Chemistry Commons^™

Kinetic Studies Of The Sulfoxidation Of Aryl Methyl Sulfides By Trans-Dioxoruthenium(Vi) Porphyrin Complexes, Chris Abebrese

Masters Theses & Specialist Projects

The development of an efficient, catalytically active, biomimetic model for cytochrome P-450 enzymes has been an area of intense research activity. Ruthenium porphyrin complexes have been the center of this research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes, the epoxidation of alkenes and aromatic rings, and the N-oxidation of amines, among others. In this project, the kinetics of two-electron sulfoxidation of para-substituted phenyl methyl sulfides to the corresponding sulfoxides with well-characterized trans-dioxoruthenium(VI) porphyrin complexes were studied by rapid stopped-flow spectroscopy. The substituent effect in sulfides and in dioxoruthenium(VI) complexes were …

Off-Metal Synthesis Of Some Aryl Substituted Rhenium N5-Cyclopenta [C] Pyridazyl Complexes, James Leif Neathery

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (e.g. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to non-aromatic analogs (e.g. polyacetylene). Our current interests focus upon the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. Pyridazines, 6-membered aromatic rings with two adjacent nitrogens, are promising candidates for a variety of materials and commercial applications. These molecular electronic materials posses several advantages over traditional inorganic semiconducting materials including lower cost of production, higher processibility, and the ability to function on flexible …

Chemistry Of Zirconia And Its Bioanalytical Applications, Oge Anazia

Masters Theses & Specialist Projects

This research studies the chemical nature of zirconia and the complex surface chemistry of zirconia in order to better comprehend its behavior under chromatographic conditions. This research shows how the physical and chemical properties of zirconia depend strongly on the thermal treatment during synthesis. The morphology of the samples was also studied. The absorption capability of Adenosine Triphosphate (ATP) on zirconia was also monitored and spectrally characterized.

The results of this research showed how the properties of zirconia vary with thermal treatment. It was observed that the zirconia prepared at a higher temperature had lower surface area, lower pore size …

A Characterization Of Caffeine Imprinted Polypyrrole Electrode, Deepika Mandadi

Masters Theses & Specialist Projects

Nanotechnology holds great potential for improving our lives by creating many new materials and devices in medical sciences, electronics and also in energy production. Molecularly imprinted polymers (MIPs) are highly stable synthetic polymers that possess molecular recognition properties due to cavities created in the polymer matrix that are complementary to an analyte both in shape and in positioning of functional groups. These MIPs have been widely employed for diverse applications (e.g., in chromatographic separation, drug screening, chemosensors, catalysis, immunoassays etc) due to their specificity towards the target molecules and high stability against physicochemical perturbations. Conductive polymers, (CPs) such as polypyrrole, …

The Study Of Variations In The Properties Of Biodiesel On Addition Of Antioxidants, Hiranmayee Kandala

Masters Theses & Specialist Projects

This research studies variations in biodiesel upon addition of different concentrations of antioxidant and petrodiesel additives. Oxidation onset temperature, oxidation induction time, oxidative stability, thermal stability, crystallization onset temperature and moisture retention properties of the biodiesel, with and without antioxidants have been studied. Antioxidants like BHT, BHA, PrG, Vit E and Vit C were added to the biodiesel during the study. These samples were analyzed using the PDSC, TGA, DSC and TGA-SA instrumentation.

The results of this research show an improvement in the OOT, OIT and Oxidative stability of biodiesel with the addition of antioxidants and by blending the biodiesel …

Increased Control Over Gold Colloid Adsorption On Substrates For Colloid Displacement Lithography, Vara Prasad Reddy Sakampally

Masters Theses & Specialist Projects

Colloid displacement lithography is proving to be very effective in the designing of nanometer scale electronic devices. Precise control of the structure of matter at the nanometer scale has brought a revolutionary change in science and technology. The use of these nanometer scale devices ranges from the diagnosis of various diseases to cell repair to ultra strong materials. This research focused on optimizing the conditions for gold colloid particle adsorption for colloid displacement lithography, an expansion on gold colloid particle manipulation techniques using a scanned probe microscope. The system consists of a scrupulously cleaned glass surface that is coated with …

Synthesis And Characterization Of Bis-Phosphine Complexes With Transition Metals, Alicia L. Mcdaniel

