Chemistry Commons^™

Investigating The Photophysical Dynamics Of Anthracene And Acridine Derivatives Using Time-Resolved Spectroscopy, Sophia Tiano

Open Access Dissertations

Anthracenes and acridines are among the simplest visible light absorbing heterocyclic and polycyclic aromatic hydrocarbons and as such are extensively used in a variety of applications including photosensitizers and fluorescent sensors. Although the photophysics of some derivatives have been studied in the past, there is still a lot of unknown fundamental information that is vital in order to optimize these molecules for particular applications. Transient absorption spectroscopy was used to study the photophysics of the 9-substituted methyl, hydroxymethyl and formyl derivatives of acridine and anthracene. The growth and decay of the triplet-triplet absorption peak were quantified for each dye in …

Ultra-Rapid Electrophilic Cysteine Arylation Using Pyridinium Salts, Bradley M. Lipka

Open Access Dissertations

Small molecule-based bioconjugation enables in vitro and in vivo functionalization of proteins and peptides, significantly expanding the chemical space of biomacromolecules. Among these transformations, nucleophilic aromatic substitution (S_NAr) of cysteine residues is a widely employed strategy for protein bioconjugation.

Although many reagents facilitate cysteine arylation, they are disadvantageous in two crucial aspects - limited synthetic modularity and undesired hydrophobicity. First, conventional cysteine arylating reagents are frequently activated by multiple electron-withdrawing groups (EWGs) on a single aromatic ring, leaving few synthetic handles to derivatize the reagents for advanced applications. Second, these labeling reagents are generally hydrophobic in nature and …

Identifying The Constituents Of Pyrolysis Oil Using Supercritical Fluid Chromatography- Fraction Collection (Sfc-Fc) And Gas Chromatography- Mass Spectrometry/Vacuum Ultraviolet Spectroscopy (Gc-Ms/Vuv), Sadid Morshed

2025 Fall Honors Capstones Projects - Archive

Plastic waste continues to accumulate as production increases and disposal methods remain insufficient. Even with recycling programs in place, much of the discarded plastic still ends up in landfills or waterways, eventually breaking down into harmful microplastics. One promising solution is the conversion of plastic waste into pyrolysis oil, which can also serve as an alternative feedstock for chemicals. Pyrolysis oil is produced by heating plastics to approximately 800 °C in the absence of oxygen, resulting in a complex mixture of hydrocarbons that includes paraffins, isoparaffins, olefins, naphthenes, and aromatics. Analyzing the amount of oxygen, nitrogen, and sulfur in these …

Direct Partial Oxidation Of Methane To Methanol Using Dioxygen Over Superhydrophobic Modified Catalysts, Oluchukwu V. Igboenyesi

Chemistry & Biochemistry Dissertations - Archive

Various methods for enhancing catalysts activity and productivity in gas to liquid synthesis like Direct Methane to Methanol Conversion and Fischer Tropsch Synthesis have been studied over the years. Some of these methods include the use of promoters, bifunctional catalysts, introducing steam, optimizing reaction conditions and catalyst modification. The choice of catalysts and their modification plays a critical role in improving the overall productivity in gas to liquid synthesis.

This research explored the superhydrophobic modification of heterogenous catalysts used in Direct Methane to Methanol Conversion (DMTM) and Fischer Tropsch Synthesis (FTS). The catalysts were modified with Perfluoro alkyls (PFSMA). The …

Copper-Based Oxide Semiconductors: Transparent Conductors And Ternary Alloys, Abhishek Rawat

Chemistry & Biochemistry Dissertations - Archive

This dissertation explores the strategic design and development of copper-based metal oxide semiconductors for photoelectrochemical (PEC) and optoelectronic applications, with a focus on advancing materials for sustainable energy technologies. Through a comprehensive investigation into copper vanadates and copper oxides, the work aims to understand and enhance charge transport, light-harvesting capabilities, and electronic structure modulation. The research integrates fundamental materials chemistry with applied photoelectrochemical studies to uncover the role of copper's d-electrons in mid-gap state formation, multifunctionality through electronic structure tuning, and the development of low-temperature transparent conductive oxides.

