Chemistry Commons^™

Corrosion Behavior Of Copper Thin Films In Organic Hf-Containing Cleaning Solution For Semiconductor Applications, Nabil George Mistkawi, Makarem A. Hussein, Malgorzata Ziomek-Moroz, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

The corrosion behavior of electrochemically deposited copper thin films in deaerated and non-deaerated commercial cleaning solutions containing HF was investigated. Potentiodynamic polarization experiments were carried out to determine active, active–passive, passive, and transpassive regions. Corrosion rates were calculated from Tafel slopes. The addition of hydrogen peroxide to the solution and its influence on corrosion was also investigated by employing inductively coupled plasma-mass spectroscopy (ICP-MS) and X-ray photoelectron spectroscopy (XPS). The ICP-MS and potentiodynamic methods yielded comparable Cu dissolution rates. Surface analysis using atomic force microscopy and scanning electron microscopy, performed before and after the cleaning solution treatment, did not reveal …

Development Of Reductive Metal Systems For The Degradation Of Energetic Compounds (Tatp, Tnt, And Rdx), Rebecca L. Albo

Electronic Theses and Dissertations

Triacetone triperoxide (TATP), a cyclic peroxide explosive, is frequently used by terrorists and amateur chemists due to the ease of synthesis and the availability of reagents. TATP is extremely sensitive to shock, heat, and friction thus a safe and rapid method for treating TATP is needed. The major objective of this dissertation was to develop in situ methodologies that could safely degrade TATP in various field situations. Initial studies focused on using zero-valent metals and mechanically alloyed metals to decompose TATP samples in both aqueous and organic solutions. The metal systems tested included zero-valent iron, magnesium, and magnesium bimetal, Mg/Pd. …

Synthesis And Applications Of Ring Opening Metathesis Polymerization Based Functional Block Copolymers, Sanchita Biswas

Electronic Theses and Dissertations

Ring opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the superparamagnetic polymeric nanocomposites. The Jaggregation properties of the porphyrin dyes were improved via self-assembly with a customized norbornene polymer. Novel multimodal copolymer probes were synthesized for two-photon fluorescence integrin-targeted bioimaging. In Chapter 1 a brief overview of ROMP along with …

Synthesis Of Novel Glycosylidene-Based Quinolines, Peter H. Dobbelaar

Seton Hall University Dissertations and Theses (ETDs)

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Development Of Novel Ahr Antagonists, Hyosung Lee

University of Kentucky Doctoral Dissertations

Aryl hydrocarbon receptor (AHR) is a sensor protein, activated by aromatic chemical species for transcriptionally regulating xenobiotic metabolizing enzymes. AHR is also known to be involved in a variety of pathogenesis such as cancer, diabetes mellitus, cirrhosis, asthma, etc. The AHR signaling induced by xenobiotics has been intensively studied whereas its physiological role in the absence of xenobiotics is poorly understood. Despite a number of ligands of AHR have been reported thus far, further applications are still hampered by the lack of specificity and/or the partially agonistic activity. Thus, a pure AHR antagonist is needed for deciphering the AHR cryptic …

Biochemical Characterization Of Human Mismatch Recognition Proteins Mutsα And Mutsβ, Lei Tian

University of Kentucky Doctoral Dissertations

The integrity of an organism's genome depends on the fidelity of DNA replication and the efficiency of DNA repair. The DNA mismatch repair (MMR) system, which is highly conserved from prokaryotes to eukaryotes, plays an important role in maintaining genome stability by correcting base-base mismatches and insertion/deletion (ID) mispairs generated during DNA replication and other DNA transactions. Mismatch recognition is a critical step in MMR. Two mismatch recognition proteins, MutSα (MSH2-MSH6 heterodimer) and MutSβ (MSH2-MSH3 heterodimer), have been identified in eukaryotic cells. MutSα and MutSβ have partially overlapping functions, with MutSα recognizing primarily base-base mismatches and 1-2 nt ID mispairs …

Explorations In Homeoviscous Adaptation And Mass Spectral Analysis Of Membrane Lipids, Michael Douglas Timmons

University of Kentucky Doctoral Dissertations

The focus of this dissertation is centered on the mass spectral analysis of lipids and changes occurring in keeping with the concept of homeoviscous adaptation [1]. Homeoviscous adaptation is the process of modification of membrane lipids in response to environmental stimuli [1]. Dissertation investigations applied this concept to prokaryotic and eukaryotic organisms, and expanded the perception of environmental factors from exogenous organic solvents to intracellular environment.