Masters Theses & Specialist Projects

Extractants and extraction methodologies play a vital role in many industrial processes, from the concentration of precious metals from ores to the separation of longlived nuclei from radioactive waste as well as the removal of heavy metals from soils and water for remediation. The vast majority of extractants rely on the use of nitrogen, oxygen, sulfur or selenium as Lewis base donor atoms to form coordination complexes with the metal ions of interest. These extractants often make use of the chelate effect and/or the macrocyclic effect in order to form stable complexes. Some of the best known types of chelate …

Synthesis And Characterization Of Some Rhenium Complexes, Joseph Brian Scott

Masters Theses & Specialist Projects

Plastics or polymers are thought to behave oppositely from metals. Ideally, polymers behave as insulators while metals conduct electricity. Shirakawa and coworkers discovered conductive polymers in 1977.1 These conductor polymers have been extensively studied, discovering that charge transfer oxidative doping of polyacteylene could increase its conductivity by 12 orders of magnitude. Polyacetylene, although showing promise as an organic conductor, because it is highly air-sensitive and oxidizes when exposed to molecular oxygen, therefore making this an unattractive use for commercial products. Attention has been focused on heterocylic aromatic polymers such as polythiophene and polypyrrole, in efforts to produce conductive polymers that …

Arsenic And Selenium Distribution In Coal-Fired Plant Samples, Pauline Rose Hack Norris

Masters Theses & Specialist Projects

Arsenic and selenium distributions in coal-fired plant samples are studied. This research includes arsenic and selenium concentrations in samples of coal, fly ash, bottom ash, economizer ash, Flue Gas Desulfurization (FGD) slurry and flue gas taken from four power plants with the goal being to examine the distribution of these metals in these materials and calculate a materials balance for the system. All samples were analyzed using ICP-ES.

This research shows that 60-80% of the arsenic in coal-fired plant samples will be associated with the fly ash. Approximately 35-55% of the selenium will be associated with the fly ash and …

Multi-Walled Carbon Nanotubes-Modified Polymer Organic Photovoltaics, Tzu-Fan Chen

Masters Theses & Specialist Projects

Since the carbon nanotubes were first discovered by Iijima in 1991, CNTs have been the focus of intense research by many groups. Nearly 7000 papers and 700 theses on carbon nanotubes can be found from the eminent journals such as Nature and Science in the last decade. Since carbon nanotubes show impressive mechanical, physical and electronic properties such as high stiffness, high strength, low density, and excellent thermal conductivity, suggesting its role in light-weight high strength material application. A great quantity of important research has evidently been done in this field. The purpose of this thesis research is to investigate …

Proposed Route To Cyclopenta[C]Thiophenes Via Activated Methylene, Vineet V. Karambelkar

Masters Theses & Specialist Projects

The synthesis of cyclopenta[c]thiophenes has been sparsely reported in the literature owing to several difficulties involved in their synthesis. The present work involves the proposed synthesis of cyclopenta[c]thiophenes and their precursors using activated methylene. Cyclopenta[c]thiophene compounds show promise in the field of polymer and catalysis chemistry. These substituted polythiophenes are potential organic semiconductors and anti-tumor agents. The research presented shows the successful and novel conversion of 3,4-bis(chloromethyl)-2,5-dimethylthiophene and 3,4-bis(bromomethyl)-2,5-dimethylthiophene to a fused 5,5'-fused membered ring which is the precursor to cyclopenta[c]thiophene the sulfone ester, 5-carbomethoxy-5- phenylsulfonyl-1,3-dimethyl-5,6-dihydro-4H-cyclopenta[c]thiophene, in just two steps as compared to four steps previously reported in the literature. …

A Selectivity Study On The Use Of Caffeine And Theobromine Imprinted Polypyrrole Surface Electrodes, Anil Kiran Kumar Vinjamuri

Masters Theses & Specialist Projects

Molecularly imprinted polymers (MIPs) are proving to be very effective in development of synthetic recognition systems and are of great interest to those interested in the field of sensor technology. The use of MIPs is receiving considerable interest due to the ability to prepare recognition matrices that possess high substrate selectivity and specificity. Conducting polymers (CP) have proved to be an excellent tool for the preparation of nano-structured biologically selective systems. Polypyrrole (Ppy) is one such CP that is extensively used for the construction of bioanalytical sensors. Ppy has shown great promise primarily due to its biocompatibility and thermal stability …

Admicelle-Based Solid Phase Extraction Of Phenols Using Dialkylammonium Surfactant In The Hydroxide Form, Kali R. Pickering

