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The Synthesis And Characterization Of Ni(Ii) And Cu(Ii) Cyanoximates, Adedamola Abraham Opalade

Graduate Theses/Dissertations

The design of one-dimensional nickel wires were attempted. Metal complexes of hydrated Cu(II) and Ni(II) with several cyanoximates were synthesized and characterized by elemental analysis, thermal analysis, IR-, electronic- (solid state diffuse reflectance) spectroscopy, and the X-ray analysis (powder diffraction and single crystal studies). Hydrolysis of the HECO and HMeCO cyanoxime ligands leads to the formation of another dianionic cyanoxime – AACO2-, which forms multimetallic Cu(II) and Ni(II) complexes and oxamide as a side product. The crystal and molecular structures of 8 compounds were determined (6 metal complexes and 2 organic compounds). Two Ni metal complexes have distorted octahedral structures …

Studies Toward A Detailed Understanding Of The Intrinsic Properties Of Nucleic Acid Constituents: Gas-Phase Conformations, Energetics, And Glycosidic Bond Stability, Ranran Wu

Wayne State University Dissertations

The gas-phase conformations of the protonated forms of the nucleic acid constituents: nucleosides and mononucleotides, were characterized by infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. The IRMPD spectroscopy experiments were performed using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) coupled to a free electron laser or a OPO/OPA laser system to measure the IRMPD action spectra over the IR fingerprint and hydrogen-stretching regions.

Theoretical calculations were performed using both mechanic dynamics and high level quantum chemical calculations to optimize structures, compute vibrational frequencies and IR intensities, and to obtain the relative stabilities of optimized …

An Ecotoxicological Survey Of Tributaries Of The Selenge River, Mongolia, August 2010, Viktor T. Komov, Ch. Javzan, William G. Brumbaugh

Erforschung biologischer Ressourcen der Mongolei / Exploration into the Biological Resources of Mongolia, ISSN 0440-1298

The biodiversity of the Selenga river basin and the receiving waters of the lake Baikal, are among the greatest in the world with over 1,700 known endemic species of plants and animals. Mining activities along the Selenga river and its tributaries pose a major threat of chemical contamination, potentially reducing habitat quality and suitability for aquatic species. Moreover, the Selenga river serves as a major water source for the lake Baikal. Little information exists on the chemical contaminant concentrations in the Selenga river basin. Thus, the objectives of our study were to evaluate the concentrations of metals in soil, sediment, …

Substrate Specificity Of The Lipn Hydrolase From Mycobacterium Ulcerans, Stephanie Raynor

Undergraduate Honors Thesis Collection

Mycobacterium ulcerans is the causative agent of Buruli ulcer, a tropical skin disease that affects thousands of individuals annually. Recent studies have revealed that lipolytic enzymes are involved in the pathogenicity processes of mycobacterium and could be potential targets for novel antibiotics. LipN is one proposed serine hydrolase in Mycobacterium ulcerans that contains the conserved α/β hydrolase protein fold and utilizes the conserved catalytic traid of serine, histidine, and aspartate/glutamate. The physiological substrate and biological role of LipN from M. ulcerans have not yet been determined. In this study, LipN was cloned into a pET28a plasmid and overexpressed in an …

Mutation Of Surface Histidines In Haemophilus Influenzae Carbonic Anhydrase To Enable Purification By Metal Affinity Chromatography, Shelby E. Scola, Kathleen Cornely

Chemistry & Biochemistry Student Scholarship

No abstract provided.