The field of lipidomics deals with the analysis of phospholipid and fatty acid components of membranes the changes that occur due to environmental stimuli and their biological significance [2-6]. The high sensitivity of mass …

In Vivo Oxidative Stress In Alzheimer Disease Brain And A Mouse Model Thereof: Effects Of Lipid Asymmetry And The Single Methionine Residue Of Amyloid-Β Peptide, Miranda Lu Bader Lange

University of Kentucky Doctoral Dissertations

Studies presented in this dissertation were conducted to gain more insight into the role of phospholipid asymmetry and amyloid-β (Aβ)-induced oxidative stress in brain of subjects with amnestic mild cognitive impairment (aMCI) and Alzheimer disease (AD). AD is a largely sporadic, age-associated neurodegenerative disorder clinically characterized by the vast, progressive loss of memory and cognition commonly in populations over the age of ~65 years, with the exception of those with familial AD, which develop AD symptoms as early as ~30 years-old. Neuropathologically, both AD and FAD can be characterized by synapse and neuronal cell loss in conjunction with accumulation of …

Degradation Of Organic Matter In Water In The Presence Of Catalyst And Uv Radiation, Bimali Bandaranayake

Masters Theses

Organic contaminants specially dyes, presents in water is a major environmental problem. Organic compounds can be degraded completely in the presence of photocatalysts and UV radiation. The kinetics of degradation of three dyes was studied using a variety of UV photocatalytic materials. The dyes (methylene blue, malachite green, chrysodoine R) were chosen based on their polarity differences. Catalysts consisting of pure TiO2, mixed oxides of TiO2 containing SiO2, and others containing SiO2 and iron oxide, SiO2/ ZrO2/ CeO2, and CeO2/SiO2 were studied. The TiO2/ SiO2 and SiO2/ZrO2/CeO2 catalysts exhibited the highest degradation rates for methylene blue. The more hydrophobic pure …

Nanoporous High Surface Area Silicas With Chelating Groups For Heavy Metal Ion Adsorption From Aqueous Solution, Kothalawalage Nuwan Kothalawala

Masters Theses

Nanoporous high surface area silicas are an ideal substrate for the design of materials with useful properties via chemical surface modification. The adsorption of heavy metals for contaminated water detoxification is one potential application. In this work we have used three different kinds of silica substrates with varying pore structures; commercially available narrow pore and wide pore silica gels, as well as surfactant templated mesoporous SBA-15 exhibiting a relatively narrow pore size distribution. These silicas have each been subjected to post-synthesis modification with an organosilane consisting of ethylenediamine triacetic acid functionalities for chelation/adsorption of metal ions from aqueous solution. The …

Ditopic Dithiophosphonates And Their Related Rotaxanes, Robert Ray Baum Jr.

Masters Theses

Grafting dithiophosphonate groups onto a naphthalenediimide core yields anionic axles, which in conjunction with the 15DN38C10 crown ether and cationic metallic systems generate neutral bimetallic rotaxanes. The association constant for the rotaxane system was calculated by the single-point method using 1H NMR spectroscopy. Metallic systems reacted with our anionic axles were SnMe3, SnPh3, Cu(PPH3)i, SnMe2, and SnPh2. The structures of several axle-metal complexes and one rotaxane were obtained by X-ray crystallography.

Shorter Still: Compressing C-C Single Bonds, Gerarso Martinez-Guajardo, Kelling J. Donald, Bernard K. Wittmaack, Miguel Angel Vazquez, Gabriel Merino

Chemistry Faculty Publications

How short can a C-C single bond get? The bonding in a set of molecules that are related structurally to previously synthesized or theoretically examined systems with short C-C bonds is investigated. According to calculations, a single C-C bond could be compressed to 1.313 A! To the best of our knowledge, this is the shortest single C-C bond reported to date. This shortening is a consequence of a change in the C-C-C bond angle, θ, to minimize strain in the cages and an effort to offset the tension in the surrounding bridges.

1, 2-Bis (Phenylsulfonyl)-1h-Indole As An Acceptor Of Organocuprate Nucleophiles, David C. Qian, Philip E. Alford, Tara L. S. Kishbaugh, Sean T. Jones, Gordon W. Gribble

Dartmouth Scholarship

1,2-Bis(phenylsulfonyl)-1H-indole is a novel example of an electron-deficient indole that undergoes nucleophilic attack at C-3. Though a variety of other organometallic nucleophiles fail to engender nucleophilic substitution, organocuprates produce 3-substituted 2-(phenylsulfonyl)-1H-indoles. These reactions contribute to the growing number of examples of nucleophilic addition to the indole core.

