Chemistry Commons^™

Excited State Processes In Radical Elaborated Platinum Donor-Acceptor Complexes, Sangita Paudel

Chemistry and Chemical Biology ETDs

Organo-transition metal complexes are being widely studied to understand their photophysical properties for their wide range of applications as efficient emitters in organic light emitting diodes (OLEDs), light emitting electrochemical cells (LEECs), etc. Cyclometalated organo-transition metal complexes such as cyclometalated square planar platinum(II) complexes are becoming suitable candidates for such applications because of their highly efficient luminescence. Understanding the excited properties of such complexes is useful in designing highly efficient and color tunable phosphors with desired excited state lifetimes. We aim to explore the influence of radical substituents on electronic structure, luminescence quantum efficiencies, and excited state lifetimes by synthesizing …

Multi-Scale Simulations Of Dynamic Protein Structures And Interactions, Yumeng Zhang

Doctoral Dissertations

Intrinsically disordered proteins (IDPs) are functional proteins that lack stable tertiary structures in the unbound state. They frequently remain dynamic even within specific complexes and assemblies. IDPs are major components of cellular regulatory networks and have been associated with cancers, diabetes, neurodegenerative diseases, and other human diseases. Computer simulations are essential for deriving a molecular description of the disordered protein ensembles and dynamic interactions for mechanistic understanding of IDPs in biology, diseases, and therapeutics. However, accurate simulation of the heterogeneous ensembles and dynamic interactions of IDPs is extremely challenging because of both the prohibitive computational cost and demanding force field …

High Resolution Mass Spectrometry As A Platform For The Analysis Of Polyoxometalates, Their Solution Phase Dynamics, And Their Biological Interactions., Daniel T. Favre

Doctoral Dissertations

Polyoxometalates (POMs) are a class of inorganic molecule of increasing interest to the inorganic, bioinorganic and catalytic communities among many others. While their prevalence in research has increased, tools and methodologies for the analysis of their fundamental characteristics still need further development. Decavanadate (V10) specifically has been postulated to have several unique properties that have not been confirmed independently. Mass spectrometry (MS) and its ability to determine the composition of solution phase species by both mass and charge is uniquely well suited to the analysis of POMs. In this work we utilized high-resolution mass spectrometry to characterize V10 in aqueous …

Development Of Salinomycin Derivatives As Potential Anticancer Agents, Viren Soni

Theses and Dissertations

Salinomycin is a poly-ionophore antibiotic that was originally isolated from Streptomyces albus by Miyazaki and colleagues from Kaken Chemicals Co., Ltd., Tokyo, Japan. Salinomycin exhibits antimicrobial activity against Gram-positive bacteria including Bacillus subtilis, Staphylococcus aureus, Micrococcus flavus, Sarcina lutea, Mycobacterium spp. Some filamentous fungi, Plasmodium falciparum, and Eimeria spp. as well as protozoan parasites responsible for the poultry disease coccidiosis. Hence, it is used in veterinary medicine. In 2009 Gupta et al demonstrated that salinomycin selectively killed human breast cancer stem cells (CSCs) with great efficacy, and the mechanism of action of this novel CSCs molecule was explored. To name …

Studies Of Oxidopyrylium Ylide Dimers And Their Utility In The Synthesis Of Densely Functionalized Troponoids, Daniel V. Schiavone

Dissertations, Theses, and Capstone Projects

Herein, we describe our efforts to investigate mechanistic considerations of oxidopyrylium ylides and their use in cycloadditions to form complex bicyclic structures and the advancement of these cycloadducts to the synthesis of densely functionalized tropolones. This work also describes applications of tropolones as biologically relevant structures and dynamic fluorophores.

In Chapter 1, we expand upon previous studies done in the Murelli Lab describing the ability of 3-hydroxy-4-pyrone derived oxidopyrylium dimers to revert back to ylides in situ and as result can be used as a clean oxidopyrylium ylide source in accessing oxabicyclic compounds. Intermolecular cycloadditions of these ylides can be …

Rational Design Of Peptide-Based Materials Informed By Multiscale Molecular Dynamics Simulations, Dhwanit Rahul Dave

Dissertations, Theses, and Capstone Projects

The challenge of establishing a sustainable and circular economy for materials in medicine and technology necessitates bioinspired design. Nature's intricate machinery, forged through evolution, relies on a finite set of biomolecular building blocks with through-bond and through-space interactions. Repurposing these molecular building blocks requires a seamless integration of computational modeling, design, and experimental validation. The tools and concepts developed in this thesis pioneer new directions in peptide-materials design, grounded in fundamental principles of physical chemistry. We present a synergistic approach that integrates experimental designs and computational methods, specifically molecular dynamics simulations, to gain in-depth molecular insights crucial for advancing the …

