Organic Chemistry Commons^™

Assessing Interatomic Potentials For Molecular Dynamics Simulation Of Soybean Oil Pyrolysis, Tanner Garrett Rust

MSU Graduate Theses

The world today relies on hydrocarbon combustion for many reasons, including its high energy density that provides ease of transportation. However, hydrocarbons sourced from fossil fuels are not expected to last forever. Biodiesel, a renewable alternative, has many attractive benefits but comes with other downsides. Biodiesel can gel in cold environments and may leave residue in an engine. Pyrolysis of biodiesel has shown promise in addressing these common detriments. Inducing pyrolysis on biodiesel feedstock (commonly soybean oil in the USA) would be an attractive option presuming it continues to produce fossil fuel analogs similar to biodiesel pyrolysis. Herein, Langevin molecular …

Green Oxidation Of Aromatic Hydrazide Derivatives Using An Oxoammonium Salt, Nidheesh Phadnis, Jessica A. Molen, Shannon M. Stephens, Shayne M. Weierbach, Kyle M. Lambert, John A. Milligan

Chemistry & Biochemistry Faculty Publications

Aromatic diazenes are often prepared by oxidation of the corresponding hydrazides using stoichiometric quantities of nonrecyclable oxidants. We developed a convenient alternative protocol for the oxidation of aromatic hydrazides using Bobbitt's salt (1), a metal-free, recyclable, and commercially available oxoammonium reagent. A variety of aryl hydrazides were oxidized within 75 min at room temperature using the developed protocol. Computational insight suggests that this oxidation occurs by a polar hydride transfer mechanism.

Covalent Inhibition Of Enzyme Sortase A As A New Pathway Against Bacterial Resistance Of Staphylococcus Aureus, Umyeena Bashir

Master's Theses

The continued rise of antibiotic-resistant bacteria, such as MRSA (methicillin-resistant Staphylococcus aureus), has made the discovery of novel antibiotics critical. While bacteriostatic and bactericidal antibiotics inevitably exert evolutionary pressure on bacteria to develop resistance, small molecules that target mechanisms of bacterial virulence present a promising alternative for treatment. Sortase A (Srt A), a cysteine protease of S. aureus, promotes bacterial virulence by covalently attaching proteins such as pilin to the bacterial surface, enabling bacterial adhesion to mammalian cells. Inhibitory studies of this enzyme have gained prominent interest as a new pathway for drug development since blocking this enzyme's ability to …

Exploring Soybean Oil-Based Polyol And Effect Of Non-Halogenated Flame Retardants In Rigid Polyurethane Foam, Sahithi Kondaveeti

Electronic Theses & Dissertations

To address the increasing demand for sustainable biomaterials due to the depletion of fossil fuel resources and growing environmental concerns, a new type of biodegradable and environmentally friendly rigid polyurethane foam (RPUF) has been synthesized. These foams are derived from chemically modified soybean oil-based polyol obtained from soybean oil by epoxidation followed by a ring-opening reaction. Polyurethane foam is generally used in construction, furniture, and automobile industries but is highly flammable and releases toxic gases and smoke during combustion. In this study, a highly efficient synergistic effect halogen-free flame-retardant (FR) melamine salt, 2-carboxyethyl(phenyl)phosphinic acid melamine salt (CMA) was synthesized from …

Enhanced Mechanical Strength Of Soybean Oil-Based Non-Isocyanate Polyurethane Adhesive For Wood Application By Introducing Nanofillers, Vatsal Chaudhari

Electronic Theses & Dissertations

Polyurethane (PU) is a versatile material that finds extensive use in various industries including bedding, construction, automotive, and packaging. Historically, this particular polymer relied significantly on petrochemical resources, a practice that was considered to have negative environmental impacts. The conventional method for preparing PU involves the use of isocyanate, which is a disadvantage due to its negative impact on the environment and human health. The resolution of this problem entails identifying an appropriate substitute for petroleum-derived products that minimize their impact on both the environment and human health. The researchers earlier utilized soybean oil, for the formulation of PUs in …

Optimization Of Transition-Metal Inclusive Carbon Aerogels For Electrochemical Energy Applications, Allen Dalton Davis

Electronic Theses & Dissertations

The ever-growing need for energy alongside rising concerns for climate change demands the development of renewable energy technologies. Hydrogen fuel cells are a promising technology that can serve to either supplement energy generation or act as a lone power source. Yet for these devices to be truly green, the hydrogen that serves as fuel must be procured from a renewable resource. Electrolytic water splitting is a process that allows for the dissociation of water into H₂ and O₂. For this process to be practical, the electrolyzer needs to demonstrate high efficiency and stability, as well as a …

Thermocatalytic Plasma-Assisted Dry Reforming Of Methane Over Ni/Al2o3 Catalyst, Tyler Wong

Seton Hall University Dissertations and Theses (ETDs)

Plasma catalysis is an advantageous approach that combines the effects of plasma with the enhancements of a catalyst. By utilizing a nickel catalyst in the plasma discharge zone of a dielectric barrier discharge (DBD), it can give an enhancement to the electrical field, boost microdischarges, and increase conversion and selectivity rates of CH₄ and CO₂ in the dry reforming of methane (DRM) reaction.

