Chemistry Commons^™

William Albert Noyes Jr. And A Systemic Study Of The Near Ultraviolet Photochemical Decomposition Of Acetone, Zildjan Bonita

Natural Sciences Student Research Presentations

Prior Knowledge

• Chemists observed that acetone vapor decomposes under UV light producing CO and hydrocarbons. The problem with their data was that it was inconsistent due to uncontrolled experimental variables (Herr and Noyes 2052–2053).
• Quantum yield data varied widely, pressure, temperature, and light intensity had never been systematically analyzed (Herr and Noyes 2052–2053).
• Noyes and Herr wanted to create a quantitative, controlled measurements to clarify the mechanisms of acetone photolysis (Herr and Noyes 2052–2053).

Importance of Acetone IV

• Serves as a fundamental model for photochemical bond cleavage (Journal of the American Chemical Society).
• Tests core photochemical laws (absorption → excitation …

Stephen J. Lippard: Chemistry Meets Medicine, Radwa Elrouby

Natural Sciences Student Research Presentations

Key Study

In "DNA Sequence Context Modulates the Impact of a Cisplatin 1,2-GpG Intrastrand Cross-Link", Pilch, Todd, and Lippard found that the DNA sequence around the binding site influences how tightly cisplatin binds (Pilch, Todd, and Lippard).

Biophysical techniques like melting temperature and circular dichroism showed that some sequences stabilize DNA more strongly after drug binding (Pilch, Todd, and Lippard).

This explains why cisplatin is more effective in some tumor genomes (Todd and Lippard).

Experiment 1--Density, Measurement And Significant Figures, Kevin Mark, Phil Mercier

Open Educational Resources

Lab objectives:

• To identify an unknown metal by measuring and calculating its density
• To determine the density of an unknown liquid by graphing mass and volume data
• To compare the accuracy and precision of water mass using measurements from a beaker and burette

Multi-Attribute Characterization Of Polymeric And Lipid-Based Drug Delivery Systems By Column Switching Liquid Chromatography-Mass Spectrometry, Brady W. Drennan

Chemistry & Biochemistry Dissertations - Archive

Drug delivery systems (DDS) are an increasingly relevant technology, owing to their ability to provide controlled release and to enable the use of otherwise toxic or labile therapeutics. However, these modalities are complex, containing a multitude of species with diverse chemical and physical properties. Their characterization, which involves the assessment of critical quality attributes (CQAs), requires numerous analytical techniques. The high-throughput demands of the biopharmaceutical industry have driven the need to consolidate these characterizations into a single analytical method. Consequently, novel analytical technologies are needed to support multi-attribute characterization. A multimodal liquid chromatography–mass spectrometry (LC–MS) system was developed to facilitate …

Structure–Property Relationships Mediated By Lone Pairs And Vacancies In Oxychalcogenides: A Combined Experimental And Theoretical Study, Hoa Hn Nguyen

Chemistry & Biochemistry Dissertations - Archive

Structure–property relationships in some oxychalcogenide materials are strongly governed by the interplay between stereochemically active lone pairs and anion vacancy formation. Through a combination of density functional theory (DFT), synchrotron and neutron total scattering and optical characterization, this work elucidates how local symmetry breaking, chemical substitution, and vacancy dynamics influence electronic and optical behavior across several lone pair-containing systems. In crystalline TeO₂, all three polymorphs exhibit wide band gaps with Te⁴⁺ 5s² lone pairs contributing significantly near the valence band edge. Oxygen vacancy formation is thermodynamically favorable and induces asymmetric charge redistribution and enhanced polarizability, supporting …

Determination Of Structural Factors Contributing To Protection Of Zinc Fingers In Estrogen Receptor Α Through Molecular Dynamic Simulations, Patricia B. Lutz, Wesley R. Coombs, Craig A. Bayse

