Chemistry Commons^™

Solvent-Free Synthesis Of Metal Coordination Compounds Using Ball Mills, Jenna Cantway

Masters Theses & Specialist Projects

Mechanochemistry utilizes mechanical energy to promote chemical reactions to completion. Samples ground with a ball mill are placed under consistent pressure and temperature, which allows for increased surface area, shorter reaction times and overall better control of reaction conditions compared to the use of a mortar and pestle. Many synthetic techniques to prepare metal coordination compounds use a solvent. The solvent promotes the reactions by providing a route for reagents to interact. While solvents facilitate reactions, there is interest in reducing or eliminating solvents altogether during the synthesis process due to potential instability of a solvent under certain experimental conditions …

Monitoring And Identifying The Rhodamine 6g-Hydroxide Ion Reaction Using In-Situ, Surface-Enhanced Raman Spectroscopy, Ryan Lamb

Masters Theses & Specialist Projects

An effective method for monitoring chemical reactions is necessary to better understand their mechanisms and kinetics. Effective reaction monitoring requires a spectroscopy technique with fast data acquisition, high sensitivity, structure-to-spectrum correlation, and low solvent interference. Surface-enhanced Raman spectroscopy (SERS) provides these features, which makes it a valuable tool for monitoring reactions. To obtain the Raman enhancement, metallic nanostructures typically made of silver or gold are aggregated using a salt. The nanoparticles aggregates must then be stabilized using a surfactant to use this method in situ due to eventual nanoparticle precipitation. In this study, gold nanoparticles stabilized with sodium dodecyl sulfate …

Synthesis And Molecular Mechanics Study Of Platinum Triamine Complex With N-Acetyl-L-Methionine And Guanosine 5’Monophosphate, Nitin Tanajirao Katare

Masters Theses & Specialist Projects

Cisplatin and its analogues have been used and tested over decades for cancer treatment, but because of the serious side effects, it is important to find ways to overcome those side effect by synthesizing a novel platinum molecule. We have synthesized triamine complex and conducted its reaction with biomolecules such as 5’GMP and Methionine in the lab as well as conducted molecular mechanics (MM). MM methods are used for predicting and designing new structures and properties, and to model geometries of small molecules. MM and dynamics calculations have been used to study the 9 Ethylguanine and N-Ac-Lmethionine complexes with platinum …

Mercury And Other Trace Metal Analysis In Bat Guano, Amanda Lee Houchens

Masters Theses & Specialist Projects

Heavy metal pollution in the environment pose risks to ecosystems and the populations that reside in them. Mercury, lead, and cadmium negatively impact humans by way of neurological disorders, various cancers, and damage the reproductive organs, kidneys, and lungs. Bats have been studied as a bioindicator species to identify possibly elevated levels of these metals in the environment. Previous studies have identified correlation between metal concentrations within bat tissues and fur. Many bat species are endangered or at risk due to white-nose syndrome so collection of tissues and fur for analysis can impose stress on bat colonies. This study investigates …

Novel Integrated Nano-Sensors For Analysis Of Chemical Compounds In Natural Gas Applications, Taylor Robinson

Mahurin Honors College Capstone Experience/Thesis Projects

Semiconductor sensors have been important environmental gas detectors since the 1990s, and are commonly used to detect hydrogen, oxygen, alcohol vapor, and even harmful gases such as carbon monoxide. A gas chromatography approach is a well-proven and compact separation technique to identify and quantify multiple compounds in a complex background such as a true natural gas environment. Real time field monitoring implementing classical GC and standard sensors (FID, PID, etc.) have a lot of limitations due to its bulky size, heavy weight, and high maintenance. In this study, we developed a portable instrument through the utilization of novel solid-state sensors …

Leaving Ligand Effects On Reactivity And Solubility Of Monofunctional Platinum(Ii) Anticancer Complexes, Heidi Linn Hruska Millay

Masters Theses & Specialist Projects

Monofunctional platinum(II) complexes, such as phenanthriplatin and pyriplatin, have notably different characteristics from the bifunctional anticancer complexes, such as cisplatin and oxaliplatin, which have detrimental toxicities and resistance associated with them. The unique properties of the monofunctional complexes may be exploited to target cancer cells without producing the toxic side effects associated with the current FDA-approved platinum-based anticancer drugs. To advance the understanding of these monofunctional platinum(II) complexes, this study replaced the chloride leaving ligand with an acetate group, which should increase solubility and alter the rate of reactivity with key amino acid and nucleotide targets. Phenanthriplatin and pyriplatin compounds …

