Chemistry Commons^™

Ozone And Reactive Oxidized Nitrogen Chemistry In The Northeast U.S, Matthew Ninneman

Legacy Theses & Dissertations (2009 - 2024)

Ongoing reductions in oxides of nitrogen concentrations ([NOx] = nitric oxide ([NO]) + nitrogen dioxide ([NO2])) throughout the continental United States (U.S.) have important implications for tropospheric ozone (O3) and reactive oxidized nitrogen chemistry (NOy ≈ NOx + nitric acid (HNO3) + particle nitrate (pNO3) + peroxy nitrates (PNs) + alkyl nitrates (ANs)). Specifically, decreasing [NOx] concentrations have likely (1) increased the sensitivity of O3 to the [NOx] level, and (2) affected NOy speciation and partitioning. An understanding of the impacts of continued [NOx] reductions is needed to inform current and future air pollution control strategies, especially since the National …

Novel Bioreactor Technology For Real Time In-Cell Nmr, Leonard Breindel

Legacy Theses & Dissertations (2009 - 2024)

Long has it been the goal of biochemists to observe a protein within the cellular environment allowing the true nature of a protein function to be determined within a cell. To understand the nature of a protein within a cell, the role of the cellular environment must be considered when determining the function as a protein. The cellular environment is a crowded place filled with macromolecules such as DNA, RNA and proteins that all interact with one another affecting the function of a protein. Intracellular macromolecules can reach concentrations of 300 g/L and occupy 30% of the available space in …

Towards Machine Learning In Chemical Sensing : Milk Differentiation And Quality Control Through Two-Dimensional Nano-Sensor Array, Yu Sheng Chen

Legacy Theses & Dissertations (2009 - 2024)

Herein, we developed a novel artificial tongue using machine learning and 12 nanoassemblies (2D-NAs) to identify and analyzed different kinds of milk beverages for quality control. This biomimetic sensor array was trained to “taste” different milk types as an “artificial tongue” which is the first time we demonstrated that this sensor array can be implemented to complex systems. Two-dimensional nanoparticles (2D-nps) and nine fluorescently labeled single stranded oligonucleotides (ssDNA) with different length and nucleobases were assembled to create 12 2D-NAs. The artificial tongue was deployed to identify and analyze five milk types. All five milk types were discriminated with 95% …

Elemental Composition And Arsenic Speciation Analysis Of Processed Seafood Products Using Atomic Spectrometric Techniques, Austin A. Roberts

Legacy Theses & Dissertations (2009 - 2024)

Arsenic (As) is a widely known toxic element that is highly ubiquitous and has been detected in soil, sediment, naturals waters, the atmosphere, and in organisms of the 5 kingdoms. The toxicity of As however, is dependent on the molecular form in which it takes as well as the route of exposure. For the general population, exposure to As mainly takes place via ingestion of food and water, which have led to numerous studies investigating As and it’s various species in these matrices. Seafood is one of the major sources of dietary exposure to As and has thus led to …

Biochemical And Chemical Methods Of Key Derivation For Cryptographic Ciphers, Leif K. Mcgoldrick

Legacy Theses & Dissertations (2009 - 2024)

Cryptography is a vital component of digital communication and digital data in general. The use of cryptography is necessary to support the veracity of data and to protect it from outside parties with malicious intent. Cryptography focuses on two main facets that are vital for this goal: data encryption and user authentication. Encryption protects the data by transforming it into an encrypted text that would not allow someone access without having or breaking the encryption method that was used to make it. User authentication is a multiple part process that allows for one to be able to identify oneself to …

Utilizing Raman Spectroscopy And Chemometrics For Novel Medical Diagnostic Purposes, Nicole M. Ralbovsky

Legacy Theses & Dissertations (2009 - 2024)

Many problems exist within the myriad of currently employed diagnostic techniques. Further, an incredibly wide variety of procedures are used to identify an even greater number of diseases which exist in the world. There is a definite unmet clinical need to improve the diagnostic capabilities of these methods, including improving test sensitivity and specificity, objectivity and definitiveness, and reducing cost and how invasive a test is, with an interest in replacing multiple diagnostic methods with one powerful tool. That is, the development of a singular technique which can accurately and objectively diagnose a wide variety of diseases in a cost-effective …

Displacement Using Fentanyl And Bullet Analysis Using Atomic Absorption Spectroscopy, Henry Hance

Legacy Theses & Dissertations (2009 - 2024)