Chemistry & Biochemistry Faculty Publications

The ERα transcription factor that induces tumor growth is a potential target for breast cancer treatment. Each monomer of the ERα DNA-binding domain (ERαDBD) homodimer has two conserved (Cys)₄-type zinc fingers, ZF1 (N-terminal) and ZF2 (C-terminal). Electrophilic agents release Zn²⁺ by oxidizing the coordinating Cys of the more labile ZF2 to inhibit dimerization and DNA binding. Microsecond-length molecular dynamics (MD) simulations show that greater flexibility of ZF2 in the ERαDBD monomer leaves its Cys more solvent accessible and less shielded from electrophilic attack by sulfur-centered hydrogen bonds than ZF1 which is buried in the protein. In the …

Unraveling Visible Spectra Of S-Type Stars: The F3Δ–A3Δ (Α System) And E3Π–A3Δ (Β System) Band Systems Of Zro, Manish Bhusal, Peter Bernath, Jacques Liévin

Chemistry & Biochemistry Faculty Publications

ZrO has many low-lying states, and its spectra are essential for the characterization of S-type stars. A high-resolution emission spectrum recorded with a Fourier transform spectrometer at the National Solar Observatory is used for the analysis. The 0–0 and 1–0 bands of the f³Δ-a³Δ system (α system) and the 0–0 band of the e³Π-a³Δ system (β system) have been rotationally analyzed using the modern spectral fitting program PGOPHER. New ab initio calculations of transition dipole moments have been performed to determine the band strengths. These band strengths are used to produce line lists that are suitable for the …

Phytochemical Analysis, Antioxidant, And Antibacterial Properties Of Partition Fractions Of Adansonia Digitata And Annona Muricata Extracts Using Chloroform, Ethyl Acetate, Ethanol, And Aqueous Solvent Systems, Fagbohun Oyenike Bushirat, Hassan Abdusalam Adewuyi, Sakariyau Adio Waheed, Maryam Nana Musa, Timothy God-Giveth Olusegun, Ayomide Babatunde Ishola, Agumage Idoko, Adeola Victor Kolawole, Adesanmi Adefunmilayo Oluwatuyi, Sarah Ngozi Agwasim

Chemistry & Biochemistry Faculty Publications

Adansonia digitata and Annona muricata are traditionally used medicinal plants with reported pharmacological properties. In this study, we aimed to elucidate the phytochemical composition, antioxidant activity, and antibacterial properties of partition fractions of Adansonia digitata and Annona muricata extracts obtained using chloroform, ethyl acetate, ethanol, and aqueous solvent systems. The plant extracts were successively partitioned using chloroform, ethyl acetate, ethanol, and aqueous solvent systems. Phytochemical analysis was performed using standard methods. Antioxidant activity was evaluated using FRAP and DPPH assays. Antibacterial activity was assessed using agar well diffusion and MIC determination. Phytochemical analysis revealed the presence of alkaloids (10.2-15.6%), flavonoids …

The Importance Of Solution Studies For The Structural Characterization Of The Enterovirus 5' Cloverleaf, Morgan G. Daniels, Meagan E. Werner, Xiaobing Zuo, Steven M. Pascal

Chemistry & Biochemistry Faculty Publications

Enteroviruses initiate genomic replication via a highly conserved mechanism that is controlled by an RNA platform, also known as the 5' cloverleaf (5'CL). Here, we present a biophysical analysis of the 5'CL conformation of three enterovirus serotypes under various ionic conditions, utilizing CD spectroscopy, size-exclusion chromatography, and small-angle X-ray scattering. In general, a tendency toward a smaller monomeric hydrodynamic radius in the presence of salts was observed, but the exact structural signature of each 5'CL varied depending upon the serotype. Rhinovirus B14 (RVB14) exhibited at least two monomeric conformations and a low propensity for dimerization, while poliovirus 1 (PV1) showed …

Characterization And Leaching Feasibility Studies Of Copper Flue Dust For The Recovery Of Main And Trace Metals, Fardis Nakhaei, Marek Locmelis, Lana Alagha, Michael S. Moats, Carlos Eyzaguirre, Cory Smith