Interaction Of A Platinum Triamine Complex Having A Seven-Membered Chelate Ring With N-Acetyl-Lmethionine And Guanosine 5'-Monophosphate, Jae Ko

Masters Theses & Specialist Projects

In the 1960s, Rosenberg and his colleagues confirmed the anti-cancer activity of cisplatin. Although cisplatin was capable of killing testicular cancer cells there were also serious side effects. It was necessary to find alternate ways of overcoming side effects, and soon many researchers have discovered novel platinum compounds that show similar reactivity. Recently, replacing one chloride group to a heterocyclic amine group showed significant cytotoxicity with a different binding activity than cisplatin. Previously in our lab, [Pt(Me5dien)(NO3)]+ and [Pt(Et2dien)Cl]+ have been synthesized and reacted with NAcetyl- L-methionine (N-AcMet) and Guanosine 5’-monophosphate (5’-GMP) showed unusual reactivity. Unlike most previously studied platinum …

Synthesis Of Bis(Imino)Pyridine Iron(Ii) Complexes And Development Of Bis(Imino)Pyridine Iron(Ii) Catalyzed Carbene Transfer Reactions, Ban Wang

Masters Theses & Specialist Projects

Metal catalysis of symmetric and asymmetric carbene transfer reactions has been widely applied in natural product synthesis and material science over years. Metal carbene can be easily generated from the extrusion of nitrogen under the catalysis of metal complexes to further undergo various organic reactions, O/N/C-H insertions, cycloadditions, and ylide formations. Currently, the dominant effective catalysts for carbene reactions are built with expensive precious metal, for example, rhodium, ruthenium, palladium, gold. Notably, the effective reactivity and enantioselectivity of the dirhodium(II) catalysts are researched and established over the decades. However, the use of precious metal catalysts is the major source of …

The Development Of An Integrated Simulation Model On Understandings On The Interaction Between Electromagnetic Waves And Nanoparticles, Xiaojin Wang

Masters Theses & Specialist Projects

To investigate the interaction between nanoparticles and electromagnetic waves, a numerical simulation model based on FEM was built in this thesis. Numerical simulation is an important auxiliary research method besides experiments. The optical properties of nanoparticles consist of scattering, absorption, and extinction, and in the case of nanoparticle suspension, the transmission is also involved. This thesis addressed two typical applications based on the established model, one was regarding the nanofluids for solar energy harvesting, and the other was regarding the optical properties of atmospheric soot. In the case of the nanofluids solar energy harvesting, the established model provided a convenient …

Synthesis And Characterization Of Degradable Polymers, Christopher Collins

Mahurin Honors College Capstone Experience/Thesis Projects

A degradable polymer with proposed applications in drug delivery was synthesized and characterized. This polymer was grown from a difunctional initiator, a "core" that is able to grow two polymer chains and able to degrade in the presence of oxidizing agents such as peroxides. During the first part of this project, poly(methyl methacrylate) was synthesized via atom transfer radical polymerization using commercially-available reagents in order to develop an optimal synthesis technique. This technique was then used to synthesize the degradable polymer. After introducing hydrogen peroxide, the molecular weight of the degradable polymer decreased in two different experiments, confirming its hypothesized …

Quantification Of Tylosin Antibiotics In Cattle Waste, Appala Keerthi

Masters Theses & Specialist Projects

Antibiotics are used as prophylactic agents to promote growth and for treating infections in animals. However, the irrational use of antibiotics in livestock management is a significant cause of the development of antibioticresistant genes in the environment. Each year 2 million people suffer from the infections caused by bacteria which are resistant to antibiotics and 23,000 of these people are estimated to die because of antibiotic resistance. New drugs are continually coming into the market but are at the risk of developing resistance. Thus, there is a need for the development of analytical methods which can be used to monitor …

Developing Tale Proteins As A Biosensor For Detecting Pathogen Specific Double-Stranded Dna, Kathrine Gaiko

