Chemistry Commons^™

The Regiochemistry And Relative Reaction Rates Of Methylbiphenyl Isomers In Electrophilic Aromatic Substitution Reaction (Eas) Nitrations Suggest A Non-Planar Geometry For 2-Methylbiphenyl While 3- And 4-Methylbiphenyl Remain Planar, Tristan Pj Wine

Honors Projects

Electrophilic aromatic substitution (EAS) reactions have long been a fundamental addition to sophomore-level organic chemistry classes, allowing students the opportunity to explore the electron donating and withdrawing effects of electrons contained in the substituents of the aromatic reactant. In this paper we present preliminary findings on the nitration of methylated biphenyls using kinetic and regioselective assessments to analyze steric influences on the planarization of 2-methylbiphenyl after EAS nitration. Our preliminary findings show that nitration favors the methylated phenyl ring of 2-methylbiphenyl, indicating that the steric influence of the methyl group restricts planarization of the carbocation intermediate. Furthermore, a competition nitration …

Modeling Biliary Polycyclic Aromatic Hydrocarbon Metabolites In Fish Using High Performance Liquid Chromatography With Fluorescence Detection, Principal Component Analysis, And Partial Least-Squares Analysis, Joshua C. Padilla

Honors Projects

Polycyclic aromatic hydrocarbons (PAHs) constitute a diverse class of highly toxic, ubiquitous environmental pollutants, and are thus of high interest in environmental monitoring and regulation. In this study, biliary samples of English soles Parophrys vetulus and smallmouth bass Micropterus dolomieu from Seattle waterways, and chum salmon Onchorynchus keta from the north Pacific Ocean were analyzed by high performance liquid chromatography with fluorescence detection (HPLC-FLD) to gauge PAH exposure. Samples were profiled in three broad molecular weight categories, to capture naphthalene-like (NAPH), phenanthrene-like (PHEN), and benzo[a]pyrene-like (BAP) metabolites. While quantification was not achieved for the chum salmon, the semi-quantitative measurements of …

Water Purification And The Industries It Supports, Zeljka Zec, Kj Bell

Symposium of Student Scholars

Water Purification and the Industries It Supports

Zeljka Zec and KJ Bell

Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw, Ga 30144

Clean and readily available water plays a crucial role in daily societal functions. The dynamic research of water purification involves the process of removing undesired chemical or biological contaminants that affect our use of fresh, consumable water. Depending on desired applications, purification quality is adjusted for use in medical settings, manufacturing, agriculture or personal use in households. Several methods and techniques have been used in the water purification process. Those processes are coagulation, flocculation, sedimentation, and filtration. …

Addressing Uncertainties Of Polychlorinated Biphenyls In Schools, Alice Fan

Master's Projects and Capstones

Despite the potential neurological health deficits resulting from polychlorinated biphenyls, there is a lack of inhalation studies and regulations to protect students and teachers who are widely exposed to PCBs in older (1950 to 1979) schools. To estimate the extent of PCB detections in Los Angeles County schools, I applied a mathematical model to estimate the range of PCB detections in schools built between 1950 and 1984. I estimate the range of 17-34% PCB detections of open schools within Los Angeles County. Next, I reviewed exposure tools provided by the US EPA to bridge the uncertainty gaps between ingestion and …

Scan Of The Advantage Of Using Biofuels, Ethanol, Ana Carla Bueno

Symposium of Student Scholars

The environment is the big sink where all the human waste produced is deposited, mainly the pollutant gases from cars. It is inevitable not to contaminate drinking water, air, and all other ecosystems on the planet, and it was from these concerns that scientists began to develop alternative ways to mitigate the side effects of pollution. Currently, there are many strategies to soften the emission of pollutant gases into the atmosphere, and the biggest competitor of traditional fossil fuel is biofuels. The big challenge in the production of this type of fuel is the competition with the conventional fossil fuel, …