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Although copper smelter dust (CSD) is classified as hazardous waste, it also serves as a valuable secondary resource, offering potential for the recovery of critical elements. In this study, CSD samples were collected from the waste heat boiler (WHB) and electrostatic precipitator (ESP) units connected to the flash smelting furnace at a copper smelter. The representative samples were extensively characterized by particle size, and chemical and mineralogical analyses. Following sample characterization, leaching experiments were performed to evaluate the potential extraction of Cu, Fe, As, Zn, Pb, In, Ga, and Ge from the flue dusts. Distilled water, H2SO4, and HCl were …

M Star Opacities: The B³Π–X³Δ Band System Of Tio, Peter F. Bernath, Manish Bhusal, Mirek R. Schmidt

Chemistry & Biochemistry Faculty Publications

The spectra of titanium monoxide (TiO) are used to classify M stars. TiO experimental cross sections based on a high-resolution emission spectrum recorded with a Fourier transform spectrometer at the National Solar Observatory are used for the analysis of the TiO B³Π–X³Δ transition (𝛾' system). The 3–2 and 4–3 vibrational bands are analyzed for the first time, and the analysis of the 2–1 band is revised. The transition dipole moment function from an ab initio calculation is used to calculate the band strengths. These band strengths are used to produce a B³Π–X³Δ line list for the vibrational levels v' ⩽ …

What Amino Acid Residue Is Responsible For The Interaction Of Atg11 With Its Autophagy Partner Atg9?, Patricia Omoyemwen Woghiren

Senior Honors Theses and Projects

Macroautophagy is a cellular function that involves the formation of a double membrane vesicle that isolates and transports cellular materials to the vacuole or lysosome for degradation and recycling. It is divided into selective and non-selective macroautophagy. Atg11 and Atg9 are two key proteins involved in selective macroautophagy, and their interaction is critical for selective macroautophagy. Specific residues on Atg9 critical for Atg11 binding have been identified, but similar residues on Atg11 have not been identified. The aim of my research was to identify a specific residue critical for Atg11’s interaction with Atg9. To this end, we carried out Yeast-twohybrid …

The Role Of Leptin In The Regulation Of The Soluble Amyloid Precursor Protein Alpha (Sappa) Levels In Non-Small Cell Lunch Cancer (Nsclc) Cell Media, Benjamin Haddad

Senior Honors Theses and Projects

We previously found that the levels of soluble amyloid precursor protein α (sAPPα) are partly regulated by acetylcholinesterase (AChE) in human non-small cell lung cancer cell lines A549 (p53 wild-type) and H1299 (p53-null). In this study, we hypothesize that sAPPα is partly regulated by leptin, a hormone classically recognized for its anorexigenic role in appetite regulation— yet recently shown to play a role in cancer cell signaling. It was observed that cells treated with leptin exhibited greater concentrations of sAPPα and lower concentrations of Aβ40/42 in the media compared to those of cells left untreated. An opposite effect was observed …

Generational Exposures To Cerium Oxide Nanoparticles And Perfluorooctanesulfonic Acid Affect The Performance Of Daughter Plants, Preston Clubb

Graduate Theses/Dissertations

The effects of parental stress on the performance of next generation exposed to another contaminant were investigated. Wheat was exposed to cerium oxide nanoparticles (CeO2-NPs) in first and second generations and exposed to perfluorooctanesulfonic acid (PFOS) in the third generation. Phenotypic or metabolic responses were assessed at 21-day (short-term exposure) or 90-day (long-term exposure) exposure periods. Biomass production, chlorophyll content, enzyme activity, and membrane damage were measured at short-term exposure, while elemental and PFOS concentrations, and grain metabolites were analyzed in long-term exposure. Results showed that continued exposures to CeO2-NPs and PFOS enhanced chlorophyll content but reduced concentrations of important …

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 …

Development Of Dual-Scan Nuclear Magnetic Resonance (Nmr) Pulse Programs For Spin-Lattice Relaxation Measurements, Zachary Mayes