Mahurin Honors College Capstone Experience/Thesis Projects

Transcription activator-like effector (TALE) proteins are important for DNA binding. They bind to specific nucleotide sequences by the use of two residues in each repeat allowing them to target specific DNA sequences. Their modular structure makes TALEs advantageous over other DNA binding proteins such as zinc finger proteins. Zinc finger proteins (ZFP) use a finger like projection to bind 3-4 subsequence base pairs while TALE proteins use two amino acid residues in each repeat to bind one nucleotide. ZFP can use SEER-Lac system for colorimetric detection, while TALE proteins can use fluorescence labeling with Alexa for detection of binding to …

The Effects Of Organic And Inorganic Nanoparticles On Bacterial Deactivation, Lauren Cooper

Mahurin Honors College Capstone Experience/Thesis Projects

Antibacterial resistance is one of the greatest problems in modern medicine, as healthcare professionals are experiencing more and more difficulty in providing effective care. As such, alternative methods of treatment are needed in order to overcome this issue. One recently proposed method of alternative treatment is photodynamic therapy. Photodynamic therapy is a light-based method of treatment that utilizes (1) a photosensitizing agent, (2) light, (3) produced oxygen species. When the photosensitizing agent is injected into an infected region of interest and then irradiated with a certain wavelength of light, the agent is photoactivated and begins to produce harmful forms of …

Ua66/1/4 Ogden College Of Science & Engineering Dean's Office Student & Faculty Organizations, Wku Archives

WKU Archives Collection Inventories

Records created by and about student and faculty organizations in the Ogden College of Science & Engineering.

Ua84 Sigma Chi, Wku Archives

WKU Archives Collection Inventories

Records created by and about the WKU chapter of Sigma Xi.

Ua66/7/1 Ogden College Of Science & Engineering Chemistry Administration, Wku Archives

WKU Archives Collection Inventories

Records created by and about the Chemistry department.

Ua66/7/2 Ogden College Of Science & Engineering Chemistry Publications, Wku Archives

WKU Archives Collection Inventories

Publications created by and about the WKU Chemistry department.

Ua66/7/3 Ogden College Of Science & Engineering Chemistry Centers & Laboratories, Wku Archives

WKU Archives Collection Inventories

Records created by and about Chemistry centers and laboratories.

Synthesis Of A Platinum Triamine Complex And Its Interactions With Guanosine 5’- Monophosphate And N-Acetylmethionine, Manal El Masri

Masters Theses & Specialist Projects

Cisplatin (cis-diamminedichloroplatinum(II)) and its analogs are known to form 1,2-intrastrand cross-links with guanine bases that lead to DNA distortion and are responsible for cytotoxicity. Reaction with proteins, especially at methionine residues, could also be responsible for cytotoxicity (Sandlin, R. D. et al. 2010). A new tridentate platinum(II) complex with a piperazine ring was successfully designed and synthesized. In this complex, the platinum is coordinating to all three nitrogens of (1,2- dimethylaminoethylpiperazine), which makes it a Platinum triamine compound. A series of chemical reactions of this compound with guanosine 5’-monophosphate (5’-GMP) and N-acetylmethionine (N-AcMet) were conducted under different conditions. Reactions with …

Synthesis And Characterization Of Graphene-Family Mesoporous Nanomaterials For Themal Energy Harvesting And Sensing Applications, Romney Meek

Masters Theses & Specialist Projects

Graphene-family nanomaterials (GFNs) have attracted a great deal of attention both in academia and in industry for a range of applications relevant for homeland security. In this thesis, an array of graphene-based hybrid materials and aerogels are synthesized for use as novel thermo-electrochemical energy harvesters and for ascorbic acid biosensing devices. The graphene-family nanomaterials include graphene oxide-GO, thermally reduced GO-rGOth, nitrogenated functionalized graphene-NFG, graphene aerogel-GA, nitrogen-doped graphene aerogel-NGA, multi-walled carbon nanotube aerogel-MWCNT, single-walled carbon nanotube aerogel-SWCNT, graphene and nanotube combined ‘hybrid’ aerogels-Gr:(SW/MW)CNT of various ratios, along with multilayered nanostructured architectures such as gold (AuNP) and silver nanoparticles (AgNP) decorated NFG …