Industrial application of nickel catalysts in DBD Plasma DRM process are limited by poor stability, which is caused by the sintering of active metal particles and coke deposition on the catalyst surface. In this work, …

Hydrogen Bond Activation Of Donor Acceptor Cyclopropanes, Matthew H.J. Pamenter

Electronic Thesis and Dissertation Repository

Donor acceptor cyclopropanes (DACs) are versatile organic building blocks used in the synthesis of many pharmaceutically relevant heterocycles. The combination of a high ring strain cyclopropane core and vicinal donor and acceptor substituents cause DACs to behave like 1,3-zwitterions. Recently, DACs have been activated by a hydrogen bond donor solvent in place of a Lewis acid catalyst, allowing the elimination of heavy metals commonly used in these transformations. Hexafluoroisopropanol (HFIP) as a hydrogen bond donor cosolvent was found to cause a downfield shift of the DACs electrophilic carbon in the 13C NMR spectrum. This indicates increased electrophilicity at this position …

Synthesis Of Block Copolymer Additives For Examining Phase Morphology And Improving Mechanical Properties Of Thermoplastics Elastomers., Bishal Upadhyay

Masters Theses

Polystyrene-block-poly(1,4-butaidene)-block-polystyrene (PS-PB-PS) triblock copolymers are one of the most widely studied thermoplastic elastomers (TPEs) due to their ease of synthesis, non-polar nature, and commercial applicability. Like many block copolymers, incompatibility between PS and PB causes these TPEs to undergo microphase segregation. Many studies have examined the mechanical properties of blends of TPEs and PS homopolymer additives. However, there have been few studies focused on understanding the morphology and mechanical properties of blends of TPEs and copolymer additives with different architectures. Herein, I describe the synthesis of linear and graft copolymer additives based on the random copolymers poly(methyl methacrylate-random-cyclohexyl methacrylate) (PrC). …

Synthesis And Characterization Of Colorimetric And Flurometric Chemosensor For Trivalent Metal Ions, Fazila Haque

Honors Program Theses and Research Projects

There are many biological and environmental uses for trivalent metals (like Fe3+, Al3+, and Cr3+) within our daily lives. Whether these trivalent metals are found in deficiency or excess can cause issues within our environment (global warming) or our bodies (can cause problems with our digestive, cardiovascular, and immune systems). Being able to detect them and understanding their importance becomes crucial in our understanding of the world that surrounds us.
One of the ways we can detect these trivalent metals is through the use of chemosensors. Chemosensors are used to sense analyte (trivalent metal) to produce a signal (fluorescence or …

Chemical Investigation Of Dichloromethane Extract Of Aloe Vera Peels: An Agricultural Waste, Nazmul Huda

Theses and Dissertations

Aloe barbadensis Miller, commonly called Aloe Vera, is a widely popular succulent plant species cultivated across subtropical regions worldwide from India to the Tex-Mex border. Besides its historical uses, Aloe juice has garnered attention as a potential remedy for various ailments, particularly in treating various skin conditions and facilitating wound recovery, including obesity, diabetes, hepatitis, Crohn's disease, and ulcerative colitis. Regrettably, the agricultural practice following sap extraction involves discarding Aloe vera peels, constituting agricultural waste. As part of our continuous research on extraction, isolation, separation, and spectral characterization of value-added chemicals present in waste botanicals herein, …

Synthesis Of Bacterial Glycerophospholipids For Biomembrane Model Studies: A Means To Advanced Biofuels, Felix Adulley

Electronic Theses and Dissertations

To reduce reliance on fossil fuels, sustainable biofuels are being pursued, especially advanced biofuels like 1-butanol that have higher energy content and greater compatibility with existing infrastructure than ethanol. A persistent challenge is the yield-limiting toxicity of biofuels and process solvents, such as tetrahydrofuran, to the microbes that ferment biomass into biofuel. The cell membrane is a focal point of toxicity, and understanding how it interacts with fuels and solvents is key to improving yield. Phospholipid bilayers are the core of biomembranes, and model biomembranes of defined composition provide the ideal platform for biophysical studies. To this end, glycerophospholipids characteristic …

Quantifying The Role Of Water Quality On Nitrogen Cycling In A Trophic Estuary, Kayla Gonzalez-Boy

Symposium of Student Scholars

Jobos Bay Estuary is an intertidal, tropical estuary located in southern Puerto Rico. The estuary covers about 12 km² and has a variety of habitats, such as seagrass beds, mangroves, mud flats, and coral reefs, which play important roles in sediment trapping and water quality maintenance. Seagrasses also serve as nursery and feeding grounds and provide shelter for macrofauna. Currently, the role of seagrasses and water quality on nitrogen (N) cycling in trophic estuaries is not well constrained. Understanding variations in sediment-based effects on N cycling rates and transformations, and how they are associated with water quality, is an …

Reactive Chemistries For Protein Labeling, Degradation, And Stimuli Responsive Delivery, Myrat Kurbanov