Masters Theses & Specialist Projects

A technique for admicelle-based solid phase extraction is presented in which a dialkylammonium surfactant in the hydroxide form is immobilized on silica. By converting dihexadecyldimethylammonium bromide to the hydroxide form, the surfactant is allowed to have the property of a strong base, aiding in the extraction of acidic phenols which are difficult to extract because of their differing polarities. The surfactant-silica admicelle parameters were optimized for the efficient extraction of eight phenols. Adsorbed phenols were eluted from the sorbent using small volumes of methanol. The phenols were preconcentrated from drinking water samples and were determined using high performance liquid chromatography …

A Study On The Protein Interaction With Different Platinum Compounds, Nayna Kotadia

Masters Theses & Specialist Projects

Since the discovery of anti-tumor activity of cisplatin in 1960, significant progress has been made in treating metastatic or advanced cancer with cisplatin and platinum compounds. Platinum compounds covalently bind to DNA and disrupt DNA function. They are also known to bind with amino acids like methionine, histidine and cysteine to form cisplatin-protein adducts which are responsible for most of its cytotoxicity and side effects. Recent articles on cisplatin-protein have shown that adding bulky adjuncts to cisplatin or using different platinum compounds varies the degree and extent of reaction thus possibly reducing cisplatin resistance and side effects.

One of the …

Optimization Of Microwave-Assisted Acid Digestion Method For Determination Of Trace Elements In Coal And Coal Fly Ash, Dejan Savic

Masters Theses & Specialist Projects

In most of the analytical and environmental laboratories today inductively coupled plasma (ICP) is a method of choice for analysis of trace metal elements present in coal and coal combustion products. This method requires use of liquid samples, so all coal and coal combustion products must be digested prior to analysis by ICP. Traditionally an open-air hot-plate acid digestion method published as ASTM D6357-04 was used to extract all trace metal elements into solution.

Recent development of microwave systems designed for digestions under extreme acidic conditions and high temperatures and pressures shifted focus toward more rapid and precise microwave-assisted digestion …

Chemistry And The Automotive Industry, Jeremy Pedigo

Masters Theses & Specialist Projects

This thesis covers the use of chemistry in the automotive industry with emphasis on environmental compliance via chemical reporting by database and internal Energy Dispersive X-ray Fluorescence (XRF) screening, third party laboratory material testing, and the future of the chemist in the United States (U.S.) automotive industry. The third party testing was performed at Western Kentucky University (WKU) via the Materials Characterization Center (MCC), Institute for Combustion Science and Environmental Technology (ICSET) Thermodynamics Laboratory, and using the Scanning Electron Microscope/Energy Dispersive X-ray Spectrometer (SEM/EDX) managed by the WKU Biotechnology Center. Furthermore, the tests conducted were used to investigate material defects, …

A Modified Route To Cyclopenta[C]Thophenes Via Grignard Reagents, Amber Bell

Masters Theses & Specialist Projects

The synthesis of cyclopenta[c]thiophenes is sparsely found in literature due to the several difficulties of their synthesis. Our research has shown that we could modify a previously known route to 1,3-disubstituted cyclopenta[c]thiophenes using traditional Grignard chemistry. Along the way we discovered the synthetic route we were using had several omissions. Therefore, we were required to completely fill in missing experimentals in order to obtain each cyclopenta[c]thiophene intermediate, in high purity and good yield. In addition, we were able to fully characterize via NMR, our intermediates which was found in the literature. Finally, we were able to show using 'H 13 …

Delivery Of Itv Chemistry Classes, David Martin

Masters Theses & Specialist Projects

Western Kentucky University (WKU) offered a course entitled Biochemistry for the Health Sciences in the spring semester of 2007. The course was taught in Interactive Television (ITV) format, and was the first time a class had been taught in the format enabling two-way communication by the Chemistry Department. One section was present in an ITV broadcast classroom on the main campus in Bowling Green, Kentucky. Another section received the broadcast on the campus of Western Kentucky University-Owensboro (WKU-O), at Owensboro Community and Technical College (OCTC), located in Owensboro, Kentucky. The purpose of this thesis is to evaluate the delivery of …

Carbon Dioxide Capture: Using Activated Carbon From Chicken Waste, Yan Zhang

Masters Theses & Specialist Projects

Carbon Dioxide (CO2) emission from hydrocarbon fuel combustion is becoming a serious concern because it is the main contributor to greenhouse gas which causes global warming. Activated carbon sorbents have been used widely in various gas-phase and/or liquid-phase separation. Currently activated carbon (AC) is being investigated and developed for CO2 capture. Chicken waste, which is produced in large quantity in U.S., is currently disposed as waste. However, it may have a large benefit to turn chicken waste into useful activated carbon. In this research, a series of activated carbon have been generated from chicken waste and coal in the lab …