Balancing Community Health And Industry Objectives, Lindsay Tudor

Symposium of Student Scholars

Balancing Community Health and Industry Objectives

Lindsay Tudor

Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw, GA 30144

The ever-changing regulatory and federal standards set by the EPA and other organizations are creating a large impact on chemical manufacturing. The Environmental Protection Agency (EPA) maintains jurisdiction under the Toxic Substances Control Act (TSCA) to enforce regulations structured to impart information regarding the health and safety of individuals, environmental impacts, and exposure thresholds of chemical substances. Flame retardants are among the chemicals assessed and restricted, most recently isopropyl phenyl phosphate. Isopropyl phenyl phosphate is a flame retardant/lubricant utilized in various …

Transmission Ir Of Phosphorus In Water-Ice, Kerrigan Greene

Symposium of Student Scholars

The possibility of life on other planets has prompted philosophical debate and scientific research for years. As more of space is explored, and more is discovered about the origin of life, various planets and moons have come under speculation for the possibility of life. The icy moons of Saturn and Jupiter are prime examples. This is because of the presence of water-ice on their surfaces. However, there are many other important chemicals and elements necessary for life to develop and thrive. One such element is phosphorus. In order to analyze the ice on the surface of these moons and other …

Elucidation Of Optoelectronic Properties Of Pyrrolo[3,2-B]Pyrrole Chromophores, Ryan Faddis

Symposium of Student Scholars

Ryan Faddis Abstract

Elucidation of Optoelectric Properties of Pyrrolo[3,2-b]pyrrole Chromophores

Ryan Faddis and Graham S. Collier

Department of Chemistry and Biochemistry

Kennesaw State University

Derivatives of phenyl substituted pyrrolo[3,2-b]pyrroles have shown promise of being useful organic opto-electric compounds due to their advantageous tunability through careful synthetic design. Furthermore, one pot synthesis and readily accessible commercial reactants such as, aromatic amines and aldehydes, makes these molecules more favorable than other, more complex syntheses traditionally required for optically active organic molecules. Although relatively simple synthesize, more information from experimentation is needed to understand the optical properties of these species, and thus, a …

The Reactivity Of Metal Phosphites: Oxidative Rate Analysis, Jamie Kitchens

Symposium of Student Scholars

Phosphorous compounds are involved in many of the biomolecular processes deemed fundamental for life. DNA, ATP, and phospholipids are a few of the molecules where phosphates can be found in the body. Phosphates are geochemically characterized by their low solubility and poor reactivity. This has led to the investigation of reaction mechanisms that could lead to the formation of the phosphorous compounds found in organisms. The oxidation of phosphite into phosphate could be how phosphates were introduced to life, due to phosphites being more soluble and more reactive than phosphates. We will present the synthesis and oxidation reactivity of four …

The Chemistry Of Fermentation As It Relates To The Art Of Winemaking, Olivia Cochran

Symposium of Student Scholars

The process of fermentation can be traced back to the beginning of civilization. Countries, over time, have learned this scientific process and turned it into the backbone of their culture through the making and manufacturing of wine. While climate-change and global-warming have impacted the commercial marketability of wine, the scientific process has remained constant. This undergraduate project analyses the production, fermentation and analytical approach of producing high quality wine. Beginning from the picking of grapes, to testing the acidity through a series of titrations, winemaking is truly where science and art collide.