Opioids are substances that bind to opioid receptors in the central nervous system and can be endogenous, naturally occurring opium alkaloids derived from opium poppy or semi-synthetic and or synthetic compounds.1 Fentanyl is a synthetic opioid that has flooded the US market in the last decade. Synthetic opioid deaths increased by 100% from 2015 to 2016.2 The synthetic opioid is still used to treat severe chronic pain and during surgeries as an anesthetic, but has flooded the black market through illegal means. Fentanyl is prescribed in the forms of patches and lozenges, but can be abused and illegal sold in …

Nmr Based Studies Of Interactions Between Ribosomes And Glycolytic Enzymes, Devin Bryan Busch

Legacy Theses & Dissertations (2009 - 2024)

Recent research has been performed to better understand what implications ribosome-mediated quinary interactions have on cellular growth. These studies demonstrated that ribosomal binding to enzymes, and their cofactors, can cause significant changes in their enzymatic activity leading to a proposal that ribosome surfaces play a greater regulatory in cellular growth than thought of in the past. To widen the scope of investigations performed on these ribosomal-mediated quinary interactions, the regulatory enzymes associated in glycolysis (hexokinase, phosphofructokinase, and pyruvate kinase) were titrated into a solution of 70S E. coli ribosome and analyzed via 1H-15N-HSQC NMR. The perturbations of the peaks associated …

Investigation Of Underpotential Deposition Of Copper At Heated Gold Loop Screen-Printed Electrodes In A Variety Of Water Samples, Eun-Ju Lee

Legacy Theses & Dissertations (2009 - 2024)

To study the underpotential deposition (UPD) of copper, three different types of water samples (TraceSelect® Ultra-pure water, Indian pond water at University at Albany and tap water) are used at a heated gold loop screen-printed electrode (GLE), which is a new type of heated working electrode for voltammetry measurements that is able to directly detect the copper content in the water samples. The anodic stripping analysis of copper is performed with these gold loop electrodes at room temperature of 25 °C and electrode temperature of 80 °C at two different deposition potentials, -0.20 V and +0.10 V. Furthermore, the concentration …

Optimal Excitation Wavelength For Raman Spectroscopic Analysis Of Organic Gunshot Residue Evidence, Ashley Hull

Legacy Theses & Dissertations (2009 - 2024)

Gunshot residue (GSR) is a type of trace evidence that can often be recovered at violent crime scenes. There are two major types of GSR, organic gunshot residue (OGSR), and inorganic gunshot residue (IGSR). Traditional forensic analysis of GSR focuses on IGSR, although with the movement towards lead-free, or non-toxic ammunition, IGSR analysis has become less informative, as lead is a major component of IGSR analysis. Because of this, OGSR has been investigated to supplement the standard IGSR analysis methods. Previous work has shown Raman spectroscopy to be effective at identifying OGSR as well as a minimally destructive and specific …

Preparation And Characterization Of Light Sensitive Tetrafluoro-Lambda6-Sulfanyl-Containing Polymers, Kelly A. Bonetti

Legacy Theses & Dissertations (2009 - 2024)

The addition of the pentafluorosulfanyl (SF5) group to an unsaturated organic starting material became popular in the 1960s, following the widening commercial availability of SF5Cl and SF5Br. However, the free radical reaction conditions required limited a broader appreciation of this critical advance. Moreover, while important thermal, photochemical and free-radical initiated addition reactions were reported, the unique photosensitivity of these compounds was not well understood. In 2012, a scalable synthetic route was developed affording aryl-SF5-containing derivatives via a novel aryl-SF4Cl intermediate. As a result, a heightened interest in hypervalent fluorinated sulfur containing materials was renewed. In 2014, the visible light addition …

Development Of Dual Functional Dna/Rna Nanostructures For Drug Delivery, Vibhav Amit Valsangkar

Legacy Theses & Dissertations (2009 - 2024)

In addition to the traditional biochemical functions, DNA and RNA have been increasingly studied as building blocks for the formation of various 2D and 3D nanostructures. DNA has emerged as a versatile building block for programmable self-assembly. DNA-based nanostructures have been widely applied in biosensing, bioimaging, drug delivery, molecular computation and macromolecular scaffolding. A variety of strategies have been developed to functionalize these nanostructures. The major advantage is that DNA is a very stable molecule and its base-pairing properties can be easily utilized to control and program the formation of desired nanostructures. In addition, some of these DNA/RNA nanostructures have …

Mixed-Valent Heterometallic Molecular Precursors : Expansion Into 4d Transition Metals, Jesse Caleb Carozza

Legacy Theses & Dissertations (2009 - 2024)

