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Synthesis And Evaluation Of Structural Analogs Of Escherichia Coli Lipid A For Application Towards Cd14-Targeting Glycotherapeutics, Aileen Fay Galos Bongat

Dissertations

Lipid A is a glucosamine-based phospholipid that anchors carbohydrate molecules to the outer membrane of most Gram-negative bacteria. During severe infection, this amphiphilic macromolecule invoke a strong and acute pro-inflammatory response that leads to sepsis and ultimately to septic shock, organ failure and death. Thus, following the convention that the best antidote is often a derivative of the parent agonistic molecule, researchers have actively pursued the idea of creating an analog of Lipid A that can block the cellular receptor for this molecule and thereby arrest the cascade of events that lead to sepsis. Consequently, we became interested in creating …

Calculations Of K-Shell Fluorescence Yields And Photoabsorption Cross Sections For Carbon Ions At The K-Edge, Muhammet Fatih Hasoglu

Dissertations

The advent of new space missions providing high-precision observations has engendered the need for reliable and precise K-shell atomic data in order to interpret these X-ray spectra. In response to this need, we focused on the calculation of K-shell fluorescence yields for 2 nd -row ions. A secondary project was undertaken in order to treat theoretically the K-shell X-ray absorption processes in carbon ions. These calculated fluorescence yields of 2nd -row ions and theX-ray photoabsorption cross sections of carbon are astrophysically important in determining (1) charge-changing probabilities, such as Auger vs. radiative decay, and (2) chemical abundances of the interstellar …

Evaluation Of Electron Donor Materials Used To Create Subsurface Permeable Reactive Barriers For Enhanced Reductive Dechlorination Of Chlorinated Ethenes, Elizabeth S. Semkiw

Dissertations

Chlorinated ethenes (CEs) are widespread ground water contaminants, apparently due to their extensive migration from numerous contamination source points. In this study, a long-term field investigation and aquifer microcosm experiments were combined to evaluate the effectiveness of electron donor materials used to create and maintain subsurface permeable reactive barriers (PRBs) for the enhanced in-situ biodegradation of CEs. The laboratory component includes the first side-by-side comparison of electron donor materials dairy whey, lactate syrup, and Hydrogen Release Compound® (HRC), in which dechlorination rates, fermentation product distributions, and H₂ production were monitored as measures of substrate efficiency. Field study allowed the …

Switch On And Switch Off Nanosensors For The Detection Of Nerve Gas Agents, Shankar Varaganti

Dissertations

The central hypothesis of this research is the development of novel nanosensors by a bottom-up approach for the detection of nerve gas agents. The nanosensor assembly consists of four main parts; nanoparticles (N), Monomer (M), Complex (C) and Receptor (R). Two novel Ru (II)-bipyridyl and zinc complexes with tryptophan receptors either in 4,4' or 5,5' position of the bipyridyl ring have been synthesized and characterized by using ¹H NMR, ¹³C NMR, mass spectrometry and absorption spectroscopy. Silica nanoparticles or quantum dots are used as a platform for the nanosensors. Highly conjugated stilbene type compounds are used as monomers. …

High School Mathematics Teachers' Evolving Understanding Of Comparing Distributions, Sandra R. Madden

Dissertations

Statistics has achieved a position of status in the secondary curriculum (College Board, 2006b; Franklin et al., 2007; NCTM, 2000) and understanding of statistics is essential for high school mathematics teachers if they are to engage students in thoughtful pursuit of statistical ideas. High school teachers typically are ill-prepared in the area of statistics (Ben-Zvi & Garfield, 2004a; CBMS, 2001; Shaughnessy, 1992, 2007). Using methods of design research, this study investigated 56 high school mathematics teachers' understanding of the statistical concept ofcomparing distributions and demonstrated that a modest four-day, statistics-oriented, technology-rich, professional development program may significantly improve teachers' understanding. …

Preparation Of Carboxylic Acid Functionalized Glycopolymers Through Raft And Post-Polymerization Modification For Biomedical Application, Husnu Alp Alidedeoglu