Energy Requirements For Abiotic Production Of Phosphorous Compounds At The Ice-Schreibersite Interface, Lindsay M. Hicks

Symposium of Student Scholars

Energy Requirements for Abiotic Production of Phosphorous Compounds at the

Ice-Schreibersite Interface

The Abbott-Lyon Lab is investigating the chemistry at the interface of simple ices and a meteoritic mineral analogue. Phosphorous is a key component of numerous biomolecules necessary for life. Lack of an abundance of biologically accessible mineral sources of phosphates on Earth, termed “The Phosphorous Problem,” has led some origin-of-life scientists to look to extraterrestrial sources like meteoritic metal phosphides as possible sources of available phosphates. Schreibersite (Fe₂NiP) is a common mineral in iron meteorites and a plausible source of biologically accessible phosphorous. This study will …

Using Eye-Tracking Data To Determine What Biochemistry Students Attend To When Completing A Revised Three-Dimensional Modeling Activity, Hailey Knoeferl

Symposium of Student Scholars

In biochemistry, three-dimensional models are being used to help students comprehend advanced topics within the subject. Because a greater cognitive load is often related to three-dimensional models, learning what raises the cognitive load is critical. From there, measures can be taken to help lower the cognitive load and make the material easier for students to understand. To understand cognitive load in relation to models, students were presented with three-dimensional serine protease models and their substrates and asked to match the clear surface plate to the backbone, and then the substrate to the surface plate. On the substrates, students were asked …

Investigation Of Chemistry At Ice-Mineral Interfaces Of Phosphorus-Containing Meteorites Analogues, Kimberly Meyberg

Symposium of Student Scholars

The search for life outside of Earth has raised questions about how life began have intrigued origin-of-life researchers, such as the incorporation of phosphorus into biomolecules. Phosphorus exists on Earth mostly as phosphate, PO₄^3-, which is insoluble and unreactive in the geochemical conditions of the early Earth. The challenge of incorporating phosphorus into biomolecules is known as the “phosphorus problem,” prompting investigations of reactive phosphorus species delivered to the prebiotic Earth. Phosphorus-laden meteorites delivered schreibersite (Fe,Ni)₃P, a possible mineral source of phosphorus recognized for its redox chemistry potential and observed reactivity with aqueous …

Chemical Industrial Safety And Environmental Considerations, James Stewart

Symposium of Student Scholars

Chemical Industrial Safety and Environmental Considerations

James Stewart

Department of Chemistry and Biochemistry, Kennesaw State University, Kennesaw, GA, 30144

Workplace safety, particularly in the chemical manufacturing and treatment industries, is always at the core of any competent business strategy of any modern industrially- or manufacturing-focused company. Due to the inherent and sometimes readily apparent nature of chemical hazards, safety in these industries has been, by necessity, a practical consideration since their inception. However, only relatively recently has it developed into a significant philosophical focus of businesses, regulatory agencies such as OSHA, and associated non-regulatory bodies such as the U.S. Chemical …

Electrochemical And Spectroscopic Characterization Of Cerium Salts And Nanoceria Material, Emily Velarde, Wei Zhou

Symposium of Student Scholars

The nanoscale form of cerium oxide, nanoceria (nano-CeO_x), has drawn great attention in recent years in electrochemical, nanomaterial research and medicinal studies due to its antibacterial properties, UV absorption, and its biochemical function as possible radical scavenger. Many new synthesis methods have achieved uniform and biocompatible nanoceria particles, and our lab has created cerium oxide particles that shows UV/Vis. absorption and X-ray patterns similar to the commercial nanoceria and nanoceria made in other research laboratories with novel synthetic methods.

This study focuses on charactering and comparing electrochemical properties of cerium inorganic salts and synthesized nanoceria. Preliminary results …

Bioanalytical Determination Of Glucose Concentration In Sports Drinks Using Uv/Vis Spectroscopy, Laney Hedgeman, Brianna Bond

Symposium of Student Scholars

Abstract

The purpose of our project is to indirectly monitor the enzymatic activity of glucose oxidase as it reacts with the glucose present in sports drinks through the quantitative analysis of the generated ferricyanide. As glucose oxidase catalyzes the oxidation of beta-D-glucose in the presence of oxygen, D-glucono-1,5-lactone is produced along with hydrogen peroxide. The hydrogen peroxide is used in a subsequent reaction with ferrocyanide catalyzed by horse radish peroxidase to produce water and the chromophore ferricyanide. This compound absorbs in the ultraviolet/visible spectrum at 420 nm, which can be quickly measured using Ultraviolet/Visible Spectroscopy. Since the molar ratio of …