Hydrogen fuel can provide an ideal carbon-free energy carrier wherever water is available, be that on Earth or throughout the solar system. The use of water electrolysis to split water molecules into contaminant-free hydrogen gas, suitable for use in fuel cells, and oxygen gas allows also for storage of excess electrical energy during periods of high production and low demand, and an easy path to release that stored energy when demand is high and active supply is low. However, liberating hydrogen from water is an energy-intensive process, and effective electrocatalysts that reduce the amount of energy wasted by the reaction …

Bioaffinity-Based Methods For Forensic, Biometric, And Clinical Purposes, Mindy Elizabeth Hair

Legacy Theses & Dissertations (2009 - 2024)

Biomarker analysis is a well-established discipline that involves the evaluation of biological samples for the presence of various substances indicative of personal attributes or illnesses. Sweat is one example of a biological fluid that is often overlooked for forensic and clinical analyses, even though it can contain DNA, various amino acids, and other low molecular weight compounds.1–3 The work presented in this dissertation focuses on the use of bioaffinity-based assays to quantify biomarkers in sweat for both forensic and clinical applications. The concentration of the biochemical content within an individual’s sweat are controlled by hormone-based metabolic pathways4 that fluctuate daily …

Metabolic Changes Associated With Adaptive Resistance To Daptomycin In Streptococcus Mitis-Oralis, Allison Parrett, Joseph M. Reed, Stewart G. Gardner, Nagendra N. Mishra, Arnold S. Bayer, Robert Powers, Greg A. Somerville

Department of Chemistry: Faculty Publications

Background: Viridans group streptococci of the Streptococcus mitis-oralis subgroup are important endovascular pathogens. They can rapidly develop high-level and durable non-susceptibility to daptomycin both in vitro and in vivo upon exposure to daptomycin. Two consistent genetic adaptations associated with this phenotype (i.e., mutations in cdsA and pgsA) lead to the depletion of the phospholipids, phosphatidylglycerol and cardiolipin, from the bacterial membrane. Such alterations in phospholipid biosynthesis will modify carbon flow and change the bacterial metabolic status. To determine the metabolic differences between daptomycin-susceptible and non- susceptible bacteria, the physiology and metabolomes of S. mitis-oralis strains 351 (daptomycin-susceptible) and 351-D10 (daptomycin …

Soil Degradation And Erosion, Anthany Ravanh

Natural Sciences Student Research Presentations

No abstract provided.

The Link Between Soil And Cancer, Adrianna (Annie) Althaus

Natural Sciences Student Research Presentations

No abstract provided.

Development Of Analytical Methods For Toxic Inhaled Hazards (Tih) And Their Metabolites, Obed Adu Gyamfi

Electronic Theses and Dissertations

Toxic inhalation hazards (TIHs), such as methyl isocyanate (MIC) and hydrogen cyanide (HCN), are noxious gases and vapors that are harmful, and often deadly, to humans. However, because of their low cost and high reactivity, they are extensively used for industrial productions, creating risk of exposure for both industrial workers (e.g., occupational exposure) and civilians (e.g., accidental release during transport). The illicit use of TIHs, including as terrorist agents, is also concerning. Considering the rapid toxicity of TIHs and the danger they pose to both human and animal lives, there is a critical need to develop of analytical methods for …

Synthesis And The Genetic Encoding Of Novel Lysine Post-Translational Modifications, Sahan A. Galbada Liyanage

Theses and Dissertations

Post-translational modifications (PTMs) play a significant role in regulating cell signaling and regulating the inner cellular environment. The study of PTMs and their primary biological functions is critical for the development of new medicines targeting the pathways and biomolecules responsible for the PTMs.

Previous studies revealed the direct coupling of the β -hydroxybutyryl lysine (K_BHB) modification with the gene expression. K_BHB in histone proteins links metabolism to epigenetics and gene expression and enables to study in-depth, how cell metabolism controls the gene expression and vice versa. Similar novel histone modification, K_Lac, attracts a special interest …

Effect Of Polyelectrolyte Complex Formation On The Antibacterial Activity Of Copolymer Of Alkylated 4-Vinylpyridine, Murat Topuzoğullari

Turkish Journal of Chemistry

Polymers bearing quaternized 4-vinylpyridine (QVP) groups are known for their antibacterial activities and these polymers can form polyelectrolyte complexes (PEC) with polyanions through electrostatic interactions. PEC formation can be used to adjust the antibacterial activity of polymers of QVP, deliver active molecules, or design antibacterial supramolecular structures. However, the antibacterial activity of PECs of QVP polymers has not been investigated. In this study, a copolymer of QVP was mixed with polyacrylic acid in various molar ratios of components to form PECs. Hydrodynamic diameters and zeta potentials of formed PECs were determined by dynamic and electrophoretic light scattering spectroscopy techniques. The …