Developing A New Sensing Technology For Double-Stranded Dna Detection Utilizing Engineered Zinc Finger Proteins And Nanomaterials, Dat Thinh Ha

Masters Theses & Specialist Projects

A specific double-stranded DNA sensing system is of great interest for diagnostic and other biomedical applications. Zinc finger domains, which recognize double-stranded DNA, can be engineered to form custom DNA-binding proteins for recognition of specific DNA sequences. As a proof of concept, a sequence-enabled reassembly of TEM-1 β- lactamase system (SEER-LAC) was previously demonstrated to develop zinc finger protein (ZFP) arrays for the detection of a double-stranded bacterial DNA sequence. Here, we implemented the SEER-LAC system to demonstrate the direct detection of pathogenspecific DNA sequences present in E. coli O157:H7 on the lab-on-a chip. ZFPs customdesigned to detect shiga toxin …

Photochemical Investigation Of High-Valent Metal-Oxo Intermediates Containing Corrole And Light-Harvesting Porphyrin Ligands, Jonathan Malone

Masters Theses & Specialist Projects

In enzymatic and synthetic catalytic oxidations, high-valent iron-oxo intermediates play a vital role as the active oxidant. In this regard, many synthetic metal catalysts are designed as biomimetic models to resemble the active site of Cytochrome P450 enzymes (P450) which are the predominant oxidation catalysts in nature. Vitamin B12 cofactors, with a corrole-like structure corrin, are also utilized in some of the more difficult reactions in nature such as rearrangement and reductase reactions.

In this work, application of the promising photochemical method to corrolecontaining ligands systems showed much success in the generation of manganese(V)-oxo corrole intermediates using two electron-deficient corrole …

Molecular Assembly Of Monolayer-Protected Gold Nanoparticles And Their Chemical, Thermal, And Ultrasonic Stabilities, Steven Ray Isaacs

Masters Theses & Specialist Projects

Gold monolayer-protected nanoclusters (MPCs) with average diameters of 1-5 nm protected by alkane- and arenethiolates were synthesized. Mixed-monolayer protected nanoparticles (MMPCs) were prepared by functionalizing hexanethiolate-protected MPCs with either 11-mercaptoundecanoic acid (MUA-MMPC), 11-mercaptoundecanol (MUO-MMPC), or 4-aminothiophenol (ATP-MMPC) using ligand place exchange. Presentation of various chemical reagents such as nucleophile, acid, or base and change in physical environment through ultrasonic and thermal irradiation resulted in changes to particles and their physical properties. Thermogravimetric analysis (TGA) was used to measure maximum temperature of the derivated thermogravimetric peaks (Tmax,DTG) as a means of comparing temperature dependence of mass loss. The absorption spectrum within …

Visible Light Generation Of High-Valent Corrole-Manganese(V)-Oxo Intermediates And Biomimetic Studies Of The Oxidation Of Organic Sulfides Catalyzed By Manganese Corroles With Iodobenzene Diacetate, Davis Ray Ranburger

Masters Theses & Specialist Projects

High-valent transition metal-oxo intermediates play essential roles as active oxidizing species in enzymatic and biomimetic catalytic systems. Extensive research has been conducted on a variety of transition metal catalysts being studied as models for the ubiquitous cytochrome P450 enzymes. In doing so, the production of enzyme-like oxidation catalysts and probing studies on the sophisticated oxygen atom transfer mechanism are taking place.

In this work, visible-light irradiation of highly-photo-labile corrole-manganese(IV) bromates and chlorates was studied in two corrole systems with differing electronic environments, i.e. 5,10,15-trisphenylcorrole (H3TPC) and 5,10,15- tris(pentafluorophenyl)corrole (H3TPFC). In both systems, homolytic cleavage of the O- …

Biomimetic Studies Of Oxidation Reactions By Metalloporphyrins Through Ligand Effect And Kinetic Studies Of Photo-Generated Porphyrin-Iron(Iv)- Oxocompound Ii Models, Dharmesh J. Patel

