Digital Commons Network^™

Electron And Ion Spectroscopy Of Metal Hydrocarbon Complexes, Sudesh Kumari

Theses and Dissertations--Chemistry

Metal-hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE and MATI spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the spectroscopic measurements with quantum chemical calculations and spectral simulations.

In this dissertation, the metal complexes of mesitylene, aniline, cyclooctatetraene, benzene, ethene, and propene were studied. For each complex, different effects from metal coordination have been identified. Although metal-bis(mesitylene) sandwich complexes …

Structures And Electronic States Of Small Group 3 Metal Clusters, Lu Wu

Theses and Dissertations--Chemistry

Group 3 metal clusters are synthesized by laser vaporization in a pulsed cluster beam source and identified with laser ionization time-of-flight mass spectrometry. The adiabatic ionization energies and vibrational frequencies of these clusters are measured using mass-analyzed threshold ionization (MATI) spectroscopy. Their structures and electronic states are determined by combining the MATI spectra with quantum chemical calculations and spectral simulations. This dissertation focuses on the study of several small molecules, which include LaO₂, La₂, M₂O₂, M₃O₄, M₃C₂, and La₃C₂O, where …

Electrode And Electrolyte Additives For Lifetime Extension In Lithium-Ion Batteries, Kishore Anand Narayana

Theses and Dissertations--Chemistry

Lithium-ion batteries (LIBs) are the most commonly used type of rechargeable batteries with a global market estimated at $11 billion, which is predicted to grow to $60 billion by 2020. The global commercialization of Li-ion batteries is impeded by issues such as poor cycle life (5000 cycles achieved in some LIBs) in high energy and power density applications because of the rising internal resistance due to aging and safety concerns such as overcharge which ultimately leads to thermal runaway and explosions. A battery’s performance mainly depends on external factors such as electrode thickness and degree of compacting, and the type …

Increase Of Basal Oxidative Stress Levels And Impairment Of Heme Oxygenase-1/Biliverdin Reductase Post-Translational Modification By The Defect Of Parkinson-Related Gene Of Pink1, Zhaoshu Zhang

Theses and Dissertations--Chemistry

Parkinson disease (PD) is the most common movement disorder and the second most common neurodegenerative disease. PINK1, PTEN-induced kinase 1, functions as a serine/threonine kinase as well as a protector of mitochondrial function. Mutations in PINK1 gene result in either mitochondria dysfunction or disruption of kinase signaling pathways involved in the pathogenesis of PD.

In this thesis, oxidative stress levels were examined in the brain of PINK1 knockout mice, and also how heme oxygenase-1 and biliverdin reductase are affected in brain of PINK1 knockout mice. In addition, posttranslational modifications are a way to control the behavior of proteins, so posttranslational …

A Study Of Lignin Depolymerization By Selective Cleavage Of The Cα-Cβ Linkages In Lignin Model Compounds Via Baeyer-Villiger Oxidation & An Investigation Of The Channeling Reaction In Nitrogen-Doped Multiwalled Carbon Nanotubes (N-Mwcnts), Nikhil Dilip Patil

Theses and Dissertations--Chemistry

A STUDY OF LIGNIN DEPOLYMERIZATION BY SELECTIVE CLEAVAGE OF THE Cα-Cβ LINKAGES IN LIGNIN MODEL COMPOUNDS VIA BAEYER-VILLIGER OXIDATION

Lignin is amorphous aromatic polymer derived from plants and is a potential source of fuels and bulk chemicals. Herein, we present a survey of reagents for selective stepwise oxidation of lignin model compounds. Specifically, we have targeted the oxidative cleavage of Cα-Cβ bonds as a means to depolymerize lignin and obtain useful aromatic compounds. In this work, we prepared several lignin model compounds that possess structures, characteristic reactivity, and linkages closely related to the parent lignin polymer. We observed that selective …

Cross Photoreaction Of Pyruvic And Glyoxylic Acids In Model Aqueous Aerosols, Shasha Xia

Theses and Dissertations--Chemistry

Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. Aerosols from natural and anthropogenic sources can be primary organic aerosols (POA), which are directly emitted to the atmosphere, or secondary organic aerosols (SOA) that are formed from chemical reactions of gas-phase precursors. At variance with the well investigated formation of SOA from gas phase precursors, the chemistry of aqueous SOAs that contribute to the total SOA budget remains unknown. Field measurements have revealed that carboxylic, dicarboxylic and oxocarboxylic acids are abundant species present in SOAs. This thesis …