Targeting Radioresistant Breast Cancer Cells By Single Agent Chk1 Inhibitor Via Enhancing Replication Stress, Yao Zhang, Jinzhi Lai, Zhanwen Du, Jinnan Gao, Shuming Yang, Shashank Gorityala, Xiahui Xiong, Ou Deng, Zhefu Ma, Chunhong Yan, Gonzalo Susana, Yan Xu, Junran Zhang

Chemistry Faculty Publications

Radiotherapy (RT) remains a standard therapeutic modality for breast cancer patients. However, intrinsic or acquired resistance limits the efficacy of RT. Here, we demonstrate that CHK1 inhibitor AZD7762 alone significantly inhibited the growth of radioresistant breast cancer cells (RBCC). Given the critical role of ATR/CHK1 signaling in suppressing oncogene-induced replication stress (RS), we hypothesize that CHK1 inhibition leads to the specific killing for RBCC due to its abrogation in the suppression of RS induced by oncogenes. In agreement, the expression of oncogenes c-Myc/CDC25A/c-Src/H-ras/E2F1 and DNA damage response (DDR) proteins ATR/CHK1/BRCA1/CtIP were elevated in RBCC. AZD7762 exposure led to significantly higher …

Functional Effects Of Calcium Regulation Of Thin Filaments At Single Particle Resolution, Christopher Solis-Ocampo

Electronic Theses and Dissertations

Heart disease is the leading cause of death in the United States. Understanding heart function at the molecular level is critical for developing of more effective treatments. In the cardiac muscle, the thin filament is composed by troponin (Tn), tropomyosin (Tm), and F-actin. It provides Ca2+-dependent regulation of contraction by modulating myosin attachment and force generation in a cooperative scheme. However, this mechanism remains unclear. To understand thin filament activation, we studied the binding and functional properties of Tn and Tm to F-actin at single particle resolution by employing fluorescence image colocalization, in vitro motility assays, and Förster resonance energy …

Use Of Extraction Technologies In Food Safety Studies, Changling Qiu

Electronic Theses and Dissertations

Food safety has become a top concern in our society. The public in general is increasingly concerned about the safety of the food products they consume every day as more and more food contamination incidents and widespread recalls arise. It is necessary to trace any presence and/or the concentration levels of contaminants, pesticides, herbicides, or other harmful substances in food samples. Sample preparation is a crucial step in a food analytical method, as it takes up most of the total analysis time, contributing highly to the total cost of analysis and greatly influencing the results of the analysis. Traditional extraction …

Inactivation Of Peptidylglycine Α-Hydroxylating Monooxygenase By Cinnamic Acid Analogs, Neil R. Mcintyre, Edward W. Lowe Jr, Matthew R. Battistini, James W. Leahy, David J. Merkler

Chemistry Faculty Publications

Peptidylglycine α-amidating monooxygenase (PAM) is a bifunctional enzyme that catalyzes the final reaction in the maturation of α-amidated peptide hormones. Peptidylglycine α-hydroxylating monooxygenase (PHM) is the PAM domain responsible for the copper-, ascorbate- and O₂-dependent hydroxylation of a glycine-extended peptide. Peptidylamidoglycolate lyase is the PAM domain responsible for the Zn(II)-dependent dealkylation of the α-hydroxyglycine-containing precursor to the final α-amidated peptide. We report herein that cinnamic acid and cinnamic acid analogs are inhibitors or inactivators of PHM. The inactivation chemistry exhibited by the cinnamates exhibits all the attributes of a suicide-substrate. However, we find no evidence for the formation …

Crystal Engineering Of A Family Of Hybrid Ultramicroporous Materials Based Upon Interpenetration And Dichromate Linkers, Hayley S. Scott, Naoki Ogiwara, Kai-Jie Chen, David G. Madden, Tony Pham, Katherine Forrest, Brian Space, Satoshi Horike, John J. Perry Iv, Susumu Kitagawa, Michael J. Zaworotko

Chemistry Faculty Publications

A new family of 2-fold interpenetrated primitive cubic (pcu) networks of formula [M(L)₂(Cr₂O₇)]_n (M = Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺; L = 4,4′-azopyridine), DICRO-3-M-i, has been synthesised and their structures, permanent porosity and gas sorption properties were comprehensively characterised. Molecular simulations indicate that CO₂ molecules occupy both of the two distinct ultramicropores that run through this isostructural series. The orientation of the Cr₂O₇²⁻ pillars is thought to contribute to high isosteric enthalpy of adsorption (Q_st) …

Experimental And Computational Study Of Methylphenylvinylidene And Its Rearrangements, Xi Yang