Dissertations

The primary theme of this dissertation involves the synthesis of well-defined primary amine functionalized polymers, subsequent modification of the polymers to produce novel carboxylic acid functionalized glycopolymers and surface polymerization of these systems utilizing controlled polymerization techniques. Additionally, the synthesis of new water-based allylic copolymer latexes is described. Carbohydrates are natural polymers which possess unlimited structural variations. They carry a huge density of information, and play major roles in recognition events and complex biological operations. For example, hyaluronic acid (HA), an anionic glycosaminoglycan, provides lubricating and cushioning properties in the extracellular matrix and has been found to be involved in …

Investigation Of The Interactions Of Cationic Polyelectrolytes With Anionic Surfactants: Effects Of Polymer, Surfactant And Solution Properties, Lisa Renee Huisinga

Dissertations

The intent of this research is to explore and understand the effects that a range of polymer, surfactant and solution parameters have on the interaction of oppositely-charged polymers and surfactants. Cationic polysaccharides were chosen for this research because they are known to interact with anionic surfactants, and they offer a wide range of adjustable polymer properties, including molecular weight, charge substitution, and backbone structure. Cationic poly(vinylpyridinium hydrochloride) polymers were chosen for these studies because they provide the opportunity to explore the effects of charge position on the interaction of cationic polymers with anionic surfactants and how this influences the mechanism …

Examination Of An Aloe Vera Galacturonate Polysaccharide Capable Of In Situ Gelation For The Controlled Release Of Protein Therapeutics, Shawn David Mcconaughy

Dissertations

A therapeutic delivery platform has been investigated with the ultimate goal of designing a sustained protein release matrix utilizing an in-situ gelling, acidic polysaccharide derived from the Aloe vera plant. The Aloe vera polysaccharide (AvP) has been examined in order to determine how chemical composition, structure, molecular weight and solution behavior affect gelation and protein/peptide delivery. Correlations are drawn between structural characteristics and solution behavior in order to determine the impact of polymer conformation and solvation on gel formation under conditions designed to simulate nasal applications. Steady state and dynamic rheology, classic and dynamic light scattering, zeta potential, pulse field …

Dispersion States And Surface Characteristics Of Physically Blended Polyhedral Oligomeric Silsesquioxane/Polymer Hybrid Nanocomposites, Rahul Misra

Dissertations

Control of dispersion and segregation states of nanostructured additives is one of the biggest challenges in realizing the optimum potential of high-performance hybrid polymer nanocomposites. Polyhedral oligomeric silsesquioxane (POSS) nanostructured chemicals, with their hybrid organic-inorganic nature and flexible functionalization with a variety of organic substituents, yield possibilities to control dispersion and tune compatibility in a wide range of polymer systems. The overall goal of this research is to investigate the fundamental parameters that influence the dispersion and segregation states of POSS nanostructured chemicals and to understand chain dynamics and conformations in physically blended POSS hybrid polymer nanocomposites (HPNC's). Multiple structural …

Synthesis, Propagation Kinetics, And Characterization Of D,L-Lactide-Based Polyols And Polyurethanes Therefrom, Scott Joseph Moravek

Dissertations

In order to expand the usefulness of degradable polyesters, degradable polyurethanes were synthesized using a mixed polyol system including poly(D,L-lactideco- glycolide) (PLGA), a well-known degradable polyester. Two isocyanate systems, methyl 2,6-diisocyantocaproate (LDI) and dicyclohexylmethane-4,4'- diisocyanate(Hi2MDI), were studied in order to achieve optimal physical and thermal properties of the thermoplastic polyurethane (TPU) while maintaining degradablity. The LDI based systems had excellent physical properties as well as thermal properties that may make them suitable for biomedical devices. The H12MDI based TPUs also had excellent physical properties as well as a higher melting temperature. The aforementioned TPUs were synthesized in small batches. Another …