In chapter 2, we have discussed the attributes of copper metavanadate (CuV …

The Impact Of Inter-Subunit Communication On F420h2:Nadp+ Oxidioreductase: A Kinetic Approach, Jamariya A. Howard

Chemistry & Biochemistry Dissertations - Archive

F₄₂₀H₂:NADP⁺ Oxidoreductase (Fno) catalyzes the reversible reduction of NADP⁺ to NADPH using reduced F₄₂₀ as the hydride donor. Both NADPH and the F₄₂₀ cofactor play significant roles in various metabolic pathways, including glycolysis and methanogenesis, particularly in methanogenic and sulfate-reducing archaea. These organisms play an essential role in global carbon cycling by converting carbon dioxide to methane through the methanogenic pathway, which is directly tied to energy production. This thesis investigates the hydride transfer mechanism of Fno from the extreme thermophile Archaeoglobus fulgidus, using fluorescence binding, steady-state and pre steady-state kinetics.

Chapter 1 outlines the structural and spectral characteristics …

Investigating The Impact Of Pfas Contamination On Mental Health, Jihyun Kim

Open Educational Resources

To explore the intersection of environmental injustice, racial disparities, and public health through an examination of PFAS contamination in drinking water and its impact on communities of color. This study will address environmental, social, and health implications of PFAS exposure, with a specific emphasis on promoting equity and advocating for policy changes to rectify systemic inequalities.

Reducing Friction In Machine Oil Via Cesium-Hybridized Graphene Oxide Quantum Dot Additives, Islam Gomaa, Sherief Elsoudy, Maryam Galal, Ahmed Azim

Nanotechnology Research Centre

Friction and wear are among the most common causes of energy loss and component failure in mechanical systems, accounting for around 20–30% of total global energy consumption. Conventional lubricants fail to provide consistent performance in harsh conditions due to inadequate additive dispersion, agglomeration, and restricted surface reactivity. Recent advances in nanomaterial-based lubricants have shown promise, but it remains difficult to achieve significant friction and wear reduction at low additive concentrations while preserving stability. In this study, we synthesized and tested cesium-hybridized graphene oxide quantum dots (Cs-GOQDs) as novel lubricant additives. When incorporated into machine oil at 0.1 wt%, Cs-GOQDs reduced …

Ex Vivo Single-Molecule Analysis Of Ryanodine Receptor 2 Assembly In Cardiac And Neuronal Tissue, Qianye Yin, Christopher I. Richards

Chemistry Faculty Publications

Understanding receptor assembly is critical for elucidating the mechanisms underlying their function and regulation in physiological processes. While traditional in vitro single-molecule studies rely on isolating proteins from heterologous expression systems, they often fail to capture the in vivo physiological complexity involved in the organization and assembly of cell surface proteins. This protocol employs Total Internal Reflection Fluorescence Microscopy (TIRFM) to study GFP-tagged Ryanodine Receptor 2 (RyR2) molecules encapsulated within nanoscale vesicles. These vesicles, generated from organs rapidly extracted from the animal, effectively provide a snapshot of the receptor's assembly state at the time of extraction, enabling detailed analysis of …

Complexometric Titration Of Terbium(Iii) Compounds: An Analytical Blast From The Past Gives Purity Assurance When Modern Instruments Fail Us., Jake E. Timbes, Cameron Bateman, Justin Stace

Science University Research Symposium (SURS)

Lanthanide ions have attracted attention for applications in microwave electronics, memory devices, lighting applications, and chemical sensors. Terbium(III)-centered homoleptic complexes show promise as potential fluorescence-based chemical sensing agents. Tb(phen)2(NO3)3 (phen = 1,10-phenothroline) exhibits striking visible emission when excited by short-wave ultraviolet light; this emission is completely quenched by exposure to water or strong acid. However, the luminescence returns under relatively benign conditions. Unfortunately, our array of terbium(III) complexes are notoriously insoluble; rendering standard analytical techniques useless to assess purity, notably, 1H and 13C-NMR. Titration is a useful technique to give us, an assurance of purity—in conjunction with the ad-hoc purity …

