Chemistry Commons^™

A Computational Study Of High Energy Density Materials And Their Detection Using Surface-Enhanced Raman Spectroscopy, Emily N. Hugo

Honors Theses

The purpose of this thesis is to theoretically predict the vibrational spectra of select high energy density materials (HEDMs) as well as some of their byproducts and to determine if using surface-enhanced Raman spectroscopy (SERS) could be a viable detection method for these compounds. Studying the vibrational patterns of these compounds will help in identifying them in the environment for remediation purposes. Because the byproducts are smaller and easier to model than the parent compounds, these were studied more in depth through analyzing their Infrared and Raman spectra. Ag2 was used to model the interactions between the Ag nanoparticles used …

Rhenium-Pyridyl-Nhcs For Photocatalytic Co2 Reduction, Emily Anne Sharpe

Honors Theses

The ability to transform CO2 into a useable fuel source would have a remarkably positive impact on the environment by taking the vast amounts of previous unusable CO2 from the atmosphere and reducing it to CO, which can then be turned into fuel. This project involves the synthesis and testing of air and water stable Re (I) pyridyl N- heterocyclic carbene (NHC) compounds for photocatalytic reduction of CO2 into CO using a simulated solar spectrum. Previous research in this area focused on the use of Re(bpy)CO3X, which quickly became the benchmark of homogeneous CO2 reduction photocatalysts. The Re (I) pyridyl …

Study Of An Active-State Cb1 Receptor Model And Jwh Compound Interactions To Predict New Emerging Synthetic Cannabinoids, Kelsey Leigh Pettus

Honors Theses

In recent years, a new class of compounds, called synthetic cannabinoids, have made their appearance in the market as a substitute for illegal marijuana or its constituent natural cannabinoids. These compounds, which are active at the same G- protein coupled receptors (GPCRS) as cannabinoids, are continuing to gain popularity because of the same cannabinoid-like effects they create. Though two cannabinoid receptors have been identified in humans, known as CB1 and CB2, synthetic cannabinoid activity at the CB1 receptor has been the focus of much research regarding synthetic cannabinoid ligand binding. In this study, the structure of the CB1 receptor is …

Indolizine-Squaraine Nir Emissive Materials, Tana A. Rill

Honors Theses

Near-infrared (NIR) emissive organic materials are an emerging area of study with an array of applications for both military and civilian purposes including night vision technologies, secure communications, surveillance, homing, fluoresence imaging, secure displays as NIR OLED materials, heat-blocking coatings, in vivo fluoresence biological imagaing, and additional optoelectronics device applications. We have developed a series of organic NIR emissive materials based on an indolizine donor and squaraine acceptor. The novel-to-squaraine donor, indolizine, exhibits a remarkable increase in absorption maximum wavelength when compared with benchmark indoline-based squaraine dyes (700 nm vs. 625 nm) with molar absorptivities ranging from 100,000-262,000 M-1cm-1. Emission …

Method Development Toward The Analysis Of The Functionalization Of Proteins, Victoria Calcote

Honors Theses

Calmodulin is a ubiquitous small intracellular protein that functions as a receptor for regulatory calcium signals and thus regulates a multitude of physiological processes in organisms as diverse as yeast, fruit flies, and mammals. Since its structure and function have been extensively studied, our goal is to create a calmodulin biomaterial, with the ultimate goal of in situ drug delivery or as a scaffold for stem cell growth and differentiation. We plan to create this biomaterial by using Click Chemistry, the rapid creation of new heteroatom bonds through a copper-catalyzed azide-alkyne cycloaddition. The bonds are created by treating calmodulin as …

The Optimization Of The Synthesis And Characterization Of Vapor-Liquid-Solid Grown Zno Nanowires, Silas R. Fiefhaus

Theses and Dissertations--Chemistry

ZnO nanowires are a promising material with great semiconductor properties. ZnO nanowires were prepared by carbothermal reduction and vapor-liquid-solid growth mechanism. Altering a variety of parameters ranging from mole to mole ratio of ZnO to C all the way to gas flow rate was examined. The nanowires were then characterized and their morphology examined under a SEM to observe what effect the parameter had on the morphology of the nanowires. From the experiments and the parameters tested it was observed that in order to produce the highest quality straight nanowires one should use a mole to mole ratio of ZnO …

