Chemistry Commons^™

Complementary Design Of Optical And Photochemical Systems, Joshua Plank

Chemistry Theses and Dissertations

The ability to manipulate chemical systems has been prized through history as the bridge between the macroscopic and microscopic worlds. As an example, the camera obscura has arguably existed since the earliest days of humanity; however, it was the discovery of early silver halide chemistry that lead to the ability to fix these images into the earliest photographs. In modern photolithography employed in electronics manufacturing, the primary resolution limits arise not from the chemistry of the molecules involved, but from the limits of the systems used to project light. Thus, as much as photochemistry advances, optical imaging and projection techniques …

Quantum Chemical Methods And Multiscale Modeling In Computer-Aided Drug Design, Hunter W. La Force

Chemistry Theses and Dissertations

Computer-Aided Drug Design (CADD) leverages a diverse toolkit of computational methods to accelerate the discovery and development of novel therapeutics. Among these, quantum chemical calculations provide unparalleled accuracy in understanding molecular interactions, albeit at a higher computational cost. This accuracy is crucial for identifying and quantifying fundamental interactions that dictate drug efficacy and selectivity, as exemplified by our investigation of ruthenium polypyridyl complexes. These metal-based compounds are model systems for studying covalent coordination bonds between ruthenium and its ligands and noncovalent interactions with DNA and protein targets. Local Mode Vibrational Theory emerges as a powerful lens within this framework, enabling …

Asymmetric, Carboxy And Ester Functionalized Fluorophthalocyanines: Synthesis, Adsorption, And Reactivity, Sean J. Scally

Seton Hall University Dissertations and Theses (ETDs)

Strong electron-deficient compounds, fluorinated metal phthalocyanines (F_xPcM), exhibit enhanced photosensitizing properties, making them optimal candidates for photocatalytic studies. Perfluoroalkyl-substituted phthalocyanines are notably thermally robust materials that are chemically inert and resistant to electrophilic, nucleophilic, and radical, including reactive oxygen species (ROS) attacks. These properties can be attributed to their ‘Teflon-like’ inert organic shield that surrounds a reactive metal center, as well as their complete (x = 16, 40, 64), or almost complete (x = 48) lack of C-H bonds. Third-generation, functionalized, asymmetric phthalocyanines are of interest due to their ability to bind to oxidic supports via a carboxyl …

A Computational Method For Detecting Compound Promiscuity In Early-Stage Pharmaceutical Discovery, John Allen Ringer

Computer Science ETDs

Modern drug discovery and chemical biology research relies heavily on analyzing bioassay data. One of the many challenges in bioassay data analysis is identifying false trails, i.e., chemical compounds which initially appear to have desirable activity but are found to be problematic upon further investigation. Badapple (the BioAssay-Data Associative Promiscuity Pattern Learning Engine) was created over ten years ago to help researchers identify promiscuous compounds and thus avoid a common source of these false trails. Through an effort involving software engineering, cheminformatics, and biomedical data science we have developed Badapple 2.0, which incorporates updated assay records and expanded data semantics. …

Enhancing Chemical Synthesis For Sustainability And Process Monitoring Utilizing Group Ten Metal Catalysis, Amanda M. Perkins

Theses and Dissertations

This thesis explores two sustainable methodologies by modifying established catalytic processes using group ten metal complexes from nickel and palladium. Efforts were made to provide alternatives for processes that often do not follow the principles of green chemistry. In the first project, a nickel(II) N-heterocyclic carbene complex was used to perform catalytic hydrogenation of 2-acetylpyridine under mild conditions. The complex was synthesized and characterized with techniques including mass spectrometry and 1H-NMR. Following this, the reactions were carried out to optimize conditions and yield moderate conversions. For the second project, the Suzuki-Miyaura cross coupling of 7-chlorotryptophan occurred utilizing a palladium complex …