Kinetic Analysis Of A Carbon-Rich Sico Model System, Takhya Holley

Chemistry & Biochemistry Theses - Archive

Kinetic Analysis of a Silicon Oxycarbide (polymethylhydrosiloxane/divinylbenzene) material was done for meaning of kinetic analysis methodology development. The material was synthesized using the standard procedure from, Blum 2005. A series of TGA’s was done using non-isothermal experiments. The analysis involved an initial isoconversional analysis using Friedman method, then decomposition of processes into individual processes using the Fraser-Suzuki function. The validation agreed within 1%, which is permissible by the ICTAC recommendations. The activation energies of the individual processes were determined using the Friedman method.The pre-dominant process #2 was found to have an activation energy of 220 +- 20 kj/mol and first-order …

Estimating Vapor Pressures Of Pheromone Compounds Using Gas Chromatographic Retention, Bipasha Sarker

Chemistry & Biochemistry Theses - Archive

Accurate determination of the vapor pressures of organic materials is important for predicting the sample’s environmental impact. It is difficult to directly measure accurate and precise vapor pressures of chemical compounds with direct experimental methods. Thus, indirect or predictive models for estimating vapor pressures are used. In this study, we follow a gas−liquid chromatography (GLC)-based approach, where retention data is correlated with vapor pressure using multiple reference standards. The method (GLC-RTyS) requires temperature-dependent retention factors (k-values) for test compounds and reference standards with known vapor pressures at matching temperatures. It has been observed that reference standards selected according to functional …

Supporting Information For: "Synthesis And Characterization Of Γ-Acyloxyl-Ε-Caprolactones”, Greyson Greischar, Tapiwa Gono Phiri, Ellie Haljun, Jenna Ray, Meheret Ourgessa, Garrett Thesing, Lila Lofving, Aidan Clark, Suzanna Bator, Durwynn Jno Baptise, Wyatt Cole, Michael Itschner, Yutan D.Y.L. Getzler

Data Sets

This dataset contains the raw, unprocessed NMR data for the title compounds of the paper "Synthesis and characterization of γ-acyloxyl-ε-caprolactones” published in iScience (DOI: 10.1016/j.isci.2026.115190. NMR spectra were acquired on a JEOL-ECZS 400 MHz spectrometer in CDCl3 (Cambridge Isotope Labs, 99.8% D) and are saved in the .jdf format. Chemical structures in this document will be represented in the SMILES format. The paper details the synthesis of eight lactones, with variation of the exocyclic ester. Within this set, we consider CC(OC(CC1)CCOC1=O)=O (7-oxooxepan-4-yl acetate or γ-acetyl-ε-caprolactone) to be the parent compound. The R group pendant from the exocylic carbonyl in this …

Progress Toward The Synthesis Of Pyridine-Containing Macrocycles Using Dynamic Alkyne And Olefin Metathesis, Stephen Kwas , '25

Senior Theses, Projects, and Awards

Tubular structures are ubiquitous in nature and possess functions ranging from the structural ones played by microtubules to transporting necessary ions across cell membranes by membrane proteins. In addition, the excellent electronic and structural properties of carbon nanotubes have made them of great interest to chemists. Yet, the functionalization of these nanotubes is hindered by unselective post-modification, often requiring harsh reaction conditions. As such, the assembly of macrocycles into nanotubular structures has been widely studied by chemists. One such way to make these materials is by using dynamic, reversible reactions to synthesize pyridine-containing macrocycles in high yields. Due to inherent …

Hydrogen Peroxide Production From Light-Driven Water Oxidation Via Nickel Oxide-Titanium Dioxide Heteronanocrystals, Mahfuz Ahammed Swadhen

Dissertations and Theses

High dependence on fossil fuels for energy carries risks for the environment, health, energy, and geopolitical stability. One of the solutions to address this is solar energy utilization, and the use of semiconductors for photocatalytic water splitting is a tantalizing prospect. An n-type semiconductor TiO2 combined with p-type NiO producing a heteronanojunction shows effective light-driven oxidation of H2O into H2O2. We developed a synthetic method to attach NiO nanoparticles on the surface of anatase TiO2 nanorods. We characterized the materials with UV-visible spectroscopy, powder X-ray diffraction, and electron microscopy. We immobilized the HNCs on fumed silica and removed organic surfactants …

Scope And Mechanism Of The Ruthenium-Catalyzed Sp3 C–H Coupling Reaction Of 2-Alkylindoles With Enones For The Synthesis Of Carbazole Derivatives, Krishna Prasad Gnyawali, Mina Son, Donghun Hwang, Nuwan Asanka Pannilawithana, Mu-Hyun Baik, Chase S. Yi