Using Conventional And In Situ Transmission Electron Microscopy Techniques To Understand Nanoscale Crystallography, Bethany M. Hudak

Theses and Dissertations--Chemistry

Transmission electron microscopy (TEM) is a powerful tool for studying solidstate crystalline systems. With the advances in aberration correction, monochromation, and in situ capabilities, these microscopes are now more useful for addressing fundamental materials chemistry problems than ever before. This dissertation will illustrate the ways in which I have been using high-resolution imaging and in situ heating in the TEM during my Ph.D. research to investigate unique solid state chemistry questions.

This dissertation will focus on four unique crystal systems: thermoelectric skutterudite crystals, vapor-liquid-solid (VLS) grown nanowires, and hafnium dioxide nanorods. Although these systems are very different from one another, …

Electrochemistry-Coupled To Mass Spectrometry In Simulation Of Metabolic Oxidation Of Methimazole: Identification And Characterization Of Metabolites, Kudzanai Chipiso, Reuben H. Simoyi

Chemistry Faculty Publications and Presentations

Methimazole (MMI), an antithyroid drug, is associated with idiosyncratic toxicity. Reactive metabolites resulting from bioactivation of the drug have been implicated in these adverse drug reactions. Mimicry of enzymatic oxidation of MMI was carried out by electrochemically oxidizing MMI using a coulometric flow-through cell equipped with a porous graphite working electrode. The cell was coupled on-line to electrospray ionization mass spectrometry (EC/ESI-MS). ESI spectra were acquired in both negative and positive modes. In acidic medium, ESI spectral analysis showed that the dimer was the main product, while in neutral and basic media, methimazole sulfenic acid, methimazole sulfinic acid and methimazole …

The Nobel Prize In Chemistry 2015: Exciting Discoveries In Dna Repair By Aziz Sancar, David K. Orren

Toxicology and Cancer Biology Faculty Publications

On October 7, 2015, the Nobel Prize in Chemistry for 2015 was awarded to three deserving scientists for their pioneering research on DNA repair. Tomas Lindahl was recognized for studies that uncovered the inherent instability of DNA as well as the mechanism of the base excision repair pathway, Paul Modrich for characterization of the mismatch repair pathway, and Aziz Sancar for mechanistic elucidation of the nucleotide excision repair (NER) pathway. For me, the announcement of these awards in my area of research was extremely gratifying, particularly so because Aziz was my mentor during my Ph.D. studies that examined the steps …

Calculating Potential Energy Curves With Fixed-Node Diffusion Monte Carlo: Co And N₂, Andrew D. Powell, Richard Dawes

Chemistry Faculty Research & Creative Works

This study reports on the prospect for the routine use of Quantum Monte Carlo (QMC) for the electronic structure problem, applying fixed-node Diffusion Monte Carlo (DMC) to generate highly accurate Born-Oppenheimer potential energy curves (PECs) for small molecular systems. The singlet ground electronic states of CO and N₂ were used as test cases. The PECs obtained by DMC employing multiconfigurational trial wavefunctions were compared with those obtained by conventional high-accuracy electronic structure methods such as multireference configuration interaction and/or the best available empirical spectroscopic curves. The goal was to test whether a straightforward procedure using available QMC codes could …

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, …

Characterization And Photocatalytic Properties Of Tio$_{2}$/Chitosan Nanocomposites Synthesized By Hydrothermal Process, Funda Okuşluk, Fatma Bi̇lge Emre

Turkish Journal of Chemistry

Nanocomposites of TiO$_{2}$/chitosan (nTC) were synthesized by hydrothermal process at 200 $^{\circ}$C. Photocatalytic activity of the nanocomposites was studied with degradation of malachite green (MG) in aqueous medium. Structural and physico-chemical properties of the obtained nanocomposites were characterized by XRD, SEM, BET, FTIR, and particle size analyzer. Complete photodegradation of MG was successfully achieved with the aid of the nanocomposites. The optimum photocatalytic degradation conditions, irradiation time, irradiation power, and amount of catalyst were studied. Photocatalytic activity of the synthesized nanocomposites in terms of degradation of MG was compared with that of undoped TiO$_{2}$ (synthesized by our team) and chitosan …