Doctoral Dissertations

This research develops and refines the Split Inversion Pulse and Recovery (SIP R) methodology for spin-lattice relaxation (T₁) measurements in NMR spectroscopy. SIP R introduces a two-scan difference technique using a split inversion pulse sequence, where the 180° pulse is split into two 90° pulses phase-shifted with respect to each other. This approach simplifies data fitting, requiring only two parameters to extract T₁ values, compared to the traditional inversion-recovery method, which needs three. The SIP-R-DS and SIP-R-S adaptations extend this framework by incorporating selective NMR resonance excitations, enhancing its applicability to cross-polarization experiments and enabling unobstructed NOE measurements. These adaptations …

Epitaxial Growth Of Metal-Organic Framwork Thin Films By Electro-Conversion And Electrodeposition, Xiaoting Zhang

Doctoral Dissertations

Electrochemical epitaxy is a facile and inexpensive soft-solution process to fabricate highly ordered thin films. This research focuses on the epitaxial growth of metal-organic framework (MOF) thin films by electrochemical methods which include electro-conversion and electrodeposition.

First, an electrochemical conversion pathway was invented to achieve epitaxial MOF thin films. Epitaxial single-domain Cu-BTC(111) thin films were manufactured by electrochemical oxidation of Cu₂O(111) films electrodeposited on single-crystal Au(111). The single-crystal-like Cu-BTC(111) thin films with out-of-plane and in-plane order provide well-aligned 3.5 Å triangular windows along the [111] direction. Cu-BTC(111) foils were fabricated from the Cu-BTC/Cu₂O system by electrochemical …

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 …

Applications Of Tetramethyl-Guanidine Supported Cationic Transition Metal Sites Towards C─N Bond Construction Methodologies And [3+2] Cycloaddition Reactions, Suraj Kumar Sahoo

Doctoral Dissertations

"We present a family of divalent cationic bipodal and tripodal M(II) reagents (M = Mn, Fe, Co) supported by superbasic tetramethyl-guanidinyl (TMG) residue framework with applications towards C─N bond construction methodologies. These cationic reagents possess unique characteristics since their enhanced Lewis acidity facilitates in situ elaboration of the primary nitrene-transfer product (aziridine). Indeed, further aziridine-ring opening and cycloaddition of several dipolarophiles (nitriles, alkenes, ketones) permits the three-component synthesis of valuable five-membered N-heterocycles, commonly found in pharmaceuticals and agrochemicals.

We undertake a more systematic study to unravel parameters that make certain divalent metal sites more suitable as catalysts for the in-situ …

Development Of Ligands And Metal Complexes With Weakly Coordinating Apical Elements And Their Application To Nitrene Insertion And Addition To C‒H And C=C Bonds, Meenakshi Sharma

Doctoral Dissertations

"We present a family of triangular coinage metal M₃Cl₃ complexes [M = Cu (I), Ag (I)] supported by antimony [Sb (III)], and bismuth [Bi (III)]-centered highly basic tetramethyl-guanidinyl [TMG₃trphen-E] (E = Sb, Bi) ligand frameworks with their applications as catalysts toward the construction of C‒N bond through aziridination and amination reaction methodologies.

The [(TMG₃trphen-Sb)Cu₃(µ-Cl)₃] catalyst gives better yields of aziridines with styrenes than [(TMG3trphen-Bi)Cu₃(µ-Cl)₃] with PhINTs as a nitrene source. However, the catalytic reactivity of both catalysts is enhanced by an electrophilic nitrene, PhINTces for …

Development Of Catalytic Membranes And Composites For Energy Storage Devices And Nonenzymatic Biosensors, Harish Singh