Chemistry Faculty Research and Publications

The catalytic system consisting of a cationic Ru–H complex 1 and 3,4,5,6-tetrachloro-1,2-benzoquinone (L1) was found to be highly effective for the dehydrative sp³ C–H coupling reaction of 2-alkyl substituted indoles with enones to form 2,4-disubstituted carbazole products. The analogous coupling reaction of 2-alkylindoles with linear enones bearing the cyclic olefinic group afforded tetracyclic carbazole products. A normal deuterium kinetic isotope effect was measured from the coupling reaction of 1,2-dimethylindole versus 1-methyl-2-(methyl-d₃)indole with (E)-3-penten-2-one (k_H/k_D = 2.5). The Hammett plot was constructed from the reaction of para-substituted …

Verification Of Real-Time Smoke Simulations: A Case Study On Early Summer North American Wildfire Events, Daniel Bonilla

Pitzer Senior Theses

As wildfire intensity and frequency escalate in times of unprecedented climate change and severe droughts, it is important to enhance forecasting models that accurately and efficiently predict wildfire smoke movement. NOAA’s experimental Rapid-Refresh Forecasting System with Smoke and Dust (RRFS-SD) aims to improve upon the High-Resolution Rapid Refresh- Smoke (HRRR-Smoke), by extending the domain to include all of North America and incorporating new developments in physics and wildfire parameterizations. Our work explores the process of adding satellite Aerosol Optical Depth (AOD) data, through AERONET, as an additional method of verification of the RRFS-SD experimental model. Using a case study on …

Cui-Derived Cuxo Thin Films Development Via Thermal Oxidation For Lead-Free Perovskite Solar Cells, Md Jakir Hossen, Md Shahinuzzaman, M. S. Jamal, Suhana Mohd Said, S. F.W.M. Hatta, Md Helal Miah, Mayeen Uddin Khandaker, Mohammad Nur-E-Alam, Mohammad Aminul Islam

Research outputs 2022 to 2026

The development of low-cost, stable, and efficient hole transport layers (HTLs) is crucial to the advancement of lead-free perovskite solar cells. In this work, a solution-based oxidation process is employed to convert spin-coated copper iodide (CuI) films into mixed-phase copper oxide (CuxO) thin films comprising Cu₂O and CuO. Oxidation occurs under moderate temperatures (200–300°C), leading to uniform, compact, and highly conductive p-type films with tunable bandgaps. Structural, morphological, and optical analysis confirms successful phase transformation, and measurements of Hall effect reveal maximum mobility of holes of 26.7 cm² V⁻¹ s⁻¹ for double-coated films annealed at 300°C. Device …

Transient Transmembrane-Electrostatically Localized Protons And Transmembrane Potential In A Laser Flashed Bacteriorhodopsin Purple Membrane Open Flat Sheet - Summary, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

The transmembrane-electrostatically localized protons/cations charges (TELCs, also known as TELPs) model may serve as a unified framework to explain a wide range of bioenergetic phenomena. Transient transmembrane-electrostatically localized protons (TELPs) and transmembrane potential in a laser flash-energized bacteriorhodopsin (bR) purple membrane (PM) open flat sheet are now better analyzed. Under the Heberle et al. (1994) experimental conditions, the number of bR molecules is now calculated to be 8200 per PM open flat sheet with a diameter of 600 nm. With a single-turnover laser flash intensity of 3 mJ/cm² to photoexcite 10% of the bR molecules, the laser flash-induced peak TELCs …

Experimental Absorption Cross Sections For Zro, Léo Lavy, Peter F. Bernath, Manish Bhusal, Jacques Liévin

Chemistry & Biochemistry Faculty Publications

Absorption cross sections for ZrO are provided and can be used as a template to interpret spectra of S-type stars. The ZrO spectrum was measured in emission from a carbon furnace at 2700 K and calibrated using synthetic spectra of ⁹⁰Zr¹⁶O. A set of nearly isolated molecular lines has been used for the calibration. We also thoroughly review the literature on the spectroscopy of ZrO. Comparison of the experimental spectrum with currently available line lists revealed issues in ZrO spectral simulation. (a) Within band systems, the relative intensities are not always well reproduced. (b) We identify yet unreported band systems, …