Synthetic Protocols On 6$H$-Benzo[$C$]Chromen-6-Ones: A Review, Ofentse Mazimba

Turkish Journal of Chemistry

6$H$-Benzo[$c$]chromen-6-ones serve as core structures of secondary metabolites and are of considerable pharmacological importance. Natural sources produce limited quantities, hence the need for synthetic procedures for 6$H$-benzo[$c$]chromen-6-ones, which are herein reviewed. The literature describes protocols such as the Suzuki coupling reactions for the synthesis of biaryl, which then undergoes lactonization, reactions of 3-formylcoumarin (chromenones) with 1,3-bis(silylenol ethers), radical mediated cyclization of arylbenzoates, metal or base catalyzed cyclization of phenyl-2-halobenzoates and 2-halobenzyloxyphenols, and benzoic acid coupling with benzoquinone using electrophilic metal-based catalyst. The efficient and simple procedures are those involving the reactions of Michael acceptor (chromenones and chalcones) with 1,3- and …

Density Functional Study Of The Structure And Water Adsorption Activity Of An Al$_{30}$O$_{30}$ Star-Shaped Alumina Nanocage, Mehdi Zamani

Turkish Journal of Chemistry

Molecular and electronic structures of a novel Al$_{30}$O$_{30}$ star-shaped alumina nanocage (SANC) were studied using the recently developed CAM-B3LYP density functional method. Comparison of the stretching vibrational modes of this compound with the corresponding modes related to an Al$_{20}$O$_{30}$ perfect cage and Al$_{50}$O$_{75}$ tubular alumina nanomaterials showed a shift to lower frequencies, while the bending modes moved to higher frequencies. The highest occupied molecular orbital (HOMO) of the SANC had 65% nonbonding character, whereas the lowest unoccupied molecular orbital (LUMO) was 72% antibonding. The HOMO and LUMO of the SANC arose mostly from Al 3s and 2p atomic orbitals. The …

Comparative Study For The Separation, Preconcentration, And Determination Of Copper And Cadmium In Real Samples By Using Two Different Ligands, Hami̇de Elvan Bayrak, Volkan Numan Bulut, Mehmet Tüfekçi̇, Hacer Bayrak, Celal Duran, Mustafa Soylak

Turkish Journal of Chemistry

Two new solid phase extraction methods have been developed for simultaneous separation and preconcentration of Cu(II) and Cd(II) in some food and environmental samples before their determination by flame atomic absorption spectrometry (FAAS). One of these methods is based on the absorption of the Cu(II) and Cd(II) complexes with [3-(cyanomethyl)-5-(4-methylphenyl)-4$H$-1,2,4-triazol-4-yl]carbamate (L1) and the other is based on the absorption of the Cu(II) and Cd(II) complexes with 4-(4-methylphenyl)-5-{[pyridine-4-yl-4$H$-1,2,4-triazole-3-yl)thio]methyl}-4$H$-1,2,4-triazole-3-thiol (L2) on Amberlite XAD-1180 resin. The metal complexes are retained on resin at pH 6.0 and eluted with 1.0 mol L$^{-1}$ HCl in acetone in both methods. After the optimum conditions were determined, …

Synthesis And Structural Properties Of $N$-3,4-(Dichlorophenyl)-3-Oxo-3- Phenyl-2-(Phenylcarbonyl)Propanamide And Its Cu(Ii) Complex, Ahmet Oral Sarioğlu, Tuğba Taşkin Tok, Mehmet Akkurt, Muhammad Nawaz Tahir, Mehmet Sönmez