Fe/Co/Ni-Doped Mos2 An Electrocatalyst For Overall Water Splitting, Himanshi Lnu

Electronic Theses & Dissertations

Electrochemical water splitting is a promising method for sustainable hydrogen production, addressing global energy challenges. However, its practical application is limited by the need for efficient and durable electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this study, MoS₂ was doped with Co, Ni, and Fe at varying concentrations (5:0.5, 5:1, and 5:1.5) using a hydrothermal synthesis method to evaluate their potential as electrocatalysts for water splitting. Characterization revealed that metal doping significantly altered the electronic and morphological properties of MoS₂, enhancing its catalytic performance. Electrochemical evaluations in alkaline media demonstrated that Co-doped MoS₂ …

The Effects Of Reprocessing, Post-Processing Conditions, And Environmental Exposure On The Physical Properties Of Post-Industrial And Post-Consumer Polyethylene, Grant M. Howard

Electronic Theses & Dissertations

THE EFFECTS OF REPROCESSING, POST-PROCESSING CONDITIONS, AND ENVIRONMENTAL EXPOSURE ON THE PHYSICAL PROPERTIES OF POST-INDUSTRIAL AND POST-CONSUMER POLYETHYLENE

An Abstract of the Thesis by

Grant Howard

Plastic pollution is a rapidly growing problem. Globally, millions of tons of plastic waste are produced, and that amount is projected to increase each year. To address this, recycling of commodity thermoplastics like polyethylene, polypropylene, and polyethylene terephthalate, have become a point of emphasis in industry. Companies have started to investigate the use of recycled plastics instead of virgin plastics in their products. The advantages of using recycled material are to receive tax breaks, …

Development Of Non-Precious Iron-Cobalt Alloy Catalyst For Electrocatalytic Reaction, Harsh Panchal

Electronic Theses & Dissertations

The development of a FeCo alloy catalyst with tunable Fe/Co ratios is examined to improve electrocatalytic performance in reactions like the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). Many energy conversion devices, such as fuel cells, metal-air batteries, and water-splitting systems, depend on these interactions to function. These technologies have huge potential to meet the increasing need for hydrogen production and renewable energy sources worldwide, which are critical to attaining a sustainable energy future. When compared with noble metal-based catalysts, the FeCo alloy catalyst shows much higher catalytic activity, according to previous studies. Hydrothermal …

Soybean Oil-Derived Acrylate/Methacrylate Ether For High Resolution Additive Manufacturing (3d Printing) Technology, Tanuj Patel

Electronic Theses & Dissertations

Additive Manufacturing is one of the rapidly developing techniques, as industries continue to explore new ways to create prototypes and end-use parts, one of the significant challenges that remains is the reliance on petroleum-based plastics for 3D printing, especially in the production of photocurable resins. that may be used to prototype complex structures and sophisticated geometries that are typically challenging to produce with conventional methods. Thus, replacing petroleum-based plastics with renewable resources is increasingly important for additive manufacturing (3D printing) of photocurable resins. The use of bio-based renewable resources in AM is a feasible alternative to traditional petroleum-based plastics. Henceforth, …

Epoxidized Castor Oil Based Thermosets With Reprocessable And Non Reprocessable Properties, Vaibhav Patel

Electronic Theses & Dissertations

Castor oil-based polymers have gained significant attention due to their renewable nature, low cost, and ease of processing, making them ideal for various applications, including biofuels and the petrochemical industry. Among these, epoxidized castor oil (ECO)-based thermosets have been extensively studied for their promising mechanical and thermal properties. This study focuses on recent advancements in ECO thermosets synthesized with 4,4-dithiodianiline (DTDA) which has aromatic disulfide bonds and 4,4-ditaminodiphenylmethane (DMPM) which has methylene bridge. FTIR spectroscopy confirmed the successful incorporation of epoxy functionalities into castor oil. The structure-reactivity relationship was examined through differential scanning calorimetry (DSC), which reveals that ECO_DMPM based …

Bio-Based Composites With Enhanced Mechanical Strength And Flame Retardancy, Riya Patel