Doctoral Dissertations

The excessive use of fossil fuels has led to their rapid depletion, causing an energy crisis and environmental issues. Consequently, there's a growing focus on sustainable energy conversion. Electrocatalysts are pivotal in this development, particularly for fuel cells and solar fuel generators, necessitating high-efficiency, cost-effective catalysts for large-scale adoption. Transition metal chalcogenides have emerged as promising electrocatalysts due to their high efficiency, electrochemical tunability, and abundant active sites. This work is divided in two parts. In Part A, we have investigated transition metal chalcogenide and few atom clusters FACs as electrocatalysts for oxygen evolution and reduction, highlighting their structure-property relationships …

Products Of Laser Ablated Actinides And Actinide Comparators In The Presence Of Carbonyl Sulfide Characterized By Rotational Spectroscopy, Joshua Edward Isert

Doctoral Dissertations

As the consumption of energy continues to rise globally, so too has interest in alternative energy sources such as nuclear power. However, a fundamental understanding of the actinide series is needed in order to safely and efficiently utilize these elements. Rotational or microwave spectroscopy, depending on if one is speaking of the physical outcome of the experiment or the region of the electromagnetic spectrum being operated in, is a gas phase molecular study utilized for structural determination. This technique can be utilized to gain an in depth understanding of bonding within the actinide series. However, when studying species that are …

Atmospheric Chemistry Experiment (Ace) Winds, Matthew Wyatt, Peter F. Bernath, Chris Boone, Léo Lavy, Ryan Johnson

Chemistry & Biochemistry Faculty Publications

The Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) uses limb geometry to measure transmittance spectra of Earth's atmosphere by solar occultation. Line-of-sight wind speeds can be derived via Doppler shifts of molecular lines in infrared spectra. The wind look direction angles relative to geodetic North are derived from geometry. We validate the new ACE version 5.3 (v.5.3) line-of-sight winds with MIGHTI and meteor radar vector wind observations and find a ±15 m/s sunrise/sunset shift above 80 km. We also compare line-of-sight winds from ACE-FTS v.5.2 and v.5.3 with vector winds from the MERRA-2, HWM14, and WACCM-X models. A ±15 m/s …

Evaluating The Chemical Reactivity Of Wildfire-Derived Dissolved Organic Molecules: Glutathione Binding Through Kendrick Mass Defect Analysis, Hannah M. Hamontree, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

The emerging risks to organisms of pyrogenic-derived dissolved organic matter (PyDOM) from forest fires are of concern due to its toxic and mutagenic potential (e.g., pro-oxidative responses in fauna through the depletion of glutathione, a nitrogen- and sulfur-containing tripeptide found in cells). This study simulates this phenomenon in a laboratory setting by identifying bonding between reduced l-glutathione and organic molecules in leachates from environmentally weathered biomass samples (charred and uncharred) using Kendrick Mass Defect (KMD) analysis from formula lists obtained from negative-mode electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry ((-)ESI-FT-ICR-MS). These formula lists reveal a 10-fold increase in nitrogen- and sulfur-containing …

The Importance Of Atomic Charges For Predicting Site-Selective Ir-, Ru-, And Rh-Catalyzed C-H Borylations, Shannon M. Stephens, Kyle M. Lambert

Chemistry & Biochemistry Faculty Publications

A supervised machine learning model has been developed that allows for the prediction of site selectivity in late-stage C-H borylations. Model development was accomplished using literature data for the site-selective (≥95%) C-H borylation of 189 unique arene, heteroarene, and aliphatic substrates that feature a total of 971 possible sp² or sp³ C-H borylation sites. The reported experimental data was supplemented with additional chemoinformatic descriptors, computed atomic charges at the C-H borylation sites, and data from parameterization of catalytically active tris-boryl complexes resulting from the combination of seven different Ir-, Ru-, and Rh-based precatalysts with eight different ligands. Of the over …

Challenges Associated With Pfas Detection Method In Africa, Abdullahi Tunde Aborode, Ridwan Olamilekan Adesola, Ibrahim Idris, Waheed Sakariyau Adio, Segun Olapade, Gladys Oluwafisayo, Israel Ayobami Onifade, Sodiq Fakorede, Taiwo Bakare-Abidola, Jelil Olaoye, Adedeji Daniel Ogunyemi, Oluwaseun Adeolu Ogundijo, Olamilekan Gabriel Banwo, Adetolase Azizat Bakre, Peter Oladoye, Grace Adegoye, Noimat Abeni Jinadu