Honors Theses

In this study, the synthesis and properties were explored of the compound methylphenylvinylidene (MPV), a vinylidene carbene with methyl and phenyl groups as substituents. A phenanthrene-based precursor, 1-(1-phenylethylidene)-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene, was synthesized in three steps and was subjected to photolysis in C₆D₆ at ambient temperature. During photolysis, the MPV carbene rearranged into 1-phenylpropyne via a 1,2-phenyl shift, instead of 1,2-methyl shift, confirmed by photolysis of ¹³C-labeled precursor. This experimental result is consistent with computational results using the CCSD(T)/cc-pVTZ//B3LYP/6-31+G* method. The calculations suggest that the 1,2-phenyl shift in singlet carbene requires 3.8 kcal/mol to overcome …

Structures And Nuclear Quadrupole Coupling Tensors Of 1,2-Dichloroethane, 1-Chloro-2-Fluoroethane And 2,3-Dichloropropene Studied Using Microwave Spectroscopy And Computational Chemistry, Asela Sampath Dikkumbura

Masters Theses

The Fourier-transform microwave (FTMW) spectra of 1,2-dichloroethane (12DCE), 1-chloro-2-fluoroethane (1C2FE) and 2,3-dichloropropene (23DCP) have been studied in the 6 to 18 GHz range to determine experimental rotational constants, nuclear quadrupole coupling constants (NQCC) and quartic centrifugal distortions constants. These three molecules have different spatial arrangements (anti and gauche) resulting from different relative orientations of chlorine and/or fluorine atoms about the C-C single bond. The lowest energy anti conformer of 12DCE is non-polar and it is not detectable by microwave spectroscopy, but rotational spectra of gauche-12DCE with three isotopologues, gauche-1C2FE with three isotopologues, and both anti- …

Theoretical Investigations Of Difluorobenzene Interacting With Ne And Infrared Analysis Of 1,1-Dichloroethylene From Synchrotron Data, Seri P. Kamari

Masters Theses

The intermolecular interactions between two molecules are of great importance in proteins, polypeptides, DNA binding, and drug binding interactions. Dimers of chemical rings such as difluorobenzene with hydrogen containing molecules such as acetylene (HCCH) and atoms such as neon are classic systems for investigating weak interactions; however, the microwave spectrum of 1,2-difluorobenzene...Ne does not behave as expected. Possible explanation of this phenomenon is that there is some large amplitude motion perturbing the spectrum.

A computational study was performed to analyze the potential energy surface (PES) of Ne or Ar with ortho, meta, and para difluorobenzene, and reveal the …

Synthesis And Characterization Of Dicopper(Ii) Complexes With Biological Relevance, Ashley E. Hall

Masters Theses

The research discussed in this study focused on the design, synthesis, and characterization of new model complexes that mimic the type-3 enzyme, catechol oxidase, which oxidizes catechols to their corresponding quinones. Our approach focused on the design and synthesis new model complexes that contain a dicopper(II) center that can be fine-tuned in a variety of ways, such as sterics and exogeneous bridging molecules. This method allows a multitude of complexes to be created and compared to determine how the overall structure affects the catecholase activity of the complexes.

Two ligands were synthesized; they contain a phenolate body, two amide groups, …

An In Vitro Study On The Effect Of Synthesized Tin (Iv) Complexes On Glioblastoma, Colorectal, And Skin Cancer Cell Lines, Jennie L. Williams, Lesley C. Lewis-Alleyne, Melinda Solomon, Long Nguyen, Robert Johnson, Jennifer Vital, Ping Ji, John Durant, Camille Cooper, Patrice Cagle, Patrick Martin, Don Vanderveer, William L. Jarrett, Alvin A. Holder