Electronic Theses & Dissertations

Composites are versatile and useful in many fields, including aerospace, automotive, construction, and healthcare, due to their high mechanical strength. It is common practice to synthesize these materials using petroleum-based chemicals. Nonetheless, in the twenty-first century, scientists are more interested in using renewable resources to create composites. The greatest substitute for petroleum-based chemicals is vegetable oil. It has unsaturated double bonds that are modifiable chemically. In the present study, bio-polyol was synthesized using castor oil, an inedible vegetable oil. A ring-opening process was used to modify it and produce castor oil-based polyol. The synthesized castor oil-based polyol was characterized by …

Trade-Off Between Limonene & Geraniol-Based Reprocessable And Non-Reprocessable Epoxy Thermosets: Role Of Aliphatic Diamines In Polymer Networks Design, Priyankkumar Kanubhai Patel

Electronic Theses & Dissertations

The growing demand for sustainable materials, driven by environmental concerns and the rapid depletion of fossil fuels, has garnered significant attention in the fabrication of bio-based epoxy thermosets as renewable alternatives to petroleum-derived thermosetting polymers. The present study focuses on the synthesis and characterization of epoxy prepolymer resins derived from limonene and geraniol via a two-step process, followed by the fabrication of thermally cross-linked flexible epoxy thermoset films using various traditional aliphatic diamine curing agents, namely 1,2-ethylenediamine (EDA), 1,4-butylenediamine (BDA), and 1,6-hexamethylenediamine (HDA). Additionally, the incorporation of cystamine, a disulfide-containing diamine, enabled the formation of a covalent adaptable network through …

Investigations Into Fluorescence Of Fluorene Dimers: Linker Impacts And Tuning Potential Through Substituent Addition, Abigail R. Ressler

Theses and Dissertations

Fluorene-based fluorescing conjugated polymers are being used to develop sensors that show great sensitivity and selectivity, however, important questions about the photophysics of these systems remain unanswered. For example, a fluorescence intensity difference was observed between fluorene dimers linked with either an acetylene (diFA) or phenyl (diFP). The polymers diFA and diFP have similar structures and extinction coefficients, yet diFA yielded a five times higher fluorescence intensity than diFP. In project one, Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) were used to calculate the ground and excited states of diFA and diFP. A python code was developed to solve …

Modeling Molten Lithium Carbonate As Pollutant Absorbing Agent, Lucian G. Forestieri

Student Summer Scholars Manuscripts

Coal burning generates gaseous pollutants that are toxic to local environments and human health, namely hydrochloric acid and sulfur dioxide ( HCl and SO₂). Current methods for capturing these pollutants are flue gas desulfurization, which utilize solid or water- dissolved carbonates. This method, however, is inefficient mainly due to the product salts blocking further reactions. Molten carbonates may be a more efficient alternative. Experimental work cannot observe these reaction mechanisms, and the small number of current computational models do not match experimental properties. This work aims to develop a computational model of gaseous HCl scattering off the surface …

Probing Binding And Allosteric Mechanisms Of The Kras Interactions With Monobodies And Affimer Proteins : Ensemble-Based Mutational Profiling And Thermodynamic Analysis Of Binding Energetics And Allostery Reveal Diversity Of Functional Hotspots And Cryptic Pockets Linked By Conserved Communication Network, Mohammed Alshahrani, Vedant Parikh, Brandon Foley, Guang Hu, Gennady M. Verkhivker

Mathematics, Physics, and Computer Science Faculty Articles and Research

KRAS, a historically "undruggable" oncogenic driver, has eluded targeted therapies due to its lack of accessible binding pockets in its active state. This study investigates the conformational dynamics, binding mechanisms, and allosteric communication networks of KRAS in complexes with monobodies (12D1, 12D5) and affimer proteins (K6, K3, K69) to characterize the binding and allosteric mechanisms and hotspots of KRAS binding. Through molecular dynamics simulations, mutational scanning, binding free energy analysis and network-based analyses, we identified conserved allosteric hotspots that serve as critical nodes for long-range communication in KRAS. Key residues in β-strand 4 (F78, L80, F82), α-helix 3 (I93, H95, …

Phosphomimetic Substitution Of Serine Residue Ser260 With Aspartate Suggests Regulation Of Activity Of Human Cytosolic Malate Dehydrogenase By Phosphorylation, Charles Pelagalli '25, Luke Tischio, Kathleen Cornely