Bases For Breadth - Insights Into How The Mechanism And Dynamics Of Nitroreductase Can Explain This Enzyme's Broad Substrate Repertoire, Warintra Pitsawong

Theses and Dissertations--Chemistry

Nitroreductase from Enterobacter cloacae (NR) is a member of a large family of homologues represented in all branches of the tree of life. However the physiological roles of many of these enzymes remain unknown. NR has distinguished itself on the basis the diverse sizes and chemical types of substrates it is able to reduce (Koder et al 1998). This might be an evolved characteristic suiting NR for a role in metabolism of diverse occasional toxins. While there are numerous studies of determinants of substrate specificity, we know less about mechanisms by which enzymes can be inclusive. Therefore, we present …

Salen Aluminum Compounds In The Dealkylation And Detection Of Organophosphates, Rahul R. Butala

Theses and Dissertations--Chemistry

The focus of this dissertation is the use of aluminum Schiff base compounds, Salen(^tBu)AlBr (SAB), in the dealkylation and detection of organophosphates (OPs). Three SAB compounds, Salen(^tBu)AlBr (1), Salpen(^tBu)AlBr (2), and Salophen(^tBu)AlBr (3) were used to dealkylate a variety of trialkyl OPs. These reactions lead to unique organic-soluble aluminum phosphate compounds containing six-coordinate aluminum. Examples include [salen(^tBu)AlOP(O)(OCH₃)₂]_n (4), [salen(^tBu)AlOP(O)(OCH₂CH₃)₂]_n (5), [salen(^tBu)AlOP(O)(OPh)₂]_{n …}

Survival After Pneumonectomy For Stage Iii Non-Small Cell Lung Cancer, Sibu P. Saha, Rohan J. Kalathiya, Daniel L. Davenport, Victor A. Ferraris, Timothy W. Mullett, Joseph B. Zwischenberger

Surgery Faculty Publications

OBJECTIVES: Stage III non-small cell lung cancer (NSCLC) has a poor prognosis. Reports suggest that five-year survival after current treatment is between 14 to 24 percent. The purpose of this retrospective study was to investigate the morbidity and mortality of patients diagnosed with stage III NSCLC and treated with pneumonectomy at the University of Kentucky Medical Center in Lexington, KY.

METHODS: We reviewed the medical record and tumor registry follow-up data on 100 consecutive patients who underwent pneumonectomy for lung cancer at the University of Kentucky.

RESULTS: We identified thirty-six patients in stage III who underwent pneumonectomy. Ten patients had …

The Interaction Between Fdi And Infrastructure Capital In The Development Process, Farrokh Nourzad, David N. Greenwold, Rui Yang

Economics Faculty Research and Publications

This paper focuses on the possible interaction between foreign direct investment (FDI) and the host country’s infrastructure base. Its central hypothesis is that the effect of FDI on per capita real income depends, at least in part, on the size of the recipient country’s infrastructure. This hypothesis is tested in a panel of 46 countries and 5-year averages over the 1980–2000 period using the size of three types of infrastructure capital: telecommunication, power generation, and network of roads or highways. The results indicate that the size of the host country’s infrastructure base helps to improve the marginal effect of FDI …

Strengthening The Vpa General Permit: Managing Animal Feeding Operations In Virginia To Meet State Law And The Bay Tmdl, Rachel Cannon, Jason Kane

Virginia Coastal Policy Center

No abstract provided.

Echo, Winter/Spring 2014, Columbia College Chicago

Echo

Student-produced magazine formerly published as Chicago Arts and Communication, changed to Echo magazine in 1997. Cover Articles: Puff puff passed: patients won the fight for pot - what's next?; Classy porn: inside the pinup revival; Jammin' jesters: Wedding Banned's peculiar appeal; Generation Q: are you having a Quarter Life Crisis?; Love, virtually: anonymous admireres, rebooting online dating, serendipity in the city. 80 pages.