From Disease Description And Gene Discovery To Functional Cell Pathway: A Decade-Long Journey For Tmco1, Helen Batchelor-Regan, Baozhong Xin, Aimin Zhou, Heng Wang

Chemistry Faculty Publications

A decade has passed since transmembrane coiled-coil domains 1 (TMCO1) defect syndrome was identified in 11 undiagnosed patients within the Old Order Amish of Northeastern Ohio-a disorder characterized by a distinctive craniofacial dysmorphism, skeletal anomalies and global developmental delay. Twenty seven patients, from diverse ethnic groups, have been reported with pathogenic TMCO1 variants now recognized to cause cerebrofaciothoracic dysplasia (CFTD). The implication of previously uncharacterized TMCO1 within disease has instigated a 10-year journey to understand the function of TMCO1 protein in Ca2+ homeostasis. TMCO1 is an ER Ca2+ leak channel which facilitates Ca2+ leak upon ER "overload" through the novel …

Using Chemical Speciation Modelling To Discuss Variations In Patch Test Reactions To Different Aluminium And Chromium Salts, Saman Nikpour, Yolanda S. Hedberg

Chemistry Publications

Background: Allergic contact dermatitis to metals is diagnosed by applying a metal salt in a patch test. The bioavailability of the metal salt might depend on the choice of metal salt, the concentration, sweat composition, and pH.

Objectives: The main purpose of this study was to apply chemical speciation modelling, which is based on experimentally derived input data and calculates the concentrations of chemical forms (species) in solutions, to reproduce and discuss clinical patch test results of aluminium and chromium.

Methods: Joint Expert Speciation System (JESS), Hydra/Medusa, and Visual Minteq were employed to study the bioavailable fraction and chemical form …

Keap1 Cancer Mutants: A Large-Scale Molecular Dynamics Study Of Protein Stability., Carter J Wilson, Megan Chang, Mikko Karttunen, Wing-Yiu Choy

Chemistry Publications

We have performed 280 μs of unbiased molecular dynamics (MD) simulations to investigate the effects of 12 different cancer mutations on Kelch-like ECH-associated protein 1 (KEAP1) (G333C, G350S, G364C, G379D, R413L, R415G, A427V, G430C, R470C, R470H, R470S and G476R), one of the frequently mutated proteins in lung cancer. The aim was to provide structural insight into the effects of these mutants, including a new class of ANCHOR (additionally NRF2-complexed hypomorph) mutant variants. Our work provides additional insight into the structural dynamics of mutants that could not be analyzed experimentally, painting a more complete picture of their mutagenic effects. Notably, blade-wise …

Theranostic Applications Of Sirna Bioconjugates In Cancer Detection And Treatment, Sunil S. Shah

Seton Hall University Dissertations and Theses (ETDs)

Abstract

The emerging field of RNA nanotechnology has led to rapid advances in the applications of RNA in chemical biology, medicinal chemistry, and biotechnology. At the forefront of its utility is the ability to self-assemble multiple siRNAs into nanostructure formulations capable of targeting selected oncogenes and potentiating the gene therapy of malignant tumors. Self-assembled siRNA integrates multiple siRNAs within a single molecular platform for silencing multiple oncogenic mRNA targets with high precision and efficacy to potentially induce cancer cell apoptosis through the RNA interference (RNAi) pathway. Furthermore, the conjugation of siRNA self-assemblies with bio-active probes results in multi-functional theranostic (therapy+diagnostic) …

Host–Guest Interactions In A Metal–Organic Framework Isoreticular Series For Molecular Photocatalytic Co2 Reduction, Philip M. Stanley, Johanna Haimerl, Christopher Thomas, Alexander Urstoeger, Michael Schuster Prof. Dr., Natalia B. Shustova Prof. Dr., Angela Casini Prof. Dr., Bernhard Rieger Prof. Dr., Julien Warnan Dr., Roland A. Fischer Prof. Dr.