Chemistry & Biochemistry Faculty Publications

Human cytosolic malate dehydrogenase (MDH1) is a key enzyme involved in the malate-aspartate shuttle of eukaryotic cells, and which catalyzes the reaction of oxaloacetate to malate. As MDH1 is responsible for maintaining redox homeostasis by regeneration of NAD+ for glycolysis, its regulation is of particular interest in pharmaceutical applications, specifically in treating cancer cells that proliferate quickly and hence rely greatly on glycolysis. While the regulation of MDH1 by the phosphorylation of key residues has been previously documented, work still remains in identifying the specific residues involved in regulation of the enzyme by phosphorylation. In this study, we used …

Enabling New Synthetic Platforms For Aryne Synthesis With Aryl Thianthrenium Reagents, Riley Augustus Roberts

Dissertations and Theses

The enormous importance of aromatic rings in organic molecules cannot be understated. Aromatic rings are present in the majority of pharmaceuticals, agrochemicals, and consumer products. The way in which these rings are arranged and substituted results in a molecule’s unique properties. Because of this, the current limitations of the chemical methods used to synthesize these molecules results in limited structural diversity and thus missed opportunities for the development of value-added products. To this end, this work demonstrates novel methods of aryne synthesis, aryl thianthrenium synthesis and a unique approach to structural scaffold hopping. The approaches presented herein allow for rapid …

Turn-On Fluorescent Glucose Transport Bioprobe Enables Wash-Free Real-Time Monitoring Of Glucose Uptake Activity In Live Cells And Small Organisms, Monica Soma Hensley, David Hutchings, Abdelrahman Ismail, Marina Tanasova

Michigan Tech Publications

The direct link between sugar uptake and metabolic diseases highlights the iminent need for molecular tools to detect and evaluate alterations in sugar uptake efficiency as approaches to identify disease-relevant metabolic alterations. However, the strict requirements of facilitative glucose transporters regarding substrate binding and translocation pose challenges for developing effective fluorescence molecular probes. Based on the state-of-the-art understanding of glucose recognition by facilitative transporters (GLUTs), we designed a glucopyranoside mimic - GluRho - that delivers the “turn-on” rhodamine B to live cells via glucose transport, including major transporters GLUTs 1-4. The high binding affinity achieved through the secondary interaction between …

Development Of New Oxidative Methods And Synthesis Of Small Molecules For Modulation Of Biological Systems, Robert Eric Anderson

Dissertations - ALL

Oxoammonium salts have commonly been used to oxidize alcohols to aldehydes and ketones. More recently these reagents have been employed in several different oxidative transformations. Utilizing these reagents a new tandem elimination-oxidation process of tertiary alcohols has been developed. The new process yields an allylic ether which can be transformed to the alcohol easily through a reduction with zinc metal, removing the tetramethylpipyridyl protecting group derived form the oxoammonium salt. Mechanistically the reaction likely proceeds through oxoammonium salt mediated elimination followed by allylic oxidation through an ene-type mechanism. Due to the alcohol being protected by the easily removed oxoammonium salt, …

Chemical Reversal Of Beta-Lactam Resistance And Induction Of Hyper-Susceptibility In Pseudomonas Aeruginosa By Limiting Horizontal Gene Transfer Under Beta-Lactam Stress, Aimee Iradukunda

Dissertations - ALL

The emergence of antibiotic resistance poses a significant threat to global health, with certain bacterial strains evolving to resist multiple drugs. Urgent action is necessary to develop new antibacterial agents that effectively target these resistant strains; however, no new classes of antibiotics have been approved in recent decades. This research employs innovative biological tools to identify and highlight factors influencing resistance dynamics. Additionally, this study refines the novel approach by utilizing adjuvants to chemically repurpose existing antibiotics and improve their effectiveness against antibiotic-resistant strains. Pseudomonas aeruginosa, recognized for its adaptability, persistent infections—especially in cystic fibrosis patients—and widespread antibiotic resistance, serves …