Photopolymerization And Characterization Of Thiol-Enes And Thiourethanes, Qin Li

Dissertations

Compared to conventional acrylic monomer systems, thiol-ene photopolymerization, an efficient click process leading to the formation of dense and uniform molecular networks, has several distinct advantages including relative insensitivity to oxygen inhibition, high monomer conversion and low shrinkage. Although there has been a revival of interest in thiol-enes in the past 6 years, the structure-property relationship of these networks has not been explored in detail. For future applications, thiol-enes with higher shelf-life stability and glass transition temperatures need to be used. Sulfur containing urethanes, thiourethanes and dithiourethanes are a class of widely used materials due to their distinct properties such …

The Relationship Betweeen Dynamic And Chemical Factors On The Morphology In Aot-Water-Polymer Systems, Jolanta Elzbieta Marszalek

Dissertations

Photopolymerization of reverse microemulsion demonstrates strong influences from dynamical and chemical factors on morphology of formed polymer systems. Upon polymerization the clear microemulsion with nanoscale structures transforms into opaque films with larger aggregates that scatter light. Studied here were microemulsions based on acrylate and on thiol-ene chemistries. The difference in the two reaction mechanisms results in the phase separation occurring at different stages of the material formation. Consequently, the morphology of the material demonstrates distinct dissimilarities in the two systems. In addition, the chemical structure of the monomers promotes these morphological differences. When the microemulsion is composed of acrylate and …

Reduction Of Toxicity In The Premature Neonate Addociated With Aluminum As A Contaminant Of Total Parenteral Nutrition Solution, Sujittra Srisung

Dissertations

Aluminum (Al) is the third most common element in the Earth?s crust. It is widely consumed in water, foods, and drugs. However, in humans, the uptake of aluminum into the body and its deposition in tissues has been linked to conditions of medical concern, including many neurological disorders such as dialysis dementia, Alzheimer?s disease, Parkinson?s dementia and Down?s syndrome. Premature neonates who receive intravenous feeding (TPN) are at a high risk for Al toxicity because the TPN solutions are contaminated with Al3+, which is not excreted effectively due to poor kidney development in these patients. The FDA has recommended regulations …

On The Rolling Motion Of Viscous Fluid On A Rigid Surface, Xinli Wang

Dissertations

This thesis considers two closely related problems. First, the influence of insoluble surfactant at a moving contact line is considered. This work is mostly motivated by the air entrainment during the coating process where there is a three-phase contact point (e.g., air, liquid and solid). For moving contact line problems, when the fluid is assumed to be an incompressible Newtonian fluid and a no-slip boundary condition is enforced at the solid boundary, the non-integrable stress singularity arises at the contact line, which is physically unrealistic. The contact angle of 180° is considered as a special case in which the singularity …

A Mathematical And Computational Exploration Of The Effect Of The A-Current In Determining The Activity Phase Of Follower Neurons, Yu Zhang

Dissertations

Bursting oscillations are prevalent in neurons of central pattern generators (CPGs) that produce rhythmic motor activity, and the activity phase plays an important role in determining the normal or dysfunctional network output. The activity phase is the delay time-with respect to some reference time in each cycle and normalized by the oscillation cycle period-of the onset of action potentials by a neuron. This dissertation investigates how the A-current, in conjunction with other intrinsic properties, sets the activity phase of a neuron driven by inhibition.

This dissertation is divided into two major components. In the first component, methods of dynamical systems …

Flexible Electronics : Materials And Sensor Fabrication, Katherine J. Duncan

Dissertations

This dissertation demonstrates how to fabricate piezoelectric/pyroelectric thin films by using different printing techniques. These techniques could replace vacuum techniques for manufacturing piezoelectric/pyroelectric sensors. Ink-jet, screen and stencil printing techniques were developed to print these devices.

This work outlines attempts to develop a solution processable conductive ink for ink-jet printing. It then details the printing of commercial conductive ink on flexible substrates employing the three printing methods. Raman spectroscopy and Fourier transform infrared spectroscopy, are both used to investigate the structure of the P(VDF-TrFE) films. Optical microscopy is used to investigate the thickness and uniformity of the deposited films. The …

Understanding Similarity: Bridging Geometric And Numeric Contexts For Proportional Reasoning, Dana Christine Cox

Dissertations

The concept of similarity is uniquely situated at the crossroads of geometric and numerical proportional reasoning. Although studies have documented the existence and nature of student difficulties with this topic, there exists a gap between documented visual insights of younger children and the quantitative inadequacies of older ones. Using a revised version of the Similarity Perception Test followed by 21 clinical interviews, this study investigated the visual and analytical strategies that are used by middle-school students to differentiate and construct similar figures.

