Organic Chemistry Commons^™

Investigation Of D-Π-A Re (1) Complexes For The Homogenous Photocatalytic Reduction Of Co2, Ryan M. Chafin

Theses and Dissertations--Chemistry

Increasing anthropogenic emission of CO₂ into the atmosphere is a global issue that shows no signs of deceleration due to the current trends in dependencies on fossil fuels for energy demand. Although deleterious in nature, this greenhouse gas can serve as a useful feed-stock for the production of small-carbon-chain commercial chemicals if the factors owing to its inertness can be overcome. Fortuitously, CO₂’s chemically inert nature is already circumvented in nature through an elegant cascade of biochemical reactions known as photosynthesis, which nearly all plants and some families of bacteria exploit to produce simple sugars for metabolic …

Exploring The Relationships Between Molecular Structure And Crystal Packing In Small-Molecule Organic Semiconductor Materials, Dean A. Windemuller

Theses and Dissertations--Chemistry

Organic semiconductor materials (OSCs) are rapidly becoming a vital part of the technological landscape. They possess unique properties that make them attractive for the electronics industry. Relatively low-temperature and low-cost processing are a large part of the promise of OSCs. Perhaps more importantly, organic materials can be modified in a relatively straightforward manner, presenting an opportunity for them to be tuned and adapted to a variety of purposes and applications. Polycyclic aromatic hydrocarbons (PAHs) form a large group within the field of OSC research. Some of the most promising high-performance materials in this category to-date are acenes and heteroacenes. This …

Organic Geochemical Evidence For Life In Archean Rocks Identified By Pyrolysis-Gc-Ms And Supervised Machine Learning, Michael L. Wong, Anirudh Prabhu, Conel O'D. Alexander, H. James Cleaves Ii, George D. Cody, Grethe Hystad, Marko Bermanec, Wouter Bleeker, C. Kevin Boyce, Andrea Corpolongo, Andrew D. Czaja, Souvik Das, Robert R. Gaines, Daniel D. Gregory, John A. Jaszczak, Emmanuelle J. Javaux, Jaganmoy Jodder, Andrew H. Knoll, Martin Van Kranendonk, Katie M. Maloney, Nora Noffke, Robert Rainbird, Emersyn Slaughter, Eva E. Stüeken, Roger E. Summons, Frances Westall, Jasmina Wiemann, Shuhai Xiao, Robert M. Hazen

OES Faculty Publications

Throughout Earth’s history, organic molecules from both abiogenic and biogenic sources have been buried in sedimentary rocks. Most of these organic molecules have been significantly altered by geologic processes through deep time. Nonetheless, the nature and distribution of those ancient fragmentary organic remains have the potential to reveal diagnostic biomolecular information after billions of years of burial. Here, we analyzed 406 fossil, modern biological, meteoritic, and synthetic samples using pyrolysis gas chromatography and mass spectrometry. We explored these analytical data via supervised machine-learning methods to discriminate samples of biogenic vs. abiogenic origin, plant vs. animal phylogenetic affinity, and photosynthetic vs. …

Functional Design Of Dissymmetric Ligands For Coordination Systems, Kaitlyn R. Brown

Theses and Dissertations (Comprehensive)

Herein, the functional design of dissymmetric ligands for coordination systems is explored with a focus on their synthesis and structural characterization. The design strategy of these ligands incorporates the ability to coordinate both metal cations and anions along with a ligand site for other functionalization. Their synthesis, structural and other characterization, Hirshfeld surface analysis, and some metal-coordinated complexes are discussed. Chapter 1 introduces supramolecular and coordination chemistry, along with relevant literature that supports this research and outlines the thesis objective. Chapter 2 investigates the hydrogen bonding of a dissymmetric pyrimidine thioether ligand in its neutral form, water solvate, protonated nitrate …

Characterization And Optimization Of Sand And Tung Oil-Based Resins For Binder-Jet 3d Printing, Daniel I. Ajiola

College of Graduate Studies: Theses & Dissertations

Binder-jet 3D printing as a transformative technology in additive manufacturing, offers the ability to fabricate complex structures with diverse materials. This thesis investigates the use of a sustainable tung oil-based resin to create composites, exploring the potential for an eco-friendly alternative to synthetic binders.