Selective Fluorescence Detection Of Cysteine And N-Terminal Cysteine Peptide Residues, Soojin Lim, Jorge O. Escobedo, Mark Lowry, Xiangyang Xu, Robert M. Strongin

Chemistry Faculty Publications and Presentations

A new fluorogenic fluorescein derivative containing an α,β-unsaturated aldehyde moiety produces a selective fluorescent signal enhancement in the presence of cysteine or peptides containing N-terminal cysteine residues. The mechanism is based on synergistic covalent and supramolecular interactions.

Copper Thin-Film Dissolution/Precipitation Kinetics In Organic Hf Containing Cleaning Solution, Nabil George Mistkawi, Makarem A. Hussein, Malgorzata Ziomek-Moroz, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

The corrosion behavior of electrochemically deposited copper thin films in deaerated and non-deaerated commercial cleaning solution containing HF has been investigated. Thin-film copper dissolution and reaction kinetics were investigated by monitoring Cu²⁺ , employing inductively coupled plasma–mass spectroscopy, and the oxidation states of copper on Si wafer surface, employing X-ray photoelectron spectroscopy. It was determined that the reaction kinetics is first order with respect to both HF and oxygen concentrations. A kinetic scheme involving reduction of oxygen and oxidation of Cu⁰ and Cu¹⁺ is proposed, which is consistent with the experimentally determined reaction kinetic orders and the …

The Population Of Sap And Tsap Isomers In Cyclen-Based Lanthanide(Iii) Chelates Is Substantially Affected By Solvent, Kyle J. Miller, Ali A. Saherwala, Benjamin C. Webber, Yunkou Wu, A. Dean Sherry, Mark Woods

Chemistry Faculty Publications and Presentations

The square antiprism/twisted square antiprism ratio in LnDOTA-tetraamide chelates is a critical parameter in governing water-exchange kinetics and ultimately the utility of a chelate as a PARACEST MRI contrast agent. In LnDOTA-tetraamide chelates with tertiary amides, this ratio and the rate of interconversion between these two structural isomers are found to be dramatically dependent upon the solvent and possibly other local environmental factors.

Design, Synthesis And Characterization Of New Two-Photon Absorbing (2pa) Fluorescent Dyes And Bioconjugates, And Their Applications In Bioimaging, Carolina D. Andrade

Electronic Theses and Dissertations

The development of new multiphoton absorbing materials has attracted the attention of researchers for the last two decades. The advantages that multiphoton absorbing materials offer, versus their one-photon absorbing counterparts, rely on the nature of the nonlinearity of the absorption process, where two photons are absorbed simultaneously offering increased 3D resolution, deeper penetration, and less photobleaching and photodamage as a result of a more confined excitation. The applications of efficient two-photon absorbing materials have been extensively expanding into the fields of photodynamic therapy, microscopy, and optical data storage. One of the fields where an increased interest in multiphoton absorbing materials …

Molecular Mechanics Studies Of Enzyme Evolutionary Mechanisms, Manoj Singh

All Dissertations

In the current dissertation, closely related studies to quantify the mechanism underlying enzyme evolution have been discussed. The HIV-1 protease and beta-lactamase enzymes were used as model systems for these studies. These are well known enzymes that are associated with drug resistance and are associated with the pathogenic diseases, and therefore, developing molecular level understanding of drug resistance through these enzymes has fundamental as well as practical importance.
In chapter 2, the relationship between errors in modeled protein structures and associated binding affinity predictions to small molecules is established. The results of this study are applicable in addressing a wide …

Analysis And Occurrence Of Disinfection By-Products In Fresh And Salt Water, Honglan Shi

Doctoral Dissertations

"Haloacetic acids, trihalomethanes, and bromate are important toxic water disinfection by-products (DBPs) that the US Environmental Protection Agency (USEPA) regulates in drinking water. Iodoacetic acids and halonitromethanes (HNMs) are the unregulated emerging DBPs that have been recently found in the disinfected drinking waters, and which have much higher toxicity than the regulated DBPs. The purpose of this study was to develop new analytical methods for analysis of these emerging DBPs, to study their occurrence in Missouri drinking water systems, and to investigate the occurrence and formation of these DBPs in saltwater and seawater based marine park aquaria. A new rapid …

Haart Drugs Induce Oxidative Stress And Mitochondrial Dysfunction In Blood-Brain Barrier, Kalyan Reddy Manda