Doctoral Dissertations

Reactive chemistries for protein chemical modification play an instrumental role in chemical biology, proteomics, and therapeutics. Depending on the application, the selectivity of these modifications can range from precise modification of an amino acid sequence by genetic manipulation of protein expression machinery to a stochastic modification of lysine residues on the protein surface. Ligand-Directed (LD) chemistry is one of the few methods for targeted modification of endogenous proteins without genetic engineering. However, current LD strategies are limited by stringent amino acid selectivity. To bridge this gap, this thesis focuses on the development of highly reactive LD Triggerable Michael Acceptors (LD-TMAcs) …

Contributions Of Tunneling In 8Π-6Π Electrocyclic Cascade Reactions Of Bicyclo[4.2.0]Octa-2,4-Diene Moieties, Ishika Jain, Claire Castro, William L. Karney

Featured Student Work

Six-electron electrocyclic reactions usually require relatively high temperatures; however recent research has shown that such reactions can occur at significantly lower temperatures in biosynthetic and biomimetic pathways. Pathways resulting in bicyclo[4.2.0]octa-2,4-diene moieties arise from thermally allowed 8π-6π electrocyclization cascade reactions of 1,3,5,7-octatetraenes, as in the biosynthesis of endiandric acids, elysiapyrones, and numerous other natural products. We report multidimensional tunneling calculations to explore the possible contribution of heavy-atom tunneling (e.g. by carbon) to biosynthetic pathways and biomimetic syntheses, and thus to provide a more complete picture of biochemical kinetics. M06-2X/cc-pVDZ calculations on the 8π-6π cascade cyclizations of methylated octatetraene model systems …

Oxidative Stress In Health And Disease, V. Prakash Reddy

Chemistry Faculty Research & Creative Works

Oxidative stress, resulting from the excessive intracellular accumulation of reactive oxygen species (ROS), reactive nitrogen species (RNS), and other free radical species, contributes to the onset and progression of various diseases, including diabetes, obesity, diabetic nephropathy, diabetic neuropathy, and neurological diseases, such as Alzheimer's disease (AD), amyotrophic lateral sclerosis (ALS), and Parkinson's disease (PD). Oxidative stress is also implicated in cardiovascular disease and cancer. Exacerbated oxidative stress leads to the accelerated formation of advanced glycation end products (AGEs), a complex mixture of crosslinked proteins and protein modifications. Relatively high levels of AGEs are generated in diabetes, obesity, AD, and other …

Developing New Strategy Toward Ruthenium And Gold Redox Catalysis, Chenhuan Wang

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) The discovery of triazole-modified Ru carbene catalysts for alkene metathesis and dynamic covalent chemistry; 2) The study of ligand assisted gold oxidative addition toward aryl iodide to achieve the alkene difunctionalization; 3) Gold redox catalysis via chiral P,N-chelating ligands. In the first part, the 1,2,3-triazole coordinated ruthenium carbene complexes (TA-Ru) were reported for the first time as a new class of modified Grubbs catalyst to achieve challenging olefin metathesis at higher temperatures without catalyst decomposition. With this new TA-Ru catalyst, cross-metathesis (CM), ring-closing metathesis (RCM) and dynamic covalent chemistry (DCvC) were achieved. The …

Chemical Analysis Of Metabolites From Mangrove Endophytic Fungus, Sefat E Munjerin

USF Tampa Graduate Theses and Dissertations

Natural products hold a significant place in drug discovery for their abundant and unique secondary metabolites. These secondary metabolites which encompass a range of organic compounds such as alkaloids, phenols, peptides, flavonoids, polyketides, and terpenoids, can easily be exploited for drug development. Endophytic fungi, residing harmoniously with its host, have emerged as generous producers of bioactive secondary metabolites, displaying efficacy against a wide array of human pathogens, including the challenging ESKAPE pathogens.

The research explores endophytic fungi and their prospective for drug discovery and development through the synthesis of distinctive secondary metabolites. Endophytic fungus, HM13-26C-2B, collected from Honeymoon Island, Florida …

Development Of Cu-Catalyzed Oxidative Alkylboron Homocoupling, Dan Khazaei, Andrew Baggett, Katie Russell

Student Presentations

No abstract provided.

A Work Towards A Single-Bridge Hydrazine Sensor, Brenden Jay Schmeltz

Theses and Dissertations

Hydrazine can currently be detected by irreversible methods, Carbazolopyridinophane (2,18-Dithia[3][1,8]carbazolo[3][2,6]pyridinophane) CP was synthesized by Brown et al. to detect hydrazine in real-time while also being reversible. The threshold for detection was 100 ppb, regulatory use requires 10 ppb as this is when permanent damage to humans can be caused. A more sensitive sensor will allow for safer workplaces for many people. A single, 3-atom bridge sensor will further examine the photophysical capabilities of carbazole-pyridine as an emitter/quencher pair. 1-Carbazole-1-methylpyridyl-2methyl sulfide SBCP will allow freedom of rotation as well as the bending of the bridge. These benefits will introduce conformers which …