Stereospecific Cross-Coupling Reactions Of Vinyl Triflates And An Investigation Of The Synthesis And Reactivity Of Activated Alkyltricyclohexylstannanes, Pejman Ghaemimohammadi

Dissertations, Theses, and Capstone Projects

Organic chemistry exists in all aspects of everyday life from polymers to pharmaceutics. Formation of carbon-carbon bonds is essential for the synthesis of complex organic compounds. This goal can be achieved by using transition metal catalysts. Second-row transition metals such as Pd, Pt, Rh, and Ir have shown remarkable efficacy in these reactions. Metal-catalyzed cross-coupling reactions form carbon-carbon bonds between electrophiles and nucleophiles using transition metal catalysts. Pd is mainly used in this reaction.

Transition metal-catalyzed cross-coupling reactions that form a bond between two C(sp²) carbons have been widely studied over the past decades. C(sp²)-C(sp^{3 …}

Evaluating The Reliability And Accuracy Of Alchemical Binding Free Energy Methods And Calculations, Fnu Sheenam

Dissertations, Theses, and Capstone Projects

Molecular recognition plays a crucial role in various biological processes, such as enzymatic reactions, signal transduction, and genetic information processing. Investigating how proteins selectively bind to their partners is an active research area, but there is a lack of experimental details on protein structures and interactions in molecular complexes. Computational techniques based on macromolecular structures offer a way to predict protein-ligand interactions and explore their recognition mechanisms. Estimating binding affinities, particularly through alchemical binding free energy calculations, has become valuable in supporting drug discovery. This work introduces new methodologies, utilizing the Alchemical Transfer Method, to address issues like poor convergence …

Analyzing Novel Metal Alloys For Glucose Sensing And Electrocatalysis, Anna Grace Boddy

Theses and Dissertations

In pharmaceutical and medicinal chemistry, metals and metal alloys often receive less attention compared to biological or organic compounds due to many factors including toxicity in the body for drug development or the cost of these metals. However, metals can play an important role in pharmaceuticals, having an impact on original cancer drugs, such as platinum used for head and neck tumors. Electrocatalysis is also another topic that receives less attention over topics such as chromatography in pharmaceuticals due to its potential toxic catalysts and voltages that could be harmful to the body. Electrocatalytic sensors can play an important role …

Development Of Stochastic And Time-Dependent Quantum Chemical Methods For Accurate Description Of Light-Matter Interactions With Applications In Photoionization And Inverse Photoemission In Nanomaterials, Nicole Spanedda

Dissertations - ALL

There are three main focuses of this work. First, the theoretical details of the Stratified Stochastic Enumeration of Molecular Orbitals (SSE-MO) method is presented, along with its application for calculating ionization potentials (IPs) of quantum dots. The SSE-MO method can readily be applied for the purpose of efficiently and accurately calculating ionization potentials, by constructing the frequency-dependent self-energy operator and then subsequently, solving the associated Dyson equation. Constructing the frequency-dependent self-energy operator is challenging because the scaling of the computational cost with respect to system size, becomes prohibitive for large systems, such as quantum dots. This is due to the …

Synthetic Studies On Ship Modulators, Hif-2Α Antagonists, And New Rhodium Carboxylate Catalysts, Angela Pacherille

Dissertations - ALL

The PI3K pathway is a major cell signaling axis in eukaryotic cells. This pathway employs the second messenger, inositol phospholipid PI(3,4,5)P3, which is responsible for activating Akt and other kinases creating a cascade of signals. The enzyme, SH2-containing inositol-5’-phosphatase (SHIP), plays a key role in this pathway by maintaining the delicate balance of PI(3,4,5)P3. Modulation of SHIP activity through the use of small molecule inhibitors may be utilized for the treatment of certain types of cancer, Alzheimer’s disease, and diabetes. A high-throughput screen identified the small molecule SHIP1 inhibitor, NSC23922, a mixture of 3α- and 3β-aminocholestane. These diastereomers were synthesized …

Luminescent Group 11 Metal (I) Chalcogen Clusters With A Conjugated Diphosphine Ligand, Kai Yu Jeffrey Li

Electronic Thesis and Dissertation Repository

Polynuclear Au (I) complexes exhibit rich photochemical properties and have the potential to find applications as molecular sensors, switches, or energy storage devices. Although dinuclear Au (I) complexes with bridging diphosphines have been extensively examined, most of those reported do not contain rigid-diphosphine ligands.