Chemistry & Biochemistry Faculty Publications

((E)-2-(2-hydroxybenzylideneamino)phenolato-2,2-diphenyl-6-aza-1,3-dioxa-2-stanna-[d,h]dibenzocyclononene, [Sn(Ph₂SB)] (compound 1, where Ph₂SB=(E)-2-(2-hydroxybenzylideneamino)phenolato Schiff base) and two novel compounds, [[SnPh2(F-azoSB)] (compound 2, where F-azoSB=4-((E)-(4-fluorophenyl)diazenyl)-2-((E)-(2-hydroxyphenylimino)methyl)phenolato Schiff base), [[SnPh2(sulf-azoSB)]0.125CHCl₃ (compound 3, where sulfamerazineazosalSB=4-((E)-(4-hydroxy-3-((E)-(2-hydroxyphenylimino)methyl)phenyl)diazenyl)-N-(4-methylpyrimidin-2-yl) benzenesulfonamide Schiff base), and the control compound, cisplatin (compound 4) were analysed to comparatively determine their effect on cancer cell growth. Anti-cancer properties of compounds 1-4 were examined using glioblastoma (U-1242 MG), colorectal (HT-29 and HCT-116), and skin (A431) human cancer cell lines. With regards to human glioblastoma cells, compounds 1 and 3 demonstrated anti-proliferative capacity in the cell line tested. Specifically, compounds 1 and 3 inhibited cell proliferation by 50% at …

Vanadium Toxicological Potential Versus Its Pharmacological Activity: New Developments And Research, Agnieszka Ścibior, Juan Llopis, Alvin A. Holder, Mario Altamirano-Lozano

Chemistry & Biochemistry Faculty Publications

Scibior, A., Llopis, J., Holder, A. A., & Altamirano-Lozano, M. (2016). Vanadium toxicological potential versus its pharmacological activity: New developments and research. Oxidative Medicine and Cellular Longevity, 2016, 1-2. doi: 10.1155/2016/7612347

A Guided Inquiry-Based Laboratory Experiment: Synthesis And Characterization Of Various Phthiocol Complexes, Turina Jangula

The Journal of Undergraduate Research

Despite proven effectiveness of constructivist guided-inquiry based instruction for college chemistry courses, teaching in advanced chemistry courses such as inorganic chemistry remains very much traditional. This persistence of traditional instructional approaches could be attributed to the lack of inquiry-based curriculum materials for these courses. In this paper a guided-inquiry based inorganic laboratory experiment on the synthesis and characterization of phthiocol complexes with four different metals is presented along with suggestions for implementation as a laboratory activity. The experiment is unique in terms of its development based on a social constructivist framework and has student discussion and conceptual understanding of inorganic …

It Is All About (U)Biquitin: Role Of Altered Ubiquitin-Proteasome System And Uchl1 In Alzheimer Disease, Antonella Tramutola, Fabio Di Domenico, Eugenio Barone, Marzia Perluigi, D. Allan Butterfield

Chemistry Faculty Publications

Free radical-mediated damage to macromolecules and the resulting oxidative modification of different cellular components are a common feature of aging, and this process becomes much more pronounced in age-associated pathologies, including Alzheimer disease (AD). In particular, proteins are particularly sensitive to oxidative stress-induced damage and these irreversible modifications lead to the alteration of protein structure and function. In order to maintain cell homeostasis, these oxidized/damaged proteins have to be removed in order to prevent their toxic accumulation. It is generally accepted that the age-related accumulation of “aberrant” proteins results from both the increased occurrence of damage and the decreased efficiency …

Environmentally Benign Extraction Processes In Analytical Separation Of Essential Oils, John Kiratu

Electronic Theses and Dissertations

Supercritical fluid extraction (SFE) technology has been well received as an environmentally friendly processing technique. Over the last two decades, its use in many processing industries has tremendously advanced. This is as a result of pressure from regulating bodies aimed at reducing the wide-scale use of organic solvents due to negative environmental impacts. Supercritical carbon dioxide (SC-CO2) is considered to be environmentally benign and has been used in the development of a wide-range of alternative processes in various industries to totally or partially eliminate the use of organic solvents. Conventional processes for essential oil extraction involve steam distillation and organic …

Mechanistic Studies Of The Structure-Photostability Relationship Of Organic Conjugated Polymers, Logan Paul Sanow