New strategies for construction and differentiation were identified, and three overarching conclusions were drawn from the work. First, …

Remote Sensing Studies For The Assessment Of Geohazards: Toxic Algal Blooms In The Lower Great Lakes, And The Land Subsidence In The Nile Delta, Richard H. Becker

Dissertations

Remote sensing techniques provide valuable tools for assessing a wide variety of environmental phenomena. They have been used for monitoring and assessment of various types of geologic and environmental hazards occurring on land, in the air, or in oceans. I present results from two studies, the first of which examines the spatial and temporal distribution of algal blooms in the Great Lakes; the second measures subsidence in the Nile Delta.

In the first study, methodologies to investigate the extent and distribution (temporally and spatially) of algal blooms in Lake Erie and Lake Ontario are studied. Millions of people in the …

Identification Of Two Distinct Glutaminyl Cyclase Isoforms In Drosophila Melanogaster, Amanda Thigpen Parker

Dissertations

Sequence analyses revealed two putative glutaminyl cyclase genes in Drosophila melanogaster with greater than 60% amino acid sequence identity to previously identified glutaminyl cyclase in humans. Expression, purification, and characterization of both putative proteins revealed two enzymatically active glutaminyl cyclase enzymes. Comparison of the Drosophila melanogaster glutaminyl cyclase enzymes to the published human glutaminyl cyclase revealed the enzymes were very similar. The Km values obtained were identical to those of human glutaminyl cyclase for three different substrates tested. However, the Drosophila glutaminyl cyclases demonstrated lower turnover numbers. Both Drosophila glutaminyl cyclase isoforms were inhibited by imidazole, imidazole derivatives, and metal …

Towards Development Of A Fully Synthetic Conjugate Vaccine: Investigation Of Structural Analogs Of Streptococcus Pneumoniae Serogroup 6, Archana R. Parameswar

Dissertations

Involvement of complex glycostructures in a variety of damaging and healing processes has already been acknowledged by development of carbohydrate-based vaccines and therapeutics. The bacteria Streptococcus pneumoniae (SPn) have become one of the most frequent causes of pneumonia, bacteremia, and meningitis in the elderly, immunocompromised, and, especially, in young children. SPn has one of the largest public health and economic impacts amongst all bacterial infectious diseases. Over 2 million children die annually worldwide due to pneumonia, accounting for almost 20% of deaths under age five with more than half of these deaths attributed to SPn. Amongst over ninety elucidated SPn …

Synthesis Of Α-Hydroxy And Fluoro Phosphonates And Cyclic Ether-Containing Natural Products, Nongnuch Sutivisedsak

Dissertations

A number of important classes of natural product (eg. amphidinolide C, (-)-centrolobine, etc) contain common structural features of tetrahydrofurans and tetrahydropyrans. This study involved the development of stereoselective mothods for the synthesis of tetrahydrofurans and tetrahydropyrans including the application of allylic hydroxy phosphonates and their derivatives as chiral, non racemic building blocks for the synthesis of biological active molecules. The enantiomeric excess of non racemic α-hydroxy phosphonates and carbonate derivatives prepared via the asymmetric Pudovik reaction can be improved by kinetic resolution. Both chemical and enzyme catalysts were utilized in the kinetic resolution of phosphonates. Enantioselective acylation of a variety …

The Effect Of Active Site Mutations On The Homodimeric Behavior Of The Pvuii Restriction Endonuclease, Grigorios A. Papadakos