Turkish Journal of Chemistry

A new N-carboxamide compound (3) was synthesized by the reaction of dibenzoylaceticacid-$N$-carboxyethyla\-mide (1) and 3,4-dichloroaniline (2). The $N$-(3,4-dichlorophenyl)-3-oxo-3-phenyl-2-(phenylcarbonyl) propanamide (3) subsequently reacted with Cu salt to produce its Cu(II) complex compound (4). The compounds were characterized by analytical and spectral methods. In addition, X-ray diffraction was performed to characterize and obtain detailed information about the structure of 3. The fully optimized geometries of compounds 3 and 4 were calculated at different basis sets by using the Gaussian09 (G09) software to investigate their 3D geometries and electronic structures. Comparisons between the calculated and experimental data including molecular structures, fundamental vibrational modes, …

Square Wave Voltammetric Determination Of Valproic Acid In Pharmaceutical Preparations, Ebru Türköz Acar, Ati̇ye Nur Onar

Turkish Journal of Chemistry

The electrochemical behavior of valproic acid (VAL) was investigated using square wave voltammetry, cyclic voltammetry, and sampled direct current polarography and a new square wave voltammetric method was developed for determination of VAL in pharmaceutical preparations. VAL showed two reduction peaks at about --0.2 V and --0.8 V vs. Ag/AgCl 3 M KCl with a hanging mercury drop electrode in 0.05 M pH 3.3 Britton--Robinson (BR) buffer. These peaks were named peak I and peak II, respectively. The types of limiting current of both peaks were determined as diffusion controlled based on cyclic voltammetry studies. A linear calibration graph was …

Durability Of Carbon/Conducting Polymer Composite Supported Pt Catalysts Prepared By Supercritical Carbon Dioxide Deposition, Gamze Bozkurt, Fulya Memi̇oğlu, Ayşe Bayrakçeken Yurtcan

Turkish Journal of Chemistry

Polypyrrole (PPy)/carbon (C) composites were synthesized by oxidative chemical polymerization and used as support material for Pt nanoparticles. PPy/C supported Pt nanoparticles were prepared by using a promising catalyst preparation method, supercritical carbon dioxide (scCO$_{2})$ deposition. The prepared materials were characterized by using BET, TGA, XRD, and TEM techniques. Cyclic voltammetry was used in order to determine the electrocatalytic activity of the prepared catalyst for hydrogen oxidation and oxygen reduction reactions that occur in proton exchange membrane fuel cells (PEMFCs). The Pt loading obtained over the composite material was around 10{\%}. TEM results showed highly dispersed and small nanoparticles over …

Synthesis And Evaluation Of A Novel N--P-Containing Oil-Based Fire-Retardant Plasticizer For Poly(Vinyl Chloride), Pu-You Jia, Guo-Dong Feng, Yun Hu, Yong-Hong Zhou

Turkish Journal of Chemistry

A novel N--P-containing soybean-oil-based fire-retardant plasticizer was synthesized using soybean oil methyl ester, 9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide (DOPO), and tris(2-hydroxyethyl) isocyanurate (THEIC). The structure was verified by Fourier transform infrared (FTIR) spectrometry and nuclear magnetic resonance (NMR) spectroscopy. The blends were characterized by thermogravimetric analysis (TGA), FTIR spectrometry, scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA). TGA showed that the thermal stability of the blends were acceptable. DMA indicated that the plasticizer had good plasticity for PVC. The limiting oxygen index (LOI) of the blends ranged from 21.3 to 29.6. The flammability and thermal stability of PVC/THEIC-DOPO-ESOME was better than that of …

Systematic Optimization Of Chemical Deposition Conditions For Synthesis Of Vanadium(V) Oxide Xerogels, Aksu Samet, Metodija Najdoski, Igor Kuzmanovski

Turkish Journal of Chemistry

We performed the optimization of conditions in chemical bath deposition using the design of experimental methodology. Factorial design (2$^{3})$ was used for finding the optimal conditions of preparing vanadium(V) oxide xerogel thin films with better electrochromic properties suitable for electrochemical applications. The thin films were prepared by acidification of NH$_{4}$VO$_{3}$ aqueous solution with chemical bath deposition. The factors and selected values we considered were as follows: the deposition time (10 and 20 min), the deposition temperature (70 and 80 $^{\circ}$C), and the mass of ammonium metavanadate (0.3 and 0.5 g). UV-vis spectrometry was used for recording the transmittance variance, $\Delta …