Diel Patterns Of Biogeochemical Indicators In Tidally-Dominated Creeks, Juliana Calderone

Honors Theses

Marshes and swashes are vital environments as a controlling barrier between land affected by various pollutants and the ocean. Eutrophication and the effects of this process can be detrimental for the areas experiencing it. I am interested in ways areas that have little contact with human interactions compare to areas that are heavily urbanized, and whether either of these locations is at a higher risk for eutrophication. Using spectrophotometry and fluorometry, I analyzed samples collected from the relatively undeveloped and restricted-access locations of Waities Island Beach and Dunn Sound monthly for dissolved nutrients, and chlorophyll. At the time of sampling, …

Effects Of Structure Of Mepegn Polymers On Hydroxide Conductivity In Anhydrous Anionic Exchange Membranes, Athan M. Gregory

Honors Theses

Anhydrous hydroxide ion (OH-) conducting polymer electrolytes composed of a 1-methyl-pyrrolidinium (1mp) head group linked to various MePEGn (n = 3, 7, 12) backbones were prepared. We have examined the structure of these anion exchange membranes to observe how the structure of the electrolyte affects the observed ionic conductivity. The structural parameters investigated were polymer length, viscosity, fractional free volume (FFV), and volume fraction of PEG (Vf,PEG), and each polymer varied in these properties. Through a comparison of the conductivity and structural parameters in the MePEGn-based anion electrolytes, we have shown that each of these structural properties weakly affects the …

Impact Of Unconventional Gas Extraction On Tributaries Of Tenmile Creek, Greene County, Pennsylvania: A 12-Year Perspective, Christian L. Beall

Electronic Theses and Dissertations

Much of southwestern Pennsylvania has been central to a rapid increase in development for unconventional natural gas extraction in the past two decades. The continued monitoring of streams over their lifetime as extraction sites is pivotal to understanding the effects of fracking on local waterways and their ability to provide for wildlife and human use. Here, using multiple indices of biotic integrity (IBI), I perform analyses of fish and macroinvertebrate communities as well as water chemistry on two streams, Bates Fork (with shale wells) and Fonner Run (without), as part of a follow-up to work performed there from 2010-2012. Fish …

Synthesis Of Sensitive Oligodeoxynucleotides Containing Acylated Cytosine, Adenine, And Guanine Nucleobases, Komal Chillar, Rohith Awasthy, Marina Tanasova, Shiyue Fang

Michigan Tech Publications

Background/Objective: Oligodeoxynucleotides (ODNs) containing base-labile modifications such as N4-acetyldeoxycytidine (4acC), N6-acetyladenosine (6acA), N2- acetylguanosine (2acG), and N4-methyoxycarbonyldeoxycytidine (4mcC) are highly challenging to synthesize because standard ODN synthesis methods require deprotection and cleavage under strongly basic and nucleophilic conditions, and there is a lack of ideal alternative methods to solve the problem. The objective of this work is to explore the capability of the recently developed 1,3-dithian-2-yl-methoxycarbonyl (Dmoc) method for the incorporation of multiple 4acC modifications into a single ODN molecule and the feasibility of using the method for the incorporation of the 6acA, 2acG and 4mcC modifications into ODNs. Methods: …

Structure Determination Of Mg2tihn And Mg3tihn (N=1-25) Clusters, Meagan Dobbs

Honors College Theses

Fossil fuels are a resource that is used in everyday life. A major problem with the reliance on fossil fuels lies in their major contributor to global warming. When fossil fuels are burned, they release greenhouse gases into the atmosphere and warm the Earth. In order to decrease the amount of greenhouse gases being emitted new fuel sources are being considered, and a leading candidate is hydrogen. This project looks at magnesium hydride clusters doped with a titanium atom. Specifically, the Mg₂TiH_n (n =1-25) and Mg₃TiH_n (n =1-25) clusters are considered. The …

Architecture Of Pseudomonas Aeruginosa Glutamyl-Trna Synthetase Defines A Subfamily Of Dimeric Class Ib Aminoacyl-Trna Synthetases, Michael K. Fenwick, Stephen J. Mayclin, Steve Seibold, Amy E. Derocher, Sandhya Subramanian, Isabelle Q. Phan, David M. Dranow, Donald D. Lorimer, Ariel B. Abramov, James M. Bullard