Electronic Theses and Dissertations

Organic Conjugated polymers (CPs) are a subject of intense research for their application in organic photovoltaics (OPVs), organic light emitting diodes (OLEDs), solid-state dye lasing, biological imaging and sensing, chemical sensing and remote sensing. CPs are key materials in the quest for more sustainable forms of renewable energy, making electronics more versatile and light weight, and increasing the functionality of everyday materials. For these applications and others that use CPs as the photoactive material, one of their main drawbacks is their susceptibility to photodegradation. Photodegradation occurs when the material is exposed to light leading to irreversible changes in the materials, …

Chiroptical Ionic Liquids, Benjamin Zercher

Undergraduate Honors Thesis Collection

The synthesis and fluorescent analysis of chiral light emitting ionic liquids made from lanthanide-doped chiral amino acid ionic liquids is described in this thesis. The ionic liquids were composed of tetrabutylammonium (TBA) cation with enantiomers of the amino acids valine, proline, and aspartate as anionic counterions. These ionic liquids of varying amino acid composition were doped with europium trifluoromethanesulfonate (triflate) and analyzed by circularly polarized luminescence (CPL). The sign of the CPL signal corresponded to the handedness of the amino acids in the ionic liquids. Europium triflate concentration dependent CPL in both [TBA][Val] and [TBA][L-Pro] ionic liquids was measured from …

Solvent Free Vanadium Mediated Organic Transformations, Garrett Oberst

Undergraduate Honors Thesis Collection

A mixture of vanadium(V) oxide and copper sulfate was used to catalyze oxidative transformations in a variety of organic compounds. Multiple functionalities were tested, including thiols, amines and alcohols. Various transformations were observed resulting in various oxidized products, including coupling reactions. Reactions were performed in a solvent-free environment due to the insoluble nature of vanadium(V) oxide in common organic solvents. Results were analyzed using HNMR and GCMS.

Physical And Electrochemical Area Determination Of Electrodeposited Ni, Co, And Nico Thin Films, Matthew Gira, Kevin Tkacz, Jennifer R. Hampton

Faculty Publications

The surface area of electrodeposited thin films of Ni, Co, and NiCo was evaluated using electrochemical double-layer capacitance, electrochemical area measurements using the [Ru(NH₃)₆]³⁺/[Ru(NH₃)₆]²⁺ redox couple, and topographic atomic force microscopy (AFM) imaging. These three methods were compared to each other for each composition separately and for the entire set of samples regardless of composition. Double-layer capacitance measurements were found to be positively correlated to the roughness factors determined by AFM topography. Electrochemical area measurements were found to be less correlated with measured roughness factors as well as applicable …

Development Of A Luminescent Polymer Sensor Array For The Discrimination Of Carboxylates And Further Improvements In A Solvent Programmable Polymer, William J. Richardson

Theses and Dissertations

This thesis summarizes the work performed on two stimuli responsive polymer projects. The first project used a lanthanide based luminescent polymer to create a sensor array for carboxylate analytes. Initial attempts incorporated molecular imprinting as a means to incorporate unique selectivity into the polymer by introducing acetate, benzoate, and phenylacetate as templates prior to polymerization. This process was successful at creating unique sensing elements for the array, but the polymers lacked the specific selectivity typically seen in molecularly imprinted polymers (MIPs). Instead, a ligand displacement mechanism that relied on multiple sensors with different labile anion ligands directly complexed with the …

Understanding The Activity Of Model Catalyst Surfaces: Ultrahigh Vacuum And Atmospheric Pressure Studies, Kangmin Xie

Theses and Dissertations

Heterogeneous Catalysis plays an extremely important role in the world. Metal particles supported on oxide supports are the most widely employed heterogeneous catalysts. In order to provide insight into the development of new catalytic materials, a fundamental understanding of surface reactions is required. Vapor-deposited metal clusters on single-crystal surfaces are well-defined systems that can be used to understand the structure-relationships in commercial catalysts. The pressure gap between fundamental surface analysis under ultra-high vacuum (UHV, P~10-10 Torr) conditions and kinetic evaluation of catalysts under realistic pressures has been bridged by constructing a micro-reactor interfaced with UHV chamber: pre- and post-reaction surfaces …