This thesis examines how the rigid diphosphine, 4,6-bis(diphenylphosphino)dibenzofuran (DBFDP) can be incorporated for the controlled assembly of photoluminescent gold (I) metal – chalcogenolate (chalcogenolate = RS^-, RSe^-; R = organic moiety) and gold (I) chalcogenide (chalcogenide = S^2-, Se^2-) bimetallic complexes. In these studies, the chalcogen …

Exploring The Reactivity Of Metal-Ligand Cooperative Complexes With Dioxazolones, Terminal Alkynes, And 2-Ethynylbenzyl Alcohol, Megan A. Hoffer Miss

Electronic Thesis and Dissertation Repository

N-Acyl ketenimines were attempted to be synthesized catalytically by [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ with phenylacetylene and 3-phenethynyl-1,2,4-dioxazol-5-one. Trapping agents were employed to identify the major product of the reaction, as many products were formed. [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ reacts with 3-phenethynyl-1,2,4-dioxazol-5-one generating an isocyanate via the Curtius rearrangement, confirmed by a forced Curtius rearrangement with 3-phenethynyl-1,2,4-dioxazol-5-one and 1,2,4-triazole. Rates of vinylidene formation using [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ and various terminal alkynes of different sterics and electronics were evaluated using a Hammett analysis for and simple rate comparisons. …

Dynamic Metal-Ligand Interactions In Semiconducting Π-Conjugated Materials, Peter Blake Joseph St Onge

Electronic Theses and Dissertations

Over the years, the development of materials has seen a vast amount of expansion into a variety of disciplines which have demonstrated usefulness in a large span of applications. One of these new and developing themes is the use of metals and ligands which are incorporated into polymers to modify their properties, which can enable different desired properties. Incorporation of metal-ligand complexes in materials chemistry has proven to be an area of rising interest, however, many of these interactions and systems remained completely unexplored. Understanding the key fundamental principles of how these materials can be changed and modified through metal-ligand …

Probing Charge Transport Mechanisms In 2d Semiconductive Metal Organic Framewoks, James Nyakuchena

Dissertations (1934 -)

Metal organic frameworks (MOFs) are a class of highly porous crystalline materials constructed from metal nodes connected by multitopic organic ligands. Due to their unique properties such as large surface area, tunable pore structure, and structural diversity, they have demonstrated potential in a wide array of applications including gas storage and separation, sensing, catalysis, and drug delivery. However, there are only a handful of MOFs reported that have electrical conductivity, which prevents their applications in photoelectronic and photocatalytic applications. This is because hard metals and redox inactive ligands with terminal hard linking bases such as carboxylates are often used in …

Medicinal Mushrooms: The Extraction And Analysis Of Bioactive Compounds From Hericium Erinaceus And Ganoderma Lucidum Mushrooms., Jhanielle Amanda-Kaye James

Electronic Theses and Dissertations

Medicinal mushrooms, such as Hericium erinaceus (lion's mane) and Ganoderma lucidum (reishi), have a rich history of traditional use in natural remedies, garnering attention for their bioactive compounds and nutritional benefits. Renowned for being protein-rich and low in fat, these fungi exhibit antimicrobial, anti-tumor, antioxidant, anti-diabetic, and anti-hypercholesterolemic properties attributed to their diverse bioactive components, including polysaccharides, proteins, terpenes, sterols, vitamins, polyphenols, and fatty acids. This study aimed to optimize extraction techniques, comparing maceration, ultrasound-assisted maceration, and Soxhlet extraction on fresh and dried lion's mane and reishi mushrooms. Varying solvent polarities and extraction times revealed that 8-hour extractions with dried …

Molecular Understanding And Design Of Deep Eutectic Solvents And Proteins Using Computer Simulations And Machine Learning, Usman Lame Abbas

Theses and Dissertations--Chemical and Materials Engineering

Hydrophobic deep eutectic solvents (DESs) have emerged as excellent extractants. A major challenge is the lack of an efficient tool to discover DES candidates. Currently, the search relies heavily on the researchers’ intuition or a trial-and-error process, which leads to a low success rate or bypassing of promising candidates. DES performance depends on the heterogeneous hydrogen bond environment formed by multiple hydrogen bond donors and acceptors. Understanding this heterogeneous hydrogen bond environment can help develop principles for designing high performance DESs for extraction and other separation applications. This work investigates the structure and dynamics of hydrogen bonds in hydrophobic DESs …