Chemoproteomic Profiling Of A Carbon-Stabilized Gold(Iii) Macrocycle Reveals Cellular Engagement With Hmox2, Sailajah Gukathasan, Chibuzor Ngozi Olelewe, Libby Ratliff, Jong H. Kim, Alyson M. Ackerman, J. Robert Mccorkle, Sean Parkin, Gunnar F. Kwakye, Jill M. Kolesar, Samuel G. Awuah

Chemistry Faculty Publications

In this work, we discovered a novel organometallic gold(III) macrocycle, Au-Mac1, that demonstrates anticancer potency in a panel of triple-negative breast cancer cells (TNBC), and based on this complex, a biotinylated-Au-Mac1 probe was designed for target identification via chemoproteomics, which uncovered the engagement of HMOX2 of the heme-energy metabolism pathway. Using orthogonal chemical biology and molecular biology approaches, including immunoblotting, flow cytometry, and cellular thermal shift assays, it was confirmed that Au-Mac1 engages HMOX2 in cells. Downstream effects of Au-Mac1 on the depletion of mitochondrial membrane proteins and bioenergetics point to the potential role of HMOX2 in cancer. Importantly, Au-Mac1 …

Electrochemical Observation And Ph Dependence Of All Three Expected Redox Couples In An Extremophilic Bifurcating Electron Transfer Flavoprotein With Fused Subunits, Debarati Das, Wassim El Housseini, Monica Brachi, Shelley D. Minteer, Anne-Frances Miller

Chemistry Faculty Publications

Bifurcating enzymes employ energy from a favorable electron transfer to drive unfavorable transfer of a second electron, thereby generating a more reactive product. They are therefore highly desirable in catalytic systems, for example, to drive challenging reactions such as nitrogen fixation. While most bifurcating enzymes contain air-sensitive metal centers, bifurcating electron transfer flavoproteins (bETFs) employ flavins. However, they have not been successfully deployed on electrodes. Herein, we demonstrate immobilization and expected thermodynamic reactivity of a bETF from a hyperthermophilic archaeon, Sulfolobus acidocaldarius (SaETF). SaETF differs from previously biochemically characterized bETFs in being a single protein, representing a …

Functional Utility Of Gold Complexes With Phosphorus Donor Ligands In Biological Systems, Adedamola S. Arojojoye, Samuel G. Awuah

Chemistry Faculty Publications

Metallo-phosphines are ubiquitous in organometallic chemistry with widespread applications as catalysts in various chemical transformations, precursors for organic electronics, and chemotherapeutic agents or chemical probes. Here, we provide a comprehensive review of the exploration of the current biological applications of Au complexes bearing phosphine donor ligands. The goal is to deepen our understanding of the synthetic utility and reactivity of Au-phosphine complexes to provide insights that could lead to the design of new molecules and enhance the cross-application or repurposing of these complexes.

Raw Data For Tailoring High Entropy Borides For Hydrogenation: The Influence Of Crystal Morphology And The Exploration Of Catalytic Pathways, Michael Yeung, Ting Wang

Chemistry Department Faculty Scholarship

The high entropy boride (HEB) Al0.2Nb0.2Pt0.2Ta0.2Ti0.2B2, with its unique crystal structure and high coordination (platinum coordinated to 12 borons), has been shown in our previous work to exhibit exceptional catalytic properties, especially in sulfur-rich environments, where traditional platinum catalysts would succumb to sulfur-poisoning. In this work, we investigate the mechanism of the HEB catalyst, first by comparing the synthesis by flux growth, as previously reported, to an arc melted preparation. It is evident that the aluminum flux growth synthesis encourages the growth of single crystals, with clear and defined crystal facets, whereas the arc melted sample results in poorly defined …

Raw Data For A Mild Alkaline Hydrothermal Etchant For Mbene Exfoliation, Michael Yeung

Chemistry Department Faculty Scholarship

Abstract for data:

Raw data for the journal publication, A Mild Alkaline Hydrothermal Ethant for MBene Exfoliation. ReadMe file provided.