Preparation, Characterization, And Binding Profile Of Imprinted Semi-Ipn Cryogel Composite For Aluminum, Shahnila Shah, Huma Shaikh, Najma Memon, Muhammad Igbal Bhanger, Tahira Qureshi, Humaira Khan, Adi̇l Deni̇zli̇

Turkish Journal of Chemistry

Human body is greatly exposed to aluminum due to its high abundance in the environment. This nonessential metal is a threat to the patients of chronic renal disorders, as it is easily retained in their plasma and quickly accumulates in different tissues. Thus, there is great need to remove it from the aqueous environment. In this study, Al$^{3+}$ imprinted semiinterpenetrating polymer network (semi-IPN)-based cryogel composite was prepared and applied for the purification of environmental and drinking water samples from aluminum. Poly (2-hydroxyethyl methacrylate) (pHEMA) discs were produced via cryogenic treatment and imprinted semi-IPN was introduced to the 3-(trimethoxysilyl) propyl acrylate-modified …

Chemical Composition, Antimicrobial, And Lipase Enzyme Activity Of Essential Oil And Solvent Extracts From Serapias Orientalis Subsp. Orientalis, İshak Eri̇k, Gözde Kiliç, Eli̇f Öztürk, Şengül Alpay Karaoğlu, Nuretti̇n Yayli

Turkish Journal of Chemistry

The volatile components of essential oil (EO), SPME, and SPME of solvent extracts (n-hexane, methanol, and water) obtained from fresh Serapias orientalis subsp. orientalis(Soo) were analyzed by GC-FID/MS. EO of Soo gave 11 compounds in the percentage of 99.97%; capronaldehyde (37.01%), 2-(E)-hexenal (23.19%), and n-nonanal (19.05%) were found to be major constituents. SPME GC-FID/MS analyses of fresh plant and solvent extracts of Soo revealed 7, 12, 7, and 4 compounds within the range of 99.7% to 99.9%. Limonene (76.5%, 41.7%, and 61.3%) was the major compound in SPMEs of the n-hexane and methanol extracts. α-Methoxy-p-cresol (52.9%) was the main component …

Reactions Of First-Row Transition Metal Complexes In Bis(Alkoxide) Ligand Environments With Diazoalkanes: Formation Of Carbenes Versus Reductive Coupling To Form Bridging Tetrazenes, Amanda Grass

Wayne State University Dissertations

This dissertation focuses on the design and reactions of novel late transition metal carbene complexes featuring alkoxide ligand environments. The high-valent cobalt carbene Co(OR)2(=CPh2) (OR = OCtBu2Ph), featuring short Co=C bond of 1.773(3) Å, was previously reported from the reaction of Co(OR)2(THF)2 with diphenyldiazoalkane. Magnetic and spectroscopic (EPR) studies demonstrated Co(OR)2(=CPh2) to be a low-spin S = ½ complex. Computational studies, in agreement with experimental data, suggested that the electronic structure of Co(OR)2(=CPh2) lies between intermediate spin Co(III) anti-ferromagnetically coupled to a carbene radical and a Co(IV) alkylidene. This dissertation began with investigation of this complex in carbene transfer reactivity. …

Synthesis Of Bradyrhizose And The Equatorial Glycosides Of 3-Deoxygenation-D-Mango-Oct-2-Ulosonic Acid, Philemon O. Ngoje

Wayne State University Dissertations

ABSTRACT

SYNTHESIS OF BRADYRHIZOSE AND THE EQUATORIAL GLYCOSIDES OF 3- DEOXY-D-MANNO-OCT-2-ULOSONIC ACID

Chapter one provides a general view on the background to the research in two parts. The first part begins with an introduction on the significance of the lectin-carbohydrate interactions in leguminous plants. Then the structure and role of O-antigen lipopolysaccharides in the symbiotic nitrogen cycle, and the mechanism and significance of the cycle in leguminous plants growth are introduced. The role, isolation and characterization of bradyrhizose are also introduced; and the previous syntheses of bradyhizose and of related bicyclic compounds presented.