Pseudostationary Phase For Solid Phase Extraction, Qing Zhao

Masters Theses & Specialist Projects

A unique pseudostationary phase for Solid Phase Extraction is presented. This pseudostationary phase consists of surfactant, which is initially immobilized onto hydrophilic cation exchange resin. The surfactant chain through hydrophobic interactions extracts hydrophobic analytes in the same manner as conventional bonded alkyl moieties on silica based non-polar sorbents. Although hydrophobic analytes can be efficiently trapped on commercially available non-polar sorbents (i.e. Ci8 silica), organic solvents that are necessary to break strong hydrophobic interactions between the analytes and the sorbent are harmful. They are also incompatible for direct introduction into a reversed phase liquid chromatographic set up. In the presented approach, …

Spectroscopic Studies Of Inclusion Host-Guest Complexes Between Cyclophane Corrals And Polcyclic Aromatic Hydrocarbons, Mark O'Brien

Masters Theses & Specialist Projects

Cyclophanes are macromolecules that are known to effectively bind with molecules to form host-guest complexes. Several cyclophane molecules, referred to as corrals (1-6) by their founders, have been synthesized. The characterization of these compounds and their complexes has been investigated using combined spectroscopic and theoretical methods. Hostguest interactions of cyclophane-anthracene (C-A), cyclophane-9-fluorenone (C-F) and cyclophane-pyrene (C-P) complex systems in dichloromethane are presented in this thesis. The stability constants, log Ka, for the C-A, C-F and C-P complexes are determined using absorption and fluorescence spectroscopy. Heats of formation of corral 2 complexes were determined by measuring the complex association constants at …

Synthesis And Characterization Of Polyaminopolycarboxylic Acid Analogs Of Edta And Their Transition Metal Complexes, Martha Watson

Masters Theses & Specialist Projects

Polyaminopolycarboxylic acids have been studied for their ability to complex with various transition metal ions. Polyaminopolycarboxylic acids are of particular interest due to their ability to form multiple chelate rings with transition metal ions. Three analogs of EDTA have been successfully synthesized and characterized by i3C NMR: 1,3 PDTA (1,3-propylenediaminetetraacetic acid), 1,3-PDTP (1,3-propylenediaminetetrapropionic acid) and EDTP (ethylenediaminetetrapropionic acid). These ligands were then combined with copper (II), iron (III), cobalt (II) and nickel (II) to form complexes. The complexes formed were analyzed using UV-Vis, and the stability constants of the complexes were determined using potentiometry.

Determination Of Atrazine And Selected Respective Metabolites Using Strong Cation Exchange Resins, Cierra Cross

Masters Theses & Specialist Projects

A new solid phase extraction procedure (SPE) for the removal of atrazine and three respective metabolites including deisopropylatrazine, desethylatrazine, and didealkylatrazine from aqueous samples is presented. Octadecyl bonded silica (C18) is widely used in analytical preconcentration schemes. While C18 presents a facile method of analyte removal, a new approach is needed to achieve greater trapping for polar analytes. In this study strong cationic exchange (SCX) resins consisting of sulfonated polystyrene are investigated for their extraction capabilities of the selected analytes. By exploiting acid-base and pi-pi interactions the analytes are trapped and therefore extracted from aqueous samples. Salt solutions are used …

Carbon-Carbon Bond Formation Via O-Lithiointermediates, Julia Raymer

Masters Theses & Specialist Projects

The process of C-C bond formation via Directed ort/zo-Metalation (DoM) consists of two separate steps. Utilizing fractional equivalents of TMEDA in hydrocarbon solvents at 60°C, o-lithiation of anisole and dimethylaniline can be effected in >95% yields. The first step in the DoM process involves preparation of solid samples of these o-lithiointermediates. Completing the sequence, the second step concerns formation of a new arene-derivative bond at the reactive site. For this thesis the arene-derivative bond formed is to carbon. Various carbon electrophiles have been studied using different solvent systems, and results reveal a possible disconnect between the reaction conditions for the …

Cesium Effect: A Mild And Efficient Synthesis Of Secondary And Tertiary Phosphines, Matthew Honaker

