, Wastewater Chlorination, and Coal Ash in Landfills
The health of our communities depends on the effective treatment of both solid and liquid waste to eradicate hazardous pollutants before they can interact with living organisms or contaminate the environment. Daily, society generates solid waste (commonly destined for landfills) and liquid waste, (commonly discharged into wastewater systems) and without proper treatment, these wastes can release hazardous primary secondary pollutants. Industries producing wastewater with high pollutant concentrations, especially those utilizing lignin-based biomass, face complex challenges because each facility may require a tailored treatment approach. In response, this work investigates the use of ozonolysis to transform lignin monomers into smaller, less hazardous components that can be more efficiently managed by public wastewater systems. Furthermore, while conventional wastewater treatment systems are effective for common water quality issues, they can inadvertently allow complex compounds, such pollutants from hospital effluent, to pass through. Under simulated treatment conditions incorporating sunlight and chlorination, a pollutant released from medical facilities is degraded, but this process may also lead to the formation of carcinogenic disinfection by-products (DBPs) that pose direct toxicological risks to nearby communities. The implications extend to solid waste management as well. Chemical phenomena, such as those occurring in poorly understood elevated temperature landfills (ETLFs), can compromise treatment methods and increase community exposure to harmful pollutants. By monitoring hazardous components, such as volatile organic compounds (VOCs), over time, this work aims to elucidate the chemical reactions occurring both during treatment and in the environment thereafter. Ultimately, this research underscores the need for fundamental, innovative approaches to pollution transformation. Bridging the gap between existing practices for solid and liquid waste treatment will be critical to safeguarding environmental and public health.
Gold(I) complexes typically bond in a linear fashion; however, an increased valence can be achieved via ligand modulation. The most prevalent therapeutic gold complex, auranofin, contains a linear Au(I) center and has shown great potential in several diseases and conditions. On the other hand, the potential of three-coordinate Au(I) complexes have scarcely been probed as therapeutics. Reported here are the synthesis, characterization, and applications of novel three-coordinate Au(I) complexes. The degree of asymmetry varies between complexes depending on the Au-X ancillary ligands. This insight suggests that the degree of asymmetry influences the potency when incubated in various cancer cell lines. In addition, the coordination of bidentate phenanthroline ligand derivatives effect the symmetry by inducing varying degrees of distortion in the crystal structure. When the center Au(I) is bound to an N-Heterocyclic Carbene (NHC), the compound shifts from a distorted trigonal planar geometry to a distorted linear geometry. These complexes were used to probe glioblastoma, an aggressive head-and-neck cancer. When the center Au(I) is bound to biaryl dialkyl phosphine ligands, the geometry varies in symmetry, but the distorted trigonal planar geometry remains intact. Structure activity relationship studies were performed on these complexes in triple negative breast cancer cell lines. Previous research shows a disruption of mitochondrial dynamics when cancer cells were treated with three-coordinate Au(I) complexes, and the novel Au(I)-NHC library indeed disrupts mitochondrial dynamics. Mitochondria are the main energy production centers in the cell and are desirable therapeutic targets due to their implication in aging, inflammation, and cancer. The Au(I)-P library shows little mitochondrial disruption; instead, these complexes induce significant stress in the endoplasmic reticulum. The endoplasmic reticulum transports and folds proteins that allow the cell to function properly and synthesizes lipids and cholesterols. When the endoplasmic reticulum undergoes stress, the several signaling pathways, known as the unfolded protein response, activate, which can lead to lipid accumulation. Both a disruption of mitochondrial dynamics and an induction of endoplasmic reticulum stress can lead to apoptotic cell death. These effects were characterized by several 
Lignin is a complex aromatic biopolymer and an important constituent in plant cell walls. The process of lignin biosynthesis, known as lignification, is poorly understood and challenging to study but has important implications in a variety of fields including sustainable energy, bioengineering, and materials science and is therefore of interest to pursue. In the final stage of lignification, H-, G-, and S-monolignols are oxidized by laccase and peroxidase enzymes to generate radical species that couple to form dimers and further oligomeric species to ultimately produce the lignin polymer. Biomimetic lignin model systems utilize in vitro oxidative coupling reactions as an important tool to further develop our understanding of this complex process. The goal of the first portion of this dissertation was to explore several aspects of monolignol oxidative coupling using high performance liquid chromatography (HPLC). These aspects included the study of relative reaction rates, both with respect to monolignol conversion and product formation, and the effects of solvent composition on product distribution. Electrospray ionization mass spectrometry (ESI-MS) was an important analytical tool for characterizing many coupling products, especially higher oligomeric compounds. The insights acquired from these experiments contributed valuable information towards a fuller understanding of the lignification process.