Abstract for journal publication:

MoBene (the boride equivalent of MXenes) has been a synthetic challenge because borides degrade in common etching media. Inspired by the intercalation of lithium ions into AlOOH, we hypothesized that a hydrothermal route enables lithium ions to intercalate the aluminum layer of MoAlB and further separate the MoB sheet apart. Here, MoBene is first synthesized through a mild hydrothermal etching method with dilute lithium hydroxide. X-ray diffraction showed a peak at 8.9°, confirming an exfoliated layered …

Toward Biocompatible Assessment Of N-15 Hyperpolarized Metronidazole For Hypoxia Sensing, Faisal Asif

Wayne State University Theses

Recent advances in hyperpolarization, particularly Signal Amplification by Reversible Exchange (SABRE), have enhanced molecular magnetic resonance imaging (MRI) for in vivo applications. This study investigates [15N3]metronidazole, a tri-nitrogen-labeled derivative of an FDA-approved antibiotic, as a hypoxia-sensitive imaging agent. Under hypoxic conditions, the nitroimidazole group undergoes stepwise reduction to an amino group, inducing significant 15N chemical shift changes (30–600 ppm). We aim to develop an iridium catalyst-free, biocompatible hyperpolarized (HP) [15N3]metronidazole formulation exhibiting robust polarization (up to 15%) and extended T1 lifetimes (~10 min). Three specific objectives guide this work: (1) formulation of a HP injectable with enhanced 15N detection, (2) …

Durable Oxyfluoride Waste Forms For Salt Wastes From Molten Salt Reactors, Alevtina A. Maksimova, Jake W. Amoroso, Matthew Page, Gregory Morrison, Hans Conrad Zur Loye

Faculty Publications

Molten salt reactors (MSRs) are promising technology to replace traditional light and heavy water reactors in the near future. Waste management for MSRs, however, remains a pressing concern that needs to be resolved prior to realizing deployment of MSRs. Specifically, the generated salt waste needs to be safely sequestered, a task made difficult by the high solubility of the salt waste that can cause the release of radionuclides into the environment. This work demonstrates a new approach to immobilize multiple fluoride salts into a single waste form by converting highly-soluble fluorides to durable and stable oxyfluorides. Notably, we report a …

Eugenol Loaded Calcium Citrate Particle As A Ph Triggered Drug Release System And A Reducing Agent For Au (Iii), Sadia Afrin

Dissertations and Theses

The study demonstrated that eugenol affects the morphology of calcium citrate particles during their formation, as confirmed by SEM micrography and PXRD analysis. Coating of eugenol loaded calcium citrate particles (CaCit MPs) with casein improves their known pH-dependent drug release profile, as confirmed by UV absorption spectroscopy. The casein-coated eugenol-loaded CaCit MPs (CCaCit(eu) MPs) can effectively control and sustain drug release under different pH conditions, particularly at acidic pH values (4.8 and 5.5), which mimics the environment of tumor tissues. To further explore the biomedical applications of calcium citrate, a bulk nanostructured precursor to the known anti-cancer calcium citrate phosphate-based …

Zinc Or Swim: Investigating Zinc Pollution From Restoration Materials, Megan R. Jensik

Honors Undergraduate Theses

Zinc is an essential nutrient, but can be toxic at high concentrations, negatively affecting various biological functions. Gabions are galvanized metals coated in zinc that are used for many human purposes, including coastal restoration efforts attempting to avoid using plastic materials. However, gabions can degrade in marine environments, potentially leaching metal into the water and soil. There is a knowledge gap regarding the occurrence and impacts of zinc pollution in the areas where these gabions are deployed, including the Indian River Lagoon (IRL). To address this, sediment samples were collected from the IRL and analyzed for their physical and chemical …

The Relevance Of Dnajb1 Protein Dimerization Against The Human Neurodegenerative Diseases, Erina Kotreli, Trang Le, Szymon Ciesielski

Dean's Leadership Council Library Research Prize

All biological functions in living organisms depend on the activity of proteins, long molecules that must twist and fold into specific shapes to become functional. A subset of proteins known as molecular chaperones is essential for maintaining cellular health by assisting other proteins in folding correctly and refolding those damaged by stress. When proteins misfold and clump together, they can form toxic aggregates linked to many neurodegenerative diseases, including Alzheimer’s disease (AD), one of the leading causes of death in the United States. In AD, these protein aggregates form organized, elongated structures referred to as amyloid-like fibrils, which damage neurons …