Patterns Of Maximum Body Size Evolution In Cenozoic Land Mammals: Eco-Evolutionary Processes And Abiotic Forcing, Juha J. Saarinen, Alison G. Boyer, James H. Brown, Daniel P. Costa, S.K. Morgan Ernest, Alistair R. Evans, Mikael Fortelius, John L. Gittleman, Marcus J. Hamilton, Larisa E, Harding, Kari Lintulaakso, S. Kathleen Lyons, Jordan G. Okie, Richard M. Sibly, Patrick R. Stephens, Jessica Theodor, Mark D. Uhen, Felisa A. Smith

School of Biological Sciences: Faculty Publications

There is accumulating evidence that macroevolutionary patterns of mammal evolution during the Cenozoic follow similar trajectories on different continents. This would suggest that such patterns are strongly determined by global abiotic factors, such as climate, or by basic eco-evolutionary processes such as filling of niches by specialization. The similarity of pattern would be expected to extend to the history of individual clades. Here, we investigate the temporal distribution of maximum size observed within individual orders globally and on separate continents. While the maximum size of individual orders of large land mammals show differences and comprise several families, the times at …

The Role Of Comparative Law In Shaping Corporate Statutory Reforms, Marco Ventoruzzo

Faculty Scholarship

This Essay discusses how comparative law played and plays a role in the statutory development of corporate laws. The influence of laws of other systems on the development of statutory law is common, explicit, and represents a tradition that accompanied legal reforms since the very beginning of the development of legislation.

Focusing on modern corporate law, I argue (but the argument could be extended to many other legal fields) that it is necessary to distinguish two basic ways in which comparative law influences legal reforms in one particular jurisdiction. The first one is through regulatory competition among different systems. In …

When Push Comes To Shove : An Equity Analysis Of A Uniform Tax Rate And Equalized Assessed Valuation In Illinois, Susan L. Farrell

Graduate Research Theses & Dissertations

The state of Illinois adopted a General State Aid per-pupil foundation level for the 2011-2012 school year of {dollar}6,119. The legislature failed to allocate enough funding to provide the adopted level to school districts. This study examines three alternative methods of attaining the 2012 Illinois adopted foundation funding level for the 864 school districts in Illinois. The three methods explored are consolidating EAV at a county level and utilizing a uniform tax rate, moving to a state support program, and applying an operational tax rate to districts as they currently exist.

Trust V. Law (In A Box): Do Organizational Forms Really Make A Difference?, Jeffrey M. Lipshaw

Suffolk University Law School Faculty Works

In this contribution to the University of Illinois College of Law’s 2013 Larry Ribstein Memorial Symposium, I assess Professor Ribstein’s approach to both to trust and the “uncorporation.” My thesis is that his disciplinary commitment to a transaction cost economics model resulted in an overstatement of the extent to which business association forms matter in the real world. In contrast to Professor Ribstein’s view that mandatory law (which includes corporate law) “crowds out” trust (implicitly making uncorporations more amenable to trust), I see the orderliness of modern and abstract business structures (of any kind) as distinct from, yet operating at …

Structure And Catalytic Properties Of Ultra-Small Ceria Nanoparticles, Xing Huang

Theses and Dissertations--Chemical and Materials Engineering

Cerium dioxide (ceria) is an excellent catalytic material due to its ability to both facilitate oxidation/reduction reactions as well as store/release oxygen as an oxygen buffer. The traditional approach to assess and improve ceria's catalytic behavior focuses on how efficiently O-vacancies can be generated and/or annihilated within the material, and how to extend established understandings of "bulk" ceria to further explain the greatly enhanced catalytic behavior of ultra-small ceria nanoparticles (uCNPs) with sizes less than 10 nm. Here, using density functional theory (DFT) calculations, we reexamine the atomic and electronic structures of uCNPs, especially their surface configurations. A unique picture …

Nanofiltration Membranes From Oriented Mesoporous Silica Thin Films, Mary K. Wooten

Theses and Dissertations--Chemical and Materials Engineering

The synthesis of mesoporous silica thin films using surfactant templating typically leads to an inaccessible pore orientation, making these films not suitable for membrane applications. Recent advances in thin film synthesis provide for the alignment of hexagonal pores in a direction orthogonal to the surface when templated on chemically neutral surfaces. In this work, orthogonal thin film silica membranes are synthesized on alumina supports using block copolymer poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123) as the template. The orthogonal pore structure is achieved by sandwiching membranes between two chemically neutral surfaces, resulting in 90 nm thick films. Solvent flux of ethanol through …

Influence Of Ferrite Phase In Alite-Calcium Sulfoaluminate Cements, Tristana Y. Duvallet

Theses and Dissertations--Chemical and Materials Engineering

Since the energy crisis in 1970’s, research on low energy cements with low CO₂-emissions has been increasing. Numerous solutions have been investigated, and the goal of this original research is to create a viable hybrid cement with the components of both Ordinary Portland cement (OPC) and calcium sulfoaluminate cement (CSAC), by forming a material that contains both alite and calcium sulfoaluminate clinker phases. Furthermore, this research focuses on keeping the cost of this material reasonable by reducing aluminum requirements through its substitution with iron. The aim of this work would produce a cement that can use large amounts …