The aim of this research is to develop and characterize a bio-based resin formulation, using tung oil as the primary binder, for application in binder-jet 3D printing with sand as the reinforcement. The resin formulation was prepared by combining tung oil, n-butyl methacrylate, divinylbenzene, and di-tert-butyl peroxide in precise proportions, ensuring a balanced mixture that supports …

Catalytic Innovation For Sustainable Styrene Production: Green Chemistry Strategies Utilizing Octahedral Ruthenium (Ii) Complexes Supported By A Single Bipyridine Ligand, Kennedy G. Musso, Brandon Quillian, Clifford Padgett, Jose Jimenez

College of Graduate Studies: Theses & Dissertations

This study investigates: 1) the synthesis and reactivity of the mono- substituted systems, [κ²-(t-bipy)Ru(NCMe)2(Ph)(PR3)][BArF'] supported by different ancillary ligands PR3 = (P(OCH3)3 and P(CH3)3) and a single bidentate ligand, 4,4′-di-tert-butyl-2,2′-bipyridine (t-bipy), and 2) UV/heat formation of di-PR3 and tri-PR3 systems supported by a single bidentate ligand to better understand the mechanism of styrene production. Utilizing [(η6-p-cymene)RuI(µ-I)]2 (1), the complexes (η6-p-cymene)RuI2(P(OCH3)3) (2) and (η6-p-cymene)RuI2(P(CH3)3) (3) were synthesized and phenylated to produce (η6-p-cymene)RuI(Ph)(PR3) (6; PR3 = P(OCH3)3 and 7; PR3 = P(CH3)3). Complex 4, (η6-p-cymene)RuCl2(P(CH3)3), was also synthesized and phenylated to produce (η6-p-cymene)RuClPh(P(CH3)3) (5) to understand the impact of chloride versus iodine …

Design And Synthesis Of Organocatalyts For Efficient Decontamination Of Organophosphate-Based Nerve Agents And Pesticides, Emmanuel Kingsley Darkwah

Doctoral Dissertations

Exposure to organophosphate-based nerve agents and pesticides poses significant health and security threats to civilians, soldiers, and first responders. Despite extensive efforts to develop chemical detoxification agents for use in topical applications on exposed skin surfaces and for intravenous injections, there remains an unmet need for effective, non-hazardous decontaminating agents. The current state-of-the-art decontaminating agent, Dekon-139 (2,3-butanedione oxime, potassium salt), exhibits adverse effects when applied to the skin.

In this study, we designed and synthesized pharmaceutically relevant aminoguanidine-derived aldimines that are relatively non-toxic and substantially more effective at decontaminating nerve agents and pesticides compared to existing agents, and they act …

Tailoring Selected Aerogels To Targeted Applications, Stephen Yaw Owusu

Doctoral Dissertations

Aerogels are ultra-lightweight, porous solid materials characterized by a three-dimensional nanostructured network. Owing to their exceptional physical and chemical properties, aerogels have garnered considerable attention within the materials science community and were recognized by IUPAC in 2022 as one of the top ten emerging technologies in chemistry. Although numerous aerogels have been synthesized, only a few have been effectively tailored for specific applications. Optimizing the properties of known aerogels for targeted uses remains challenging. This dissertation investigates strategies for tailoring aerogels derived from isocyanate-benzoxazine, benzodiazine, and phenolic resins to meet the requirements of various advanced applications. The approaches employed include …

Metal-Free Photoredox Catalysis For The S-Trifluoromethylation Of Thiols And Investigation Of Ph-Dependent Decontamination Of Dimethyl Chlorophosphate, A Nerve Agent Simulant, Via Hydrolysis With Azoles, Raheemat Rafiu

Doctoral Dissertations

"Organofluorine chemistry plays a critical role in synthetic chemistry due to the unique properties of fluorine. However, the S-trifluoromethylation of thiols remains underexplored, with existing methods often relying on toxic and expensive organometallic catalysts. Given the advantages of S-trifluoromethylated compounds, including enhanced pharmacological activity and improved metabolic stability, we developed a green and cost-effective method for the synthesis of S-CF3 compounds using diacetyl as the organic catalyst and Langloi's reagent as the trifluoromethylating reagent. This reaction, which proceeds under mild conditions using visible light photoredox catalysis, works across various substrate scopes, including aromatic, heteroaromatic, and aliphatic thiols.