Dissertations

The PvuII restriction endonuclease, a homodimer of two 18 kDa subunits, belongs to the type II family of restriction enzymes. Located in the active site of PvuII, Tyrosine 94 has previously been shown to be involved in the metal ion binding by the enzyme. The profile of the Ca2+ dependence of the DNA binding to the Y94F variant is shown to be clearly biphasic. The application of a sequential binding model yielded a coupling energy (ΔGcoop) at -0.54 for the upper phase and -1.15 kcal/mole for the lower phase. The similar metal binding pattern between the Y94F and the WT …

Mechanistic Studies Of Specific Dna Cleavage By Pvuii Restriction Endonuclease, Xie Fuqian

Dissertations

PvuII restriction endonuclease is a homodimeric protein which recognizes and cleaves the palindromic sequence (CAG?CTG) in the presence of Mg(II) ions. Starting with PvuII as a model system, pKa calculations with crystallographically defined metal ligated water are applied to PD?D/ExK motif metallonucleases in order to investigate the activation of nucleophile in metal dependent DNA hydrolysis. These results establish the electrostatic contributions of the metal ions and the conserved Lys in lowering water pKa. The calculated pKa values of metal ligands have been used to simulate the pH dependence of Mg(II) binding to PvuII. The bell shaped pH-rate profile is dissected …

Synthesis, Characterization, And Catalytic Application Of Gold Nanoparticles, Junhyung Kim

Dissertations

Properties of nanometer-sized gold(Au) particles, especially those that are protected by a monolayer coating of thiolate ligands, called 'Monolayer Protected Clusters' (MPCs), are of rigorous multidisciplinary interest for their potential applications in catalysis and electronics due to their variation with size.

In larger core diameter sizes (>1.5nm) AuMPCs show metallic behavior as observed from electrochemical measurements. On the other hand, sub-nanometer ([approximate]1.1nm) AuMPCs exhibit molecule-like electronic behavior which is typical of Au38 nanoparticles. The various alkane chain thiols(C4 S-C12 S) capped Au38 MPCs have been examined with independent analytical tools, producing a remarkably consistent picture of these materials.

The …

Exploration Of The Chemical And Biological Processes Through Molecular Dynamics Simulation And Blocklocalized Wavefunction Method, Yuchun Lin

Dissertations

Computer simulation plays a crucial role in interpreting, unifying and guiding experimental observations. In this dissertation, molecular dynamics (MD) simulations and the block-localized wavefunction (BLW) method have been used to explore the chemical and biological processes.

Detailed MD simulations were performed to study the transportation of NH₄⁺, NH₃ and H₂O through the Escherichia coli ammonium transporter (AmtB) membrane protein. A periplasmic recruitment vestibule was identified and the entrance of an NH₄⁺ into this vestibule requires only 3.1 kcal/mol. In the end of this vestibule, the phenyl ring of Phe107 dynamically opens and …

Remote Sensing Solutions For Estimating Runoff And Recharge In Arid Environments, Adam M. Milewski

Dissertations

Efforts to understand and to quantify the interplay between precipitation, runoff, and recharge are often hampered by the paucity of appropriate monitoring systems. We developed methodologies for rainfall-runoff and groundwater recharge computations that heavily rely on observations extracted from a wide-range of global remote sensing data sets (TRMM, SSM/I, AVHRR, and AMSR-E,) using the arid Sinai Peninsula (SP; area: 61,000 km²) and the Eastern Desert (ED; area: 220,000 km²) of Egypt as our test sites. A two-fold exercise was conducted. Temporal remote sensing data (TRMM, AVHRR and AMSR-E) were extracted from global data sets over the …

The Role Of Short Term Synamptic Plasticity In Temporal Coding Of Neuronal Networks, Lakshmi Chandrasekaran

Dissertations

Short term synaptic plasticity is a phenomenon which is commonly found in the central nervous system. It could contribute to functions of signal processing namely, temporal integration and coincidence detection by modulating the input synaptic strength. This dissertation has two parts. First we study the effects of short term synaptic plasticity in enhancing coincidence detecting ability of neurons in the avian auditory brainstem. Coincidence detection means a target neuron has a higher firing rate when it receives simultaneous inputs from different neurons as opposed to inputs with large phase delays. This property is used by birds in sound localization. When …

Projecting Land Use Changes Using Parcel-Level Data : Model