Doctoral Dissertations

"The era of highly active antiretroviral therapy (HAART) has controlled AIDS and its related disorders considerably; however, the prevalence of HIV-1-associated neurocognitive disorders (HAND) has been on the rise in the post-HAART era. In view of these developments, we investigated whether a HAART drug combination of 3'-Azido-2', 3'-deoxythymidine (AZT) and Indinavir (IDV) can alter the functionality of the blood-brain barrier (BBB) endothelial cells, thereby exacerbating the condition. Viability of hCMEC/D3 cells (in vitro model of BBB) that were exposed to the drugs was significantly reduced after a 72 hr treatment, in a dose-dependent manner. Reactive oxygen species (ROS) were highly …

The Stereochemistry Of Selected Supramolecular Complexes Of Cucurbiturils And The Effect Of Homogeneous Equilibria And Electron Transfer Of The Guest, Arumugam Thangavel

Doctoral Dissertations

"From a practical perspective, host-guest complexes are vehicles for understanding and using supramolecular interactions for purposeful function in sensors, molecular machines and switches, while from a fundamental perspective they may lead to novel supramolecular protection schemes in basic organic reactions. This dissertation examines the interactions of cucurbiturils as barrel-shaped hosts, exhibiting a hydrophobic cavity, with substituted benzoylpyrydinium, phenypyrylium, and diazaanthraquinonediium cations as guests. In water, N-methyl-4-(p-substituted benzoyl)pyridinium cations exist in equilibrium with their hydrated forms (gem-diols), whose concentrations depend on the para substituent. In the presence of cucurbit7uril (CB[7]), the benzoyl group shows a preference for the CB[7] cavity, and …

Adsorption And Segmental Dynamics Of Acrylate And Methacrylate Polymers Adsorbed On A Silica Surface, Piyawan Krisanangkura

Doctoral Dissertations

"Poly(isopropyl acrylate)-d₇ (PIPA- d₇) was studied using ²H solid-state NMR and modulated differential scanning calorimetry (MDSC). The polymer was deuterated on the methyl groups and side-chain methine. The PIPA- d₇ was adsorbed onto Cab-O-Sil silica. These two types of deuterons each showed their own characteristic deuterium nuclear magnetic resonance (NMR) spectra for bulk PIPA- d₇. The ²H NMR spectra of adsorbed PIPA- d₇ samples showed the presence of heterogeneity of the segmental dynamics. A residual powder pattern was found in the spectra of the surface samples at higher temperatures, indicating that the segments were tightly attached to the silica. The …

Nmr Investigations Of Biomass-To-Fuel Conversions By Hydrothermal Processes, Wenjia Zhang

Doctoral Dissertations

"Biofuels have gained significant attention as the most promising alternative energy and fuel supply for the near future because of two dominant reasons: first, biofuels are environmentally friendly; and second, they afford a sustainable technology. Biofuels can be synthesized from biomass by several different processes, among which, hydrothermal conversion is considered to be more energy efficient. However, scientific efforts to improve hydrothermal biomass-to-fuel (HT-BTF) conversion efficiencies are severely limited because little is known about the salient reaction mechanisms and intermediates. This study is aimed at a better understanding of the hydrothermal biomass degradation kinetics by advanced NMR spectroscopy and, accordingly, …

Effect Of Structure And Plasticizer On The Glass Transition Of Adsorbed Polymer, Boonta Hetayothin

Doctoral Dissertations

"The effect of molecular mass on adsorbed poly(methyl methacrylate) (PMMA) on silica was determined using temperature-modulated differential scanning calorimetry (TMDSC). A two-component model, based on loosely-bound polymer (glass transition temperature, T_g, similar to that of bulk) and tightly-bound polymer (T_g higher than that of bulk) was used to interpret the thermograms. Similar amounts of tightly-bound polymer were found for 450 and 85 kDa PMMA (0.78 mg/m²), while the 32 kDa sample had a smaller amount (0.48mg/m²). A comparison of adsorbed PMMA, poly(vinyl acetate) (PVAc), and poly(methyl acrylate) (PMA) on silica was made using the same technique. The …

Part I: Syntheses, Characterizations, And Investigations Of Molecular Micelles And Imidazolium-Based Ionic Liquids For Protein Separations In Electrophoresis Part Ii: Investigating The Mentoring Canon Through Exploration Of Thirty Years Of Mentoring By An Exemplar, Monica R. Sylvain

LSU Doctoral Dissertations

The research reported in this dissertation is presented in two parts. The first part is the Syntheses, Characterizations, and Investigations of Molecular Micelles and Imidazolium-Based Ionic Liquids for Protein Separations in Electrophoresis, and the second part is a case study entitled Investigating the Mentoring Canon through Exploration of Thirty Years of Mentoring by an Exemplar. Protein separations in the gel electrophoretic format are ubiquitous analyses used on a daily basis throughout biochemistry, analytical chemistry, and biotechnology. The goal of the research reported in the first part of this dissertation is to synthesize and characterize molecular micelles and ether-functionalized imidazolium-based ionic …