Quartz Crystal Microbalance Investigation Of Cellulosome Activity From Clostridium Thermocellum On Model Cellulose Films, Shanshan Zhou

Theses and Dissertations--Chemical and Materials Engineering

The cost of deconstructing cellulose into soluble sugars is a key impediment to the commercial production of lignocellulosic biofuels. The use of the quartz crystal microbalance (QCM) to investigate reaction variables critical to enzymatic cellulose hydrolysis is investigated here, extending previous studies of fungal cellulase activity for the first time to whole cell cellulases. Specifically, the activity of the cellulases of Clostridium thermocellum, which are in the form of cellulosomes, was investigated. To clearly differentiate the activity of free cellulosome and cell-bound cellulosome, the distribution of free cellulosome and cell-bound cellulosome in crude cell broth at different growth stages …

The Development And Biocompatibility Of Low Temperature Co-Fired Ceramic (Ltcc) For Microfluidic And Biosensor Applications, Jin Luo

Theses and Dissertations--Chemical and Materials Engineering

Low temperature co-fired ceramic (LTCC) electronic packaging materials are applied for their electrical and mechanical properties, high reliability, chemical stability and ease of fabrication. Three dimensional features can also be prepared allowing integration of microfluidic channels and cavities inside LTCC modules. Mechanical, optical, electrical, microfluidic functions have been realized in single LTCC modules. For these reasons LTCC is attractive for biomedical microfluidics and Lab-on-a-Chip systems. However, commercial LTCC systems, optimized for microelectrics applications, have unknown cytocompatibility, and are not compatible with common surface functionalization chemistries.

The first goal of this work is to develop biocompatible LTCC materials for biomedical applications. …

Functionalized Membranes For Environmental Remediation And Selective Separation, Li Xiao

Theses and Dissertations--Chemical and Materials Engineering

Membrane process including microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have provided numerous successful applications ranging from drinking water purification, wastewater treatment, to material recovery. The addition of functional moiety in the membranes pores allows such membranes to be used in challenging areas including tunable separations, toxic metal capture, and catalysis. In this work, polyvinylidene fluoride (PVDF) MF membrane was functionalized with temperature responsive (poly(N-isopropylacrylamide), PNIPAAm) and pH responsive (polyacrylic acid, PAA) polymers. It’s revealed that the permeation of various molecules (water, salt and dextran) through the membrane can be thermally or pH controlled. The introduction of …

Nanometer-Scale Membrane Electrode Systems For Active Protein Separation, Enzyme Immobilization And Cellular Electroporation, Zhiqiang Chen

Theses and Dissertations--Chemical and Materials Engineering

Automated and continuous processes are the future trends in downstream protein purification. A functionalized nanometer-scale membrane electrode system, mimicking the function of cell wall transporters, can selectively capture genetically modified proteins and subsequently pump them through the system under programmed voltage pulses. Numerical study of the two-step pulse pumping cycles coupled with experimental His-GFP releasing study reveals the optimal 14s/1s pumping/repel pulse pumping condition at 10 mM bulk imidazole concentration in the permeate side. A separation factor for GFP: BSA of 9.7 was achieved with observed GFP electrophoretic mobility of 3.1×10^-6 cm² s^-1 V^-1 at 10 …

Cnt Membrane Platforms For Transdermal Drug Delivery And Aptamer Modulated Transport, Tao Chen

Theses and Dissertations--Chemical and Materials Engineering

CNT membrane platforms are biomimetic polymeric membranes imbedded with carbon nanotubes which show fast fluid flow, electric conductivity, and the ability to be grafted with chemistry. A novel micro-dialysis probe nicotine concentration sampling technique was proposed and proved in vitro, which could greatly improve the efficiency and accuracy of future animal transdermal studies. To enhance the scope of transdermal drug delivery which was limited to passive diffusion of small, potent lipophilic drugs, a wire mesh lateral electroporation design was also proposed which could periodically disrupt the skin barrier and enhance drug flux.

It was shown that AMP binding aptamer …

Magnesium-Titanium Alloys For Biomedical Applications, Ilona Hoffmann

Theses and Dissertations--Chemical and Materials Engineering

Magnesium has been identified as a promising biodegradable implant material because it does not cause systemic toxicity and can reduce stress shielding. However, it corrodes too quickly in the body. Titanium, which is already used ubiquitously for implants, was chosen as the alloying element because of its proven biocompatibility and corrosion resistance in physiological environments. Thus, alloying magnesium with titanium is expected to improve the corrosion resistance of magnesium.