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The aminoacyl-tRNA synthetases (AaRSs) are an ancient family of structurally diverse enzymes that are divided into two major classes. The functionalities of most AaRSs are inextricably linked to their oligomeric states. While GluRSs were previously classified as monomers, the current investigation reveals that the form expressed in Pseudomonas aeruginosa is a rotationally pseudosymmetrical homodimer featuring intersubunit tRNA binding sites. Both subunits display a highly bent, “pipe strap” conformation, with the anticodon binding domain directed toward the active site. The tRNA binding sites are similar in shape to those of the monomeric GluRSs, but are formed through an approximately 180-degree rotation …

Preparation, And Characterization Of Gypsum-Levan Composites And Evaluation Of Their Preliminary In Vitro And Antibacterial Characteristics, Jamileh Sultan El Arab

Thesis/ Dissertation Defenses

Orthopedic surgery has to contend with a myriad of issues with bones, injuries such as fractures as well as chronic ailments, like osteoporosis. There is a widespread understanding and execution of polymethylmethacrylate (PMMA) bone cement and calcium phosphate cements (CPCs), however their drawbacks like being non-biodegradable, generating heat, low bioactivity, and other issues reserve the development of better substitutes This study intends to develop and incorporate microbial levan squaring as a β-2,6-linked fructan polysaccharide into gypsum-based formulations of bone cements to make them biodegradable, bioactive and amplify their mechanical properties. The research aims to address the performance drawbacks of traditional …

California Red Hummingbird Flowers: Color Convergence Across Four Biochemical Categories, Melissa León-Osper, Victor Rossi, Katie Conrad, Josephine Hernandez Mena, Elaine Meslow, Amelia A. Fuller, Eduardo Narbona, Justen B. Whittall

Chemistry and Biochemistry

There are 129 red-flowered species in western North America that fit the hummingbird pollination syndrome. Theory predicts that these flowers should produce a specific red color that is conspicuous to hummingbirds but not to bees. In a few well-studied cases, red flowers can be produced with pelargonidin, cyanidin, or both—sometimes complemented with the addition of yellow carotenoids and sometimes not. Which pigment combinations are most common in California and whether they affect conspicuousness to hummingbirds and bees remain unknown. To determine the taxonomic distribution of the pigments responsible for red hummingbird-pollinated flowers, we quantified the color of 36 red-flowered species …

High-Quality Factor Phase Gradient Metasurfaces With Dynamic Reconfigurability, Lin Lin

Arts & Sciences Graduate Student Theses and Dissertations

Free-space optical communication holds immense potential for surpassing the bandwidth limitations of conventional physically defined channels. Achieving flexible and efficient communication in free space requires compact, robust optical components capable of dynamically tuning laser light without relying on bulky lenses or mechanically driven mirrors. Metasurfaces, or flat optics, have garnered significant attention due to their densely arranged subwavelength nano-resonators, which impart phase, amplitude, and polarization changes comparable to those of traditional bulky optics. However, conventional phase gradient metasurfaces are constrained by passive designs based on geometric configurations and the weak light-matter interaction inherent in most dielectric materials, limiting their applicability …

Bottom-Up Mechanochemical Synthesis Of Nanographene, Sarah Kerr

Honors Theses

This research explores the application of mechanochemistry in the bottom-up synthesis of nanographene, specifically focusing on the mechanochemical Diels-Alder (DA) reaction. The study investigates the effect of different reaction conditions and dienophiles on the mechanochemical DA reaction, aiming to optimize reaction efficiency and yield using a ball mill. The initial trials with a sterically hindered dienophile (2) and an electron-deficient diene experienced repeated failure, while reactions using dienophile (B), a terminal alkyne showed more promising results. Various variables were examined, including reaction time, jar size, ball size, ball number, shaking frequency, liquid-assisted grinding (LAG), heating, and diene to dienophile ratio, …