Masters Theses & Specialist Projects

A mild and efficient method to synthesize a variety of secondary and tertiary, as well as disecondary and ditertiary phosphines has been developed. Using reaction conditions that include cesium hydroxide, molecular sieves, and DMF, at room temperature, a wide range of alkyl halides has been coupled to primary or secondary phosphines to yield secondary or tertiary phosphines. Included were activated and aliphatic halides, as well as base sensitive functional groups. In addition, examples of disecondary and ditertiary ligands have also been prepared using similar reaction conditions. The synthesis of a P-N-P ligand was also accomplished with these procedures. Optically active …

Directed Ortho Metalation In Hydrocarbon Solvents: Opposing Pi-Resonance Effects, Barry Woosley

Masters Theses & Specialist Projects

Hydrocarbon solvents are known to be unreactive toward organolithium reagents and do not typically support ortho-metalation reactions without the aid of a promoter. An exception would be an arene substrate having the capability to bidentate complex to the reactive alkyllithium dimer, which enables ortho-metalation to occur in high yields. A second, more limiting exception, would be that the arene substrate possesses localized lone pairs of electrons, as is the case when the directed ortho metalating group (DMG) is located in the benzyl position. The work reported here centers upon developing a third and larger class of arene substrates that are …

Spectroscopic Studies Of Chlorophyll A Complexes With Trinitro-Substituted Flourene Derivatives, Stephanie Smalley

Masters Theses & Specialist Projects

Absorption, fluorescence, and excited-state lifetime studies of chlorophyll a (Chl a) with fluorene, 2-(2,4,7-Trinitro-fluoren-9-ylideneaminooxy)-propionic acid (TFPR), 2- (2,4,7-Trinitro-fluoren-9-ylidenemethyl)-phenol, (TFPH), and 9-Isopropylidene-2,4,7- trinitro-9H-fluorene (ITNF) have been investigated. These systems were studied in acetonitrile and dichloromethane at room temperature. Absorption data were analyzed with the Nash plot. Linearity of the Nash plots proved that a 1:1 complex was formed between the donor and acceptor. Ground state binding constants (Ka) of each system were also determined from the y-intercept of these plots. Fluorescence data were analyzed with a Stern-Volmer plot. The quenching constants (Ksv) were obtained from the slope of these plots. These …

Determination Of Carbon Nanotube Modification By Tg-Ms And Pyrolysis-Gc/Ms, Quentin Lineberry

Masters Theses & Specialist Projects

Uniform dispersion of carbon nanotubes (CNTs) has been one of the major impediments to the full development of the incredible suite of properties offered by CNTs, specifically single-walled carbon nanotubes (SWNTs). However, investigators at NASA Langley and the National Institute of Aerospace Research have recently obtained (SWNTs) that are soluble in select solvents, including THF, DM Ac, and ODCB. The SWNTs were exposed to reagents used in cited fullerene modification chemistry in an attempt to produce soluble SWNTs. Upon further examination, it was determined that the intended functionalization had not occurred, and some other phenomenon was responsible for the SWNTs …

Development Of A Gene Transfer System In Clostridium Scindens Vpi 12708, Rashmi Ramasubbaiah

Masters Theses & Specialist Projects

Clostridium scindens VPI 12708 (previously known as Eubacterium sp. VPI 12708) is a bile-acid dehydroxylating bacterium originally isolated from the feces of a colon cancer patient. Many genes required for bile acid 7-a dehydroxylation are found on a large bile acid inducible operon (bai) that has been extensively studied. However the bai promoter, which directs expression of the bai operon, has yet to be characterized due, in part, to a lack of a functional genetic transfer system for this strain. A spontaneous rifampinresistant Clostridium scindens VPI 12708 mutant was used as a recipient to determine the efficacy of conjugation as …

Development Of An Analytical Method For Distinguishing Ammonium Bicarbonate From The Products Of An Aqueous Ammonia Co2 Scrubber And The Characterization Of Ammonium Bicarbonate, Lingyu Meng

Masters Theses & Specialist Projects

The link between anthropogenic emissions of CO2 with increased atmospheric CO2 levels and, in turn, with increased global temperature has been well established and accepted. Using aqueous ammonia to capture CO2 and produce an inexpensive nitrogen fertilizer, ammonium bicarbonate (ABC) has been thought as a feasible approach to CO2 sequestration.

Due to the different concentrations of reactants and reaction conditions, different carbon-ammonium composites can be produced. In view of achieving a maximum of NH3 utilization in the capture of CO2, the product of ABC will be ideal. Hence the ABC in the products needs to be identified. Various analytical techniques …