Iron (Iii) Oxide And Copper (Ii) Oxide Mediated Formation Of Pcdd/Fs From Thermal Degradation Of 2-Mcp And 1,2-Dcbz, Shadrack Kirwa Nganai

LSU Doctoral Dissertations

Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) which occurs inexorably from most thermal and combustion processes constitutes a major toxic component of environmental pollutants. Generally, it is well established that transition metal-mediated reactions account for the majority of PCDD/F emissions from combustion sources. Specifically, both copper and iron ions, which occur abundantly in combustion generated particulate matter, are considered probably the most active in promoting PCDD/F formation typically in the low temperature post-combustion zone and flue gas pollution control devices. It has also been demonstrated that chlorinated phenols are key intermediates in essentially all pathways of PCDD/F formation. Chlorinated benzenes …

S-Nitrosothiols: Formation, Decomposition, Reactivity And Possible Physiological Effects, Moshood Kayode Morakinyo

Dissertations and Theses

Three biologically-active aminothiols cysteamine (CA), DL-cysteine (CYSH) and DL-homocysteine, were studied in this thesis. These aminothiols react with nitrous acid (HNO₂), prepared in situ, to produce S-nitrosothiols (RSNOs): S-nitrosocyteamine (CANO), S-nitrosocysteine (CYSNO) and S-nitrosohomocysteine (HCYSNO). They also react with S-nitrosoglutathione (GSNO) and S-nitroso-N-acetylpenicillamine (SNAP) through a transnitrosation reaction to produce their corresponding RSNOs. A detailed kinetics and mechanistic study on the formation of these RSNOs and their subsequent decomposition to release nitric oxide (NO) were studied.

For all three aminothiols the stoichiometry of their reaction with nitrous acid is strictly 1:1 with the formation of one mole …

Synthesis And Characterization Of A [Ru(Bpy)2(Ncs)2] Derivative For Use As A Dye-Sensitizer In Nanocrystalline Solar Cells, Joel Thomas Kirner

Honors Program Theses

After extensive review of the field of dye-sensitized solar cells, the molecule [Ru(4,4’- dicarboxy-2,2’-bipyridine)(4,4’-di-(2-(2-pyridyl)ethenyl)-2,2’-bipyridine)(NCS)2] has been designed as an original contribution to the field. This dye sensitizer was chosen by derivatizing upon the structure of the standard sensitizer, cis-diisothiocyanatobis(4,4’-dicarboxylic acid-2,2’- bipyridine)ruthenium(II) (N3), by extending the conjugation of one bipyridine ligand. This structural derivatization should enhance light harvesting by red-shifting the dye’s absorbance and increasing the dye’s molar absorptivity, which should result in a dye-sensitized solar cell with higher efficiency. The Density Functional Theory (DFT) molecular orbital calculations of the new dye complex indicate that the HOMO is highly localized …

Affinity Capillary Electrophoretic Study Of K+/Na+ Selectivity Of Hexaarylbenzene-Based Polyaromatic Receptor, Sille Ehala, Rajendra Rathore, Emanuel Makrlik, Petr Toman, Václav Kašička

Chemistry Faculty Research and Publications

Affinity capillary electrophoretic (ACE) study has proved the selectivity of hexaarylbenzene-based polyaromatic receptor (R) for K+ ion over Na+ ion. The apparent binding constants of the R complexes with K+ and Na+ ions were determined from the dependence of effective electrophoretic mobility of R on the concentration of the above alkali metal ions in the background electrolyte using a non-linear regression analysis. The apparent binding constants (Kb) of the K-R+ and Na–R+ complexes in methanolic medium were evaluated as log Kb = 3.20 ± 0.22 for the K–R+ complex, and log Kb≅−0.7 for the Na–R+ complex.

Modeling Hydrophobic Effects At Different Lengthscales, Jihang Wang

Theses and Dissertations

Understanding hydrophobic effects at different length scales is relevant to many complex and poorly understood everyday phenomena in materials science and biology. In this thesis, a variety of theory/computational methods in statistical physics and statistical mechanics are used to address three separated, but interconnected problems: (1) How solvation free energy scales with a partical size that is charged? This problem has never been attempted to solve before despite its immense importance in colloidal and protein solutions (J. Wang, D. Bratko, K. Leung and A. Luzar, Hydrophobic hydration at different length-scales: manipulating the crossover by charges, to be submitted to J. …