Chemical Warfare Agents …

Polybenzodiazine Aerogels: All-Nitrogen Analogues Of Polybenzoxazines - Synthesis, Characterization, And Their Application In Carbon Dioxide Capture, Vaibhav Edlabadkar

Doctoral Dissertations

"The rapidly risen concentration of carbon dioxide in the atmosphere over recent years contributed to global warming and ocean acidification. Carbon capture is viewed as an essential tool from keeping atmospheric CO₂ levels from rising further. This thesis focuses on the development of new materials for high capacity and selective adsorption of CO₂. One such material was based on a newly synthesized tetrahydroquinazoline (THQ), which was designed as an all-nitrogen analogue of main-stream benzoxazine monomers. THQ solutions in DMF gelled at 100 °C via HCl-catalyzed ring opening polymerization to polybenzodiazine (PBDAZ) wet gels, which were dried in …

Instantaneous Hydrolysis Of Methyl Paraoxon Nerve Agent Simulant Is Catalyzed By Nontoxic Aminoguanidine Imines, Emmanuel Kingsley Darkwah, Puspa Aryal, Chi Zhang, Charles B. Musgrave, William A. Goddard, V. Prakash Reddy

Chemistry Faculty Research & Creative Works

Exposure to organophosphate-based nerve agents and pesticides poses health and security threats to civilians, soldiers, and first responders. Thus, there is a need to develop effective decontamination agents that are nonhazardous to human health. To address this, we demonstrate that instantaneous hydrolysis of methyl paraoxon (Me-POX), a nerve agent simulant, can be achieved in the presence of aminoguanidine imines at pH 10: ● the pyridine-4-aldehyde aminoguanidine-imine (1) and ● the 2,3-butanedione aminoguanidine-imine (2). The hydrolysis of Me-POX under these conditions is substantially faster than that of the state-of-the-art decontaminating agent, Dekon-139 (2,3-butanedione oxime, potassium salt). Furthermore, Dekon-139 shows adverse effects …

Functionalized 2d Hexaazatriphenylene As Hydrogen Storage Platform: A Dft-Guided Design Approach, Islam Gomaa

Nanotechnology Research Centre

No abstract provided.

Light-Driven Chemistry: Photoswitch In Rna Activity Control And Development Of Photoredox Catalysis, Juncheng Li

Electronic Theses & Dissertations (2024 - present)

This dissertation is structured into two principal segments. The initial segment elucidates a series of synthetic works involving artificial molecules, specifically featuring the photosensitive azobenzene. These molecules facilitate remote control over the structure and functionality of biomolecules, with subsequent applications in regulating biological processes. The latter segment concentrates on the design and enhancement of organic photocatalysts, utilizing traditional acridine ions as a foundation. This section details the development of diverse organic photocatalyst-promoted processes, including photo Lewis acid catalysis, photo Brønsted acid catalysis, and photoredox reactions.

Identification Of Fentanyl And Fentanyl Analogs Found In Human Urine Using Gas Chromatography-Mass Spectrometry, Adam M. Fisher

Electronic Theses & Dissertations (2024 - present)

Identification of fentanyl and its analogs in unknown samples is a frequent practice completed in forensic crime labs, as the fentanyl epidemic continues. With the continued increase in illicit drug use, crime labs are not able to keep up with the flooding of new fentanyl analogs being developed, resulting in new analogs slipping past the crime labs’ authority. This research is to start to develop a database of commonly found fentanyl analogs in New York State. Gas Chromatography-Mass Spectrometry (GC-MS) is a widely used method for the detection and identification of illicit drugs in forensic crime labs. A database that …

Metal-Free Photoredox Catalysis For The S-Trifluoromethylation Of Thiols, Raheemat Rafiu, Puspa Aryal, V. Prakash Reddy

Chemistry Faculty Research & Creative Works

The S-trifluoromethylation of thiols is accomplished using a simple and cost-effective organic catalyst (diacetyl) along with a bench-stable and environmentally friendly trifluoro methylating reagent (Langloi's reagent). Under optimized conditions (2.5 equivalents of Langlois reagent, Blue LED irradiation, 48-h reaction time at room temperature), the reaction yielded up to 81% S-trifluoro methylated product. This method's high yields, compatibility with a broad substrate scope (aliphatic, heteroaromatic, and aromatic thiols), and environmentally friendly conditions demonstrate its potential for broader synthetic applications. In contrast to traditional methods that rely on organometallic catalysts and environmentally hazardous reagents, this novel photoredox catalysis method offers a more …