The second part of chapter one starts …

Characterization Of Clear Coat And Base Coat Automotive Paint Analysis Using Dart-Hrms And Comparison Of Ftir Spectroscopy, Py-Gc-Ms, And Dart-Hrms For Clear Coat Analysis, Kaitlin Jones

Electronic Theses and Dissertations, 2020-2023

Current techniques used to analyze automotive paint samples include microscopy, fourier – transform infrared (FTIR) spectroscopy, and pyrolysis gas chromatography - mass spectrometry (Py-GC-MS). These techniques are performed in the respective order listed above. Out of the three techniques currently used in this field, the one that has the highest discriminatory power is py-GC-MS; however, this technique is time consuming and destructive toward the sample. One hundred automotive paint samples were analyzed using FTIR, Py-GC-MS and direct analysis in real time-high resolution mass spectrometry (DART-HRMS) to determine how DART-HRMS compared to Py-GC-MS in terms of discriminatory capability. DART-HRMS takes approximately …

Total Synthesis Of Natural Products From Oxidative Dearomatization, Nameer Ezzat

Electronic Theses and Dissertations, 2020-2023

The goal of our research is to prepare natural products and related core structures through oxidative dearomatization. The development of a stereoselective iron (III)-mediated intramolecular cascade dearomatization of phenol allowed access to various spirocyclohexadienones and tropons in one step using potassium ferricyanide via single electron transfer (SET). Using this oxidative dearomatization reaction, the thesis focuses on three main parts. The first part is the synthetic efforts toward total synthesis of Harringtonolide. The second part focused on the synthesis of spiro[4.5]decane, a core structure in multiple natural products. The spiro compounds were prepared from ortho hydroxyphenyl nitroalkanes using SET reaction with …

Tuning Dynamics, Sterics, And Ion Conductivities In Reticular Materials, Demetrius Vazquez-Molina

Electronic Theses and Dissertations, 2020-2023

The goal of this thesis is to synthesize libraries of organic building blocks with systematic functionalizations for tuning dynamics and steric traits in crystalline frameworks. Chapter 1 will introduce the materials being studied, their targeted applications, and a brief outline of each chapter will also be included. Chapters 2 explores the impact of mechanical processing in Covalent Organic Frameworks (COFs) from the point of view of crystallographic effects and pressure induced preferred orientation. This chapter also studies solid-state ionic conduction for Li ions in crystallographically aligned COFs studied by solid-state NMR and Electrochemical Impedance Spectroscopy (EIS), we observed fast ionic …

Structural Dynamics Of Inosine Triphosphate Pyrophosphatase (Itpa) Protein And Two Clinically Relevant Mutants: Molecular Dynamics Simulations, Yao Houndonougbo, Bethany Pugh, Kandise Vanwormer, Caitlin April, Nicholas Burgis

Chemistry and Biochemistry Faculty Publications

The inosine triphosphate pyrophosphatase (ITPA) protein is responsible for removing noncanonical purine nucleoside triphosphates from intracellular nucleotide pools. Absence of ITPA results in genomic instability and increased levels of inosine in DNA and RNA. The proline to threonine substitution at position 32 (P32T) affects roughly 15% of the global population and can modulate treatment outcomes for cancer, lupus, and hepatitis C patients. The substitution of arginine with cysteine at position 178 (R178C) is extremely uncommon and has only been reported in a small cohort of early infantile encephalopathy patients suggesting that a functional ITPA protein is required for life in …

Investigating Heterogeneous Nucleation Of Barite Using Hydrothermal Atomic Force Microscopy And Optical Microscopy, Ankita B. Gurav

Browse all Theses and Dissertations

In order to develop a better understanding heterogeneous nucleation of barite, barite precipitation was studied under varying experimental parameters. Hydrothermal atomic force microscopy (HAFM) and optical microscopy were used to investigate the effect of change in temperature, supersaturation and varying ratios of ions on heterogeneous nucleation of barite. In the experiments conducted at higher temperatures, the particles thus nucleated were found to display characteristic hexagonal and rhomboidal shapes. In comparing results of particle densities among different ion ratios, there is evidence suggesting that barium to sulfate ratio plays a role of promoter. Wherein, the ratios with higher [Ba2+] concentration were …

Benzoporphyrin-Based Photosensitizing Nanocomposites For Optoelectronic Applications, Wittawat Keawsongsaeng

Chulalongkorn University Theses and Dissertations (Chula ETD)

A new series of meso-bifunctionalized benzoporphyrin derivatives bearing a p-diphenylaminophenylethynyl and a p-carboxylphenylethynyl meso-groups, and 2 p-carboxyl groups in a trans-fashion on a benzoporphyrin core is successfully synthesized and characterized by spectroscopic techniques. Impact of electron-donating diphenylamino and electron-withdrawing surface-anchoring carboxyl groups on photophysical and electrochemical properties of the target benzoporphyrins was investigated in comparison with those of their benchmark analog containing one carboxylphenylethylnyl and three phenyl meso-groups by UV-visible spectrophotometry and cyclic voltammetry. The results show that while the p-carboxylphenylethynyl group give electronic contribution to the molecules by lowering energy gap, a role of the p-diphenylaminophenylethynyl group is found …