Mg-Ti alloys with a titanium content ranging from 5 to 35 at.-% were successfully synthesized by mechanical alloying. Spark plasma sintering was identified as a processing route to consolidate the alloy …

Iron And Iron Oxide Functionalized Membranes With Applications To Selected Chloro-Organic And Metal Removal From Water, Minghui Gui

Theses and Dissertations--Chemical and Materials Engineering

The development of functionalized membranes with tunable pores and catalytic properties provides us an opportunity to manipulate the membrane pore structure, selectivity and reactivity. By introducing the functional groups into membrane pores, dissolved metal ions and reactive particles can be effectively immobilized within the polymer matrix for toxic chloro-organic and heavy metal remediation in water.

A polyelectrolyte functionalized membrane platform with tunable pore size and ion exchange capacity has been developed for iron/iron oxide nano-catalyst synthesis and chlorinated organic compound (trichloroethylene, TCE and polychlorinated biphenyls, PCBs) degradation. Highly robust polyvinylidene fluoride (PVDF) microfiltration membranes are used as the support with …

Layer-By-Layer Assemblies For Membrane-Based Enzymatic Catalysis, Andrew R. Tomaino

Theses and Dissertations--Chemical and Materials Engineering

While considerable progress has been made towards understanding the effect that membrane-based layer-by-layer (LbL) immobilizations have on the activity and stability of enzymatic catalysis, detailed work is required in order to fundamentally quantify and optimize the functionalization and operating conditions that define these properties. This work aims to probe deeper into the nature of transport mechanisms by use of pressure-induced, flow-driven enzymatic catalysis of LbL-functionalized hydrophilized poly(vinyldiene) (PVDF)-poly(acrylic acid) (PAA)-poly(allylamine hydrochloride) (PAH)-glucose oxidase (GOx) membranes. These membranes were coupled in a sealed series following cellulose acetate (CA) membranes for the elimination of product accumulation within the feed-side solution during operation. …

Generation Of Multicomponent Polymer Blend Microparticles Using Droplet Evaporation Technique And Modeling Evaporation Of Binary Droplet Containing Non-Volatile Solute, Venkat N. Rajagopalan

Theses and Dissertations--Chemical and Materials Engineering

Recently, considerable attention has been focused on the generation of nano- and micrometer scale multicomponent polymer particles with specifically tailored mechanical, electrical and optical properties. As only a few polymer-polymer pairs are miscible, the set of multicomponent polymer systems achievable by conventional methods, such as melt blending, is severely limited in property ranges. Therefore, researchers have been evaluating synthesis methods that can arbitrarily blend immiscible solvent pairs, thus expanding the range of properties that are practical. The generation of blended microparticles by evaporating a co-solvent from aerosol droplets containing two dissolved immiscible polymers in solution seems likely to exhibit a …

Microstructure And Work Function Of Dispenser Cathode Coatings: Effects On Thermionic Emission, Phillip D. Swartzentruber

Theses and Dissertations--Chemical and Materials Engineering

Dispenser cathodes emit electrons through thermionic emission and are a critical component of space-based and telecommunication devices. The emission of electrons is enhanced when coated with a refractory metal such as osmium (Os), osmium-ruthenium (Os-Ru), or iridium (Ir). In this work the microstructure, thermionic emission, and work function of thin film Os-Ru coatings were studied in order to relate microstructural properties and thermionic emission.

Os-Ru thin film coatings were prepared through magnetron sputtering and substrate biasing to produce films with an array of preferred orientations, or texture. The effect of texture on thermionic emission was studied in detail through closely-spaced …

A Multidisciplinary Techno-Economic Decision Support Tool For Validating Long-Term Economic Viability Of Biorefining Processes, Sumesh Sukumara

Theses and Dissertations--Chemical and Materials Engineering

Increasing demand for energy and transportation fuel has motivated researchers all around the world to explore alternatives for a long-term sustainable source of energy. Biomass is one such renewable resource that can be converted into various marketable products by the process of biorefining. Currently, research is taking strides in developing conversion techniques for producing biofuels from multiple bio-based feedstocks. However, the greatest concern with emerging processes is the long-term viability as a sustainable source of energy. Hence, a framework is required that can incorporate novel and existing processes to validate their economic, environmental and social potential in satisfying present energy …