Approaches To The Synthesis Of Highly Substituted Arenes, Kh Tanvir Ahmed

Graduate Theses, Dissertations, and Problem Reports (ETD)

While benzene rings and their derivatives are among the most frequently encountered ring systems in natural products, pharmaceuticals, agrochemicals, dyes, and functional materials, polysubstituted arenes are relatively scarce. The analysis of FDA-approved small molecules provides valuable insights into the characteristics of successful drugs while also highlighting gaps in the availability of synthetic methods capable of efficiently accessing diverse substitution patterns on aromatic rings. Highly substituted arenes are typically synthesized through sequential modification of a pre-existing benzene core; however, this stepwise approach becomes increasingly challenging with each additional substitution. An alternative strategy involves the direct construction of benzene rings via annulation …

Functionalized Carbon Nanohoops: Synthesis, Structural Insights, And Pathways To Carbon Nanobelts, Liu Li

Graduate Theses, Dissertations, and Problem Reports (ETD)

The development of structurally defined carbon nanostructures has gained significant attention due to their unique electronic, optical, and mechanical properties. Cycloparaphenylenes (CPPs), also known as carbon nanohoops, and carbon nanobelts (CNBs) represent key molecular segments of carbon nanotubes (CNTs), offering a bottom-up approach to precise nanotube construction. This dissertation focuses on the synthesis, structural characterization, and functionalization of CPPs, as well as the development of novel synthetic pathways for CNBs. A series of functionalized CPPs, including [9]-, [12]-, [15]-, and [18]CPPs, were synthesized using a modular approach involving a Diels-Alder adduct formation followed by a Ni(cod)2/bpymediated macrocyclization reaction. The influence …

Photoswitchable Inhibitors Of Eaat3, Karly Suhr

Electronic Theses & Dissertations (2024 - present)

Azobenzene is a photoswitchable molecule known for its high conversion yield and repeatability. The inclusion of an azobenzene moiety with a known inhibitor of your target of interest allows for greater study of function as well as potential therapies. Three derivatives were designed from azobenzene and known inhibitor of EAATs, TBOA, to synthesize photoswitchable inhibitors of EAATs. Further investigation into the function of EAATs and development of a specific inhibitor for EAAT3, an important glutamate transporter in the brain required for proper function, can then be conducted. Photoisomerization studies on the derivatives were conducted using UV/vis spectroscopy and NMR spectroscopy. …

The Development Of A One Pot, Two Reaction Synthetic Preparation Of 1,2,4-Oxadiazole, And Synthesis Of Ataluren, A Novel Drug In The Fight Against Duchenne Muscular Dystrophy. Efforts Towards The Synthesis Of A Potential Protease Inhibitor Against The Main Protease (3clpro) Of Covid-19, Austin J. Carter

Theses and Dissertations

1,2,4-Oxadiazoles are five-membered heterocyclic structures first synthesized by Tiemann and Krüger in 1884. Recent discoveries suggest an array of useful biological properties.In preparation of 1,2,4-oxadiazoles, the most prevalent precursors are amidoximes, which can be created via the reaction of nitriles with hydroxylamine hydrochloride and a base. The amidoximes are reacted with an activated carboxylic acid to yield an acylated intermediate. This intermediate can be exposed to a base to cyclize into the 1,2,4-oxadiazole. This thesis describes the efforts in combining these three steps into a unified one-pot synthesis.

Currently, there are a significant number of commercially available FDA approved and …

Asymmetric Synthesis Of The Hiv Protease Inhibitor Tmc-126 And An Anti-Malarial Agent Via A Titanium Tetrachloride Mediated Asymmetric Glycolate Aldol Addition Reaction. Redefining The Curtius Rearrangement Reaction Via Dehomologation Of Carboxylic Acids Bearing Alpha-Leaving Groups, Kweku Amaning Affram

Theses and Dissertations

Acquired Immune Deficiency Syndrome (AIDS) and malaria are two devastating infectious diseases caused by HIV and Plasmodium parasites. AIDS is caused by HIV-1 and HIV-2, transmitted through sexual contact, blood transfusions, needle sharing, and perinatal routes. Malaria, caused by plasmodium parasites through mosquito bites. Today, millions of people around the world have been infected with HIV and malaria and much research has been done to treat it. However, despite advancements in therapeutic options, these diseases remain a significant global health threat, particularly in developing countries due to the emergence of drug-resistant strains for both HIV and malaria complicating eradication efforts. …