Faculty Publications

A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3(4,4′-dcbpy)] and a photosensitizer [Ru(bpy)2(5,5′-dcbpy)]Cl2 using the isoreticular series of metal–organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location—either at the outer MOF particle surface or inside the MOF cavities—affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, …

Photochemistry Of Nh2No2 And Implications For Chemistry In The Atmosphere, Vincent J. Esposito, Tarek Trabelsi, Joseph S. Francisco

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Recent studies have indicated that nitramide (NH₂NO₂) may be formed more plentifully in the atmosphere than previously thought, while also being a missing source of the greenhouse gas nitrous oxide (N₂O) via catalyzed isomerization. To validate the importance of NH₂NO₂ in the Earth’s atmosphere, the ground and first electronic excited states of NH₂NO₂ were characterized and its photochemistry was investigated using multireference and coupled cluster methods. NH₂NO₂ is non-planar and of singlet multiplicity in the ground state while exhibiting large out-of-plane rotation in the triplet …

Advancing The Preclinical Development Of Secondary Metabolites From Cacospongia Mycofijiensis For The Treatment Of Cancer, Joseph Morris

Natural Sciences and Mathematics | Biological Sciences Master's Theses

The marine sponge Cacospongia mycofijiensis from the Indo-Pacific has proven to be a source of structurally diverse secondary metabolites that are biologically active against a variety of distinct targets. Current interest in the secondary metabolites of C. mycofijiensis largely stems from a) their potent and preferential cytotoxicity for cancer cell lines versus normal cells, making many of them promising leads as cancer therapeutics and b) the novel mechanisms of action responsible for their impressive cytotoxicity. However, limited compound availability has resulted in a paucity of studies aimed at advancing the preclinical development of these secondary metabolites from C. mycofijiensis for …

Methodology Utilizing Triphosgene To Promote Cyclization Of Epoxy Ketones To Pyranoside Derivatives Via Proposed Epoxonium Ions, Isaac Camargo Dos Reis

LSU Master's Theses

The development of new methodologies in organic chemistry is of great importance. In fact, the discovery and creation of new reactions frequently uncovers new chemical reactivities and creates new areas of chemistry. The purpose of this thesis is to present the development of new synthetic reactions that were discovered through previous findings. Additionally, the main theme of this work relies on the intermediacy of a cationic reactive intermediate: epoxonium ions. Chapter 1 provides a brief review of bicyclic epoxonium ions and methods for their generation, as well as their utility in the synthesis of interesting heterocycles. Furthermore, Chapter 1 illustrates …

Records Of Enriched Uranium Atmospheric Deposition In Pond Sediments In Piketon, Oh, Brianna Herner, Brian Majestic, Michael Ketterer

DU Undergraduate Research Journal Archive

The enrichment of uranium, often for nuclear weapons programs and commercial nuclear reactors, produces higher concentrations of radioactive uranium 235 (²³⁵U) than what naturally occurs, which can pose a human health hazard. The most abundant naturally occurring uranium isotope is ²³⁸U, which is still radioactive, however a higher concentration of ²³⁵U skews the observed isotopic uranium distribution. The Department of Energy Portsmouth Gaseous Diffusion Plant, located near Piketon, OH, enriched uranium from 1954 to 2001 and ²³⁵U pollution has recently been detected in air and sediment samples in the surrounding community. The extent of the …

Cyclobutanone Inhibitor Of Cobalt-Functionalized Metallo-Γ-Lactonase Aiia With Cyclobutanone Ring Opening In The Active Site, Cory T. Reidl, Romila Mascarenhas, Thahani S. Habeeb Mohammad, Marlon R. Lutz Jr, Pei W. Thomas, Walter Fast, Dali Liu, Daniel P. Becker Ph.D.