Chemistry & Biochemistry Faculty Publications

Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that are widely present in many industries. Monitoring and analyzing PFAS in Africa is challenging due to the limited availability of mass spectrometry (MS), which is an essential technique for detecting PFAS. This review assesses the scope and impact of the shortage of mass spectrometry instruments in Africa, emphasizing the resulting limitations in monitoring environmental and public health threats. The review analyzes the existing PFAS monitoring, the accessibility of MS instruments, and the technical capabilities within the continent. This study suggests that fewer African countries have sufficient MS instruments, …

Nucleotide-Derived Bacterial Alarmones Attenuate The Induction Of Type-I Interferon Responses In A Murine Macrophage Reporter Cell Line, Ryan P. Kilduff, Erin B. Purcell, Lisa M. Shollenberger

Chemistry & Biochemistry Faculty Publications

The stringent response is a well-studied phenomenon in many bacterial systems and regulates resource-consuming activities such as transcription, translation, and replication. The stringent response is a well-conserved signaling framework, as are the nucleotide-derived signaling mediators, collectively referred to as (p)ppGpp or as alarmones. There is a wealth of research evaluating nucleotide-derived alarmone signaling in bacterial models, however, their potential to modulate innate immune signaling has not yet been evaluated. Several common pathogen-synthesized molecules, such as lipopolysaccharide (LPS) and cyclic-di-AMP (c-di-AMP), act as pathogen-associated molecular patterns (PAMPs), which are common patterns that alert the innate immune system of bacterial infection. The …

Synthesis And Luminescence Studies Of Europium Doped Zinc Lead Germanate Phosphors, Anika Nawar Chowdhury

Dissertations and Theses

Phosphors are luminescent materials that emit light upon excitation, which have significant uses in optoelectronics, bioimaging, sensors, security, and other fields. Inorganic luminescent materials are well known for their stability and broad applications. Among these, germanate based phosphors have recently caught attention because of their inertness, excellent chemical and thermal stability, structural flexibility, and unique properties. For optimizing the properties of the materials, impurities are added to the host intentionally, which are known as dopants. Rare earth elements are often applied as dopants because of their unique f-f transitions. Eu3+ is one of the broadly studied rare-earth dopants among these, …

Demystifying Misconceptions In Introductory Undergraduate Chemistry Education With 3d Printed Molecular Orbitals, Hiwot Endeshaw, Daniel J. O'Leary

Pomona Senior Theses

Spatial abilities are invaluable skills for the science, technology, engineering, and mathematics (STEM) subjects. However, women, people from low socioeconomic backgrounds, and ethnic minorities are more likely to have less developed spatial abilities, which is one of the many contributing factors for the lack of diversity in STEM subjects like chemistry. Teaching spatial skills to undergraduate chemistry students may address this issue and help increase the diversity of students who go on to continue their education in the subject. 3D printing technology in higher education has exploded in recent years, presenting a unique opportunity to teach “hard to grasp” concepts …

Modified N-Heterocyclic Carbene Catalysts For Polyurethane Synthesis, Charise D. Young

Pomona Senior Theses

Polyurethanes are widely used polymers synthesized from diisocyanate and diol molecules. They are ubiquitous polymeric materials with important industrial applications. Their increasing market value prompts the need for selective and efficient production which can be achieved through N-Heterocyclic carbene (NHC) catalysis. N-heterocyclic carbenes are heterocyclic molecules containing a carbene atom and at least one nitrogen adjacent to the carbene center. The nitrogen substituents on the adjacent nitrogen play an important role in influencing their steric and electronic properties and resultant reactivity.^1,2 There is a lack of a comprehensive understanding of the steric and electronic properties of NHCs and how …