Investigation Of Heavy Metals In Zebrafish Tissue By Total Reflection X-Ray Fluorescence, Martina Schmeling, E. Jamka, J. Arroyo, K. Niaz, T. Trinh

Chemistry: Faculty Publications and Other Works

Heavy metals are present in the environment, in many consumer products and can be found in food. Some heavy metals like zinc and copper are essential for enzymatic and metabolic function while others like lead and mercury are toxic and interfere with biological pathways. Zebrafish are a very popular model organism for monitoring toxicity of heavy metals and investigating vertebrate development. In this study we explore the possibility of using total reflection X-ray fluorescence spectrometry to analyze histological sections of zebrafish embryos after exposure to nickel and lead. A methacrylate resin embedding protocol and a paraffin embedding protocol were evaluated …

Size And Chemistry Selective Membranes From Block Polymer Templates, Ryan A. Mulvenna

Open Access Dissertations

The use of block polymers continues to gain attention with their myriad applications in industry for advanced applications in biology, medicine, electronics, and separations. The ability of block polymers to self assemble into ordered states on the nanometer level makes these materials suitable for applications that mandate structural order on this scale. By tuning the chemistry of these block domains, we may explore their utilization for advanced separations.

In this dossier, we detail the efforts into the controlled radical polymerization of polyisoprene-b-polystyrene-b-poly( N,N-dimethylacrylamide) (PI-PS-PDMA) via. a facile reversible addition-fragmentation chain transfer (RAFT) mechanism. For this …

The Origin Of Amino Acids In Lunar Regolith Samples, Jamie E. Elsila, Michael P. Callahan, Jason P. Dworkin, Daniel P. Glavin, Hannah L. Mclain, Sarah K. Noble, Everett K. Gibson Jr.

Chemistry and Biochemistry Faculty Publications and Presentations

We analyzed the amino acid content of seven lunar regolith samples returned by the Apollo 16 and Apollo 17 missions and stored under NASA curation since collection using ultrahigh-performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Consistent with results from initial analyses shortly after collection in the 1970s, we observed amino acids at low concentrations in all of the curated samples, ranging from 0.2 parts-per-billion (ppb) to 42.7 ppb in hot-water extracts and 14.5–651.1 ppb in 6 M HCl acid-vapor-hydrolyzed, hot-water extracts. Amino acids identified in the Apollo soil extracts include glycine, D- and L-alanine, D- and L-aspartic …

Preparation And Characterization Of Photoactive Antimicrobial Graphitic Carbon Nitride (G-C3N4) Films, John H. Thurston, Necia M. Hunter, Kenneth A. Cornell

Chemistry and Biochemistry Faculty Publications and Presentations

Photoactive films derived from nanostructured samples of the metal-free, intermediate band gap semiconductor graphitic carbon nitride (ns-g-C₃N₄) have been synthesized and characterized for their particle properties and antimicrobial activity. Physical characterization reveals that these materials are composed of discrete nanoparticles whose dimensions range from 200 nm to 700 nm. Investigation of the photochemical reactivity of ns-g-C₃N₄ using coumarin-3- carboxylic acid (3-CCA) indicates that this material produces reactive oxygen species (ROS) under visible radiation. When irradiated with 0.31J visible light, ns-g-C₃N₄-based materials reduced the …

Ionic Liquid Based Fluorescent Sensors For Cations, Jaelene M. Torres

Theses, Dissertations and Culminating Projects

The development of novel fluorescent sensors for cations is an area of current interest. Most of these sensors are large organic molecules that have a low solubility in water and are not suitable to be used as sensors in water. The goal of this study is to develop a new sensor by attaching an ionic liquid group to make it water-soluble. We have used a well-known photoinduced electron transfer (PET) sensor for protons as our first test. This sensor is based on a chromophore-spacer-receptor design that is based on an anthracene chromophore and a morpholine proton receptor. The sensor is …