Chemistry: Faculty Publications and Other Works

An α-amido cyclobutanone possessing a C10 hydrocarbon tail was designed as a potential transition-state mimetic for the quorum-quenching metallo-γ-lactonase autoinducer inactivator A (AiiA) with the support of in-house modeling techniques and found to be a competitive inhibitor of dicobalt(II) AiiA with an inhibition constant of Ki = 0.007 ± 0.002 mM. The catalytic mechanism of AiiA was further explored using our product-based transition-state modeling (PBTSM) computational approach, providing substrate-intermediate models arising during enzyme turnover and further insight into substrate–enzyme interactions governing native substrate catalysis. These interactions were targeted in the docking of cyclobutanone hydrates into the active site of …

Lipoates As Building Blocks Of Macromolecules, Mojdeh Raeisi

Chemistry Theses and Dissertations

Since the discovery of Lipoic acid in the early 1950s, there have been several studies to further investigate properties and applications of this interesting, naturally occurring compound. In 1956, the dynamic nature of disulfide bonds in Lipoic acid was reported, which can exist through conversions of monomeric disulfide, polymeric disulfide, and reduced form (dithiol) from one to another under proper conditions. This dynamic nature and reducibility of disulfide bonds via thiol-disulfide exchange, opened doors to the use of Lipoic acid in drug delivery systems, especially for delivery to cancer cells that suffer from overexpression of glutathione – a thiol-bearing tripeptide …

Aerosol Vapor Synthesis Of Organic Processable Pedot Particles And Measuring Electric Conductivity Using A 3d Printed Probe Station, Yang Lu

McKelvey School of Engineering Graduate Student Theses & Dissertations

Conducting polymers are organic semiconductors characterized by conjugated backbones (alternating single-double bonds) that enable mixed ionic-electronic conductivity. Their polymeric nature, tunable band structure and reversible redox capability have demonstrated fundamental advances in the fields ranging from electrochemical energy storage, sensing, to electro/photo catalysis and neuromorphic engineering. Conjugated backbones, the origin of all the unique physical and chemical properties associated with conducting polymers, prevent their solubility due to high lattice energy which hinders processing. Current solution utilizes a long-chain polymer (PSS) as dopants to render conducting polymer water dispersible (PEDOT:PSS). Nonetheless, PSS is highly acidic and hydrophilic limiting applicability with acid-incompatible …

Cu-Promoted C-H Bond Hydroxylation Inspired By Cu-Dependent Metalloenzymes, Rachel Trammell

Chemistry Theses and Dissertations

From 2003 to 2015, Schӧnecker and Baran proposed a dinuclear Cu/O₂ species in their mechanistic proposal for the hydroxylation of sp³ C-H bonds within their systems (proposed based on yields). Inspired from the site selectivity of this methodology and poor analysis of the mechanism, the first project was inspired to re-examine the sp³ C-H bond hydroxylation by Schrӧnecker and Baran and perform an intensive investigation into understanding how Cu/O₂ interact which led us to propose a new mechanism based on the evidence collected (i.e., LCu^II-hydroperoxide species that undergoes homolytic O-O bond cleavage). From there …

Targeted Combination Therapy Of Nsclc Using Taxol And Fingolimod Loaded Nanoceria, Raghunath Narayanam

Electronic Theses & Dissertations

Among various types of cancers, lung cancer reports highest death rate and Non-Small cell lung cancer causes highest mortality in lung cancers. This is mainly due to the scarcity of treatment options and the available treatment shows numerous adverse effects. In the recent times, nanotechnology paved a new path for the diagnosis and therapy of cancer. In this study, we worked on a novel, multifunctional nanoceria (NC) platform loaded with two unique drugs taxol and fingolimod, which acts in their own ways providing synergic therapeutic effect. We hypothesized that the usage of the polyacrylic acid (PAA) coated nanoceria (PNC) increases …