Masters Theses & Specialist Projects

High-valent iron(IV)-oxo porphyrins are the central oxidizing species in hemecontaining enzymes and synthetic oxidation catalysts. Many transition metal complexes have been extensively studied as models of the ubiquitous cytochrome P450 enzymes to probe the sophisticated oxygen atom transfer (OAT) mechanism as well as to invent enzyme-like oxidation catalysts. In this work, two metalloporphyrin complexes have been successfully synthesized, and spectroscopically characterized. A new photochemical entry to porphyrin-iron(IV)-oxo derivatives, commonly referred to as compound II models, was also investigated in two porphyrin ligands that differ in electronic and steric environments. As determined by their distinct UV-vis spectra and kinetic behaviors, iron(IV)-oxo …

Kinetic Modeling Of The Atmospheric Photooxidation Of Reduced Sulfur And Nitrogen Compounds, Jesus Alejandro Berlanga

Masters Theses & Specialist Projects

Atmospheric aerosols encapsulate a wide variety of particles with different compositions, sizes and sources of origin. They also directly and indirectly affect climate by their interactions with sunlight, clouds, atmospheric chemical species, and even other suspended particles. To understand the atmospheric aerosol processes and the effects they have in global and regional climate is of utmost importance for the future establishment of environmental regulations and emission policies that affect aerosol precursor compounds in an effective and beneficial manner. In particular, aerosols are known to be formed from emissions from human activities, such as fossil fuel burning, agriculture, or concentrated animal …

Foutier Transform Infrared Spectroscopy Instrumentation And Integration With Thermogravimetry, Junjie Xiang

Masters Theses & Specialist Projects

To discover the potential of IR spectroscopy and explore the details of FTIR instrumentation, a FTIR was built from most basic parts to provide access to every aspect of a IR spectrometer including the hardware and software. The optical system followed the most widely used double-interferometer design. The software control system was developed with LabVIEW to perform data acquisition of the detectors, data processing and controls of the actuators. The FTIR built will be able to provide a full optical IR spectroscopy platform which has a complete control and data acquisition system and can be continuously improved in accuracy and …

Secondary Electronic And Solvent Effects On Regiospecific P-Bromination Of Aromatic Systems, Selahaddin Gumus

Masters Theses & Specialist Projects

Bromoarenes are important aromatic building blocks that are commonly used to synthesize various functional compounds in pharmaceutical, agrochemical and related industries.^1,2 This great demand for bromoarenes makes their preparation a widely studied area of synthetic organic chemistry. However, further understanding of the reactivity and regiochemistry of aromatic functionalization reactions is still necessary, as much about the secondary substitution and solvent effects remain unknown.

Resonance Theory is a widely used theoretical model to predict the regiospecifity and reactivity of the bromination of various aromatic compounds.³ The reactivity and regiospecificity of many substituted aromatic compounds is well explained using resonance …

Imidazolium Ionic Liquids As Multifunctional Solvents, Ligands, And Reducing Agents For Noble Metal Deposition Onto Well-Defined Heterostructures And The Effect Of Synthetic History On Catalytic Performance, Michael Drake Ballentine

Masters Theses & Specialist Projects

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM]Tf2N) was investigated as a multifunctional solvent, ligand, and reducing agent for platinum deposition onto well-defined CdSe@CdS nanorods. Platinum deposition was carried out thermally and photochemically using Pt(acac)2 as the metal precursor. Thermal deposition was investigated in [BMIM]Tf2N with and without addition of a sacrificial reducing agent, and product topology was compared with the products obtained from polyol reduction using 1,2-hexadecanediol, oleic acid, and oleylamine in diphenyl ether. Photochemically induced platinum deposition was carried out at room temperature in [BMIM]Tf2N, and product topology was compared with the photodeposition products obtained from a toluene dispersion. Thermal deposition of platinum …

Temperature And Electric Field Dependency Of Asymmetric Stretching Of Nitrate And Carbonate Ions, Konnor Jones

Masters Theses & Specialist Projects

Photolysis of nitrate ion in the natural environment produces NO, NO2, and O3, releasing these toxic gases into the atmosphere. Work done by other groups has shown ionic strength dependence of the ratio of products from photolysis of aqueous nitrate ion. To better understand the kinetic mechanisms of nitrate photolysis, the effects that ionic strength in solution have on nitrate ion symmetry breaking are needed. Different solvation environments induce nitrate bonding motifs that may be correlated to the product ratio. Fourier-transform infrared spectra of aqueous nitrate–ion solutions were obtained over a range of temperatures for several total electrolyte concentrations. The …