Design, Synthesis, And Characterization Of Complex Chalcogenides For Energy Storage And Energy Conversion Applications, Srikanth Balijapelly

Doctoral Dissertations

"Through this investigation, complex chalcogenides with the combination of main group metals, transition metals, and rare earth metals have been synthesized using the building block approach and their structure-property relationships are evaluated. The main emphasis of research is on rationally designing new materials for applications in sodium and lithium ion conducting solid electrolytes, cathodes, thermoelectrics, and nonlinear optics. Along with the experimental studies, theoretical calculations are also employed to better understand the physicochemical properties of the synthesized compounds.

The first part of the research will discuss designing alkali ion containing complex chalcogenides using the building block approach. This investigation resulted …

Chirality Determination Using Three-Wave Mixing Microwave Spectroscopy, Nicole Taylor Moon

Doctoral Dissertations

"Rotational spectroscopy has established itself as a reliable gas-phase spectroscopic technique for the structural determination of molecules. This reliability has stemmed from both advancements in microwave technology and a willingness from the community to push the boundaries of the field. In this dissertation, the boundaries are tested in both how well the technique can determine the structure of molecules exhibiting large amplitude motion and through chirality determination. The first half of this dissertation explores the use of deep averaging to determine the structure of silicon containing molecules in collaboration with Dr. Guirgis from the College of Charleston. For each of …

Role Of Relative Humidity In New Particle Formation From Ozonlysis Of Atmospheric Volatile Organic Compounds, Christopher Snyder

Graduate College Dissertations and Theses

The impact of relative humidity (RH) on organic new particle formation (NPF) from ozonolysis of biogenic volatile organic compounds (BVOCs) remains an area of active debate. Previous reports provide contradictory results indicating both depression and enhancement of NPF under conditions of moderate RH, while others ignore the potential impact. Only several reports have suggested that the effect may depend on absolute mixing ratio of the precursor volatile organic compound (VOC, ppbv). However, before any experiments could be completed, development of new methods was necessary to overcome the limitation of sampling ultrafine nanoparticles (<50 nm aerodynamic diameter) with aerosol mass spectrometry. This dissertation includes a report on a new Particle Growth Apparatus (PaGA) that artificially grows particles from as small as 17 nm to over 110nm. Considerable effort was made to identify the most suitable growth matrix (squalane) and optimize particle growth for reproducibility and sensitivity.

The PaGA was then utilized in the …

Impact Of Solar Radiation On Perchlorate Formation In The Atmosphere: Evidence From Ice Core Measurements, Bishnu Kunwar

Electronic Theses and Dissertations

Perchlorate, which derives from both anthropogenic and natural sources in the current environment, poses a substantial health hazard to humans as it competes with iodine uptake in the thyroid gland. Consequently, there has been considerable concern about minimizing human exposure to environmental perchlorate by restricting its release from man-made sources. However, the absence of a clear understanding regarding the respective contributions of man-made and natural sources has hindered widespread regulation efforts. A 300-year (1700–2007) Summit, Greenland ice core record from a previous study showed relatively stable perchlorate concentrations in Greenland snow prior to 1980, with some elevated perchlorate levels associated …

Synthesis Of Chiral Amino Acids Via Direct Amination Of Diazo Ester With A Rhodium-Based Catalyst, Steven J. Boyles

Honors College Theses

Amino acids are critical molecules within living organisms as they are the building blocks of proteins. In organisms, proteins serve as regulators of necessary processes, structural components in tissue, hormones, and neurotransmitters. Amino acid therapy is an emerging treatment in the medical field used to treat symptoms of diseases such as Alzheimer’s disease, Parkinson’s disease, and multiple sclerosis. Amino acid therapies have also shown promising effects when it comes to treating mood disorders and weight management. In order to increase the number of amino acids available and increase the potential treatments for other ailments, there is a drive to increase …

Amination Of 2-Bromo-6-Methylaminopyridine, Matthew H. Elterman

Honors College Theses

Extended metal atom chains (EMACs) represent molecular structures comprising a linear arrangement of metal ions, accompanied by supporting ligands. These compounds possess intriguing properties, yet remain understudied, drawing interest from diverse fields such as physics. However, synthesizing these multimetallic complexes poses significant challenges due to their intricate nature and specificity. Bridging ligands like silyl aminopyridine (SAP) and dipyridyl amine (DAP) have been utilized successfully to support EMACs, with SAP's application in this context being limited to a single published case, highlighting the urgent need for stabilization. This project aims to address this challenge through the synthesis of a novel scaffolded …

Inorganic Chemical Reasoning Skills: An Exploratory Study Into Understanding Students’ Choices And Thought Processes, Hannah P. Thompson

MSU Graduate Theses

Predicting the products of reactions is a fundamental skill for practicing inorganic chemists. However, the current knowledge of the strategies that students use to solve them is limited. Presumably, instructors of inorganic chemistry courses give complete-the-reaction assessment items hoping that students will use their knowledge of inorganic concepts to solve them; but it is conceivable that a successful student could use heuristics or domain general problem-solving methods. I proposed this study to determine which strategies were used by students when solving complete-the-reaction tasks in inorganic chemistry, and also to make qualitative connections between strategy and accuracy. This was done in …

Gas Evolution Of A Nickel-Zinc Cell, Niklas Landgraf

MSU Graduate Theses

Batteries are a foundational technology in some of the industries most essential to humanity. Often, their advancement to achieve better performance impacts human lives positively. There are a wide variety of battery chemistries that have been utilized, and the differences in their properties have caused them to be used in many distinct niche applications. Nickel-Zinc (NiZn) batteries are desirable because of their recyclable materials, high cell voltage, and high cycle-life. However, it experiences undesirable shape-change of its electrode materials and gas production due to the electrolysis of the aqueous electrolyte. These can lead to a decrease in capacity over many …

Investigating The Effect Of Relative Humidity On Organic New Particle Formation From The Dark Ozonolysis Of Biogenic Volatile Organic Compounds, Austin Callum Flueckiger

Graduate College Dissertations and Theses

Solid or liquid particulate matter suspended in the air, also known as atmospheric aerosols, are a ubiquitous component of Earth’s atmosphere. It is important to understand the chemical and physical processes that lead to the formation of these aerosols as they have an impact on climate health and human health. An important subset of atmospheric aerosols are secondary organic aerosols (SOA) that form from the gas-phase oxidation of volatile organic compounds (VOCs). VOCs can be emitted via biogenic and anthropogenic pathways, however, global estimates place biogenic sources as the major contributor. Although widely studied, some of the fundamental mechanisms that …

Development Of Novel Protein Digestion And Quantitation Methods For Mass Spectrometic Analysis, Yongling Ai

Dissertations

Proteins are the workhorses of biology, playing multifaceted roles in maintaining cellular function, signaling, and response to environmental cues. Understanding their abundance and dynamics is pivotal for unraveling the complexities of biological processes, which underpins the foundations of molecular and cellular biology. Accurate measurement of protein quantities provides insights into cellular homeostasis, facilitates the discovery of biomarkers, and sheds light on the molecular mechanisms of diseases, bridging the gap between the molecular intricacies of proteins and their functional consequences in health and disease. The evolution of protein quantitation methodologies, from classical colorimetric assays to sophisticated mass spectrometry-based approaches, has expanded …

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 …

Investigation Of Zinc And Iron In Wildflower Honey, Savannah Simpson

Honors Theses

Honey acts as a valuable food source for both animals and humans. When found in contaminated environments, there is an increased likelihood that honey samples will have high metal concentrations. It has been discovered that honey concentrations in metals can be different based on location. This experiment aims to determine the amount of two valuable metals, zinc, and iron, in various honey sources. These metals can be important to the human body because they help boost immunity and allow the body to carry out the functions required for survival. However, if these elements are present in copious quantities, then it …

Microplate-Like Metal Pyrophosphate Engineered On Ni-Foam Towards Multifunctional Electrode Material For Energy Conversion And Storage, Rishabh Srivastava

Electronic Theses & Dissertations

High clean energy demand, dire need for sustainable development, and low carbon footprints are the few intuitive challenges, leading researchers to aim for research and development for high-performance energy devices. The development of materials used in energy devices is currently focused on enhancing the performance, electronic properties, and durability of devices. Tunning the attributes of transition metals using pyrophosphate (P₂O₇) ligand moieties can be a promising approach to meet the requirements of energy devices such as water electrolyzers and supercapacitors, although such a material’s configuration is rarely exposed for this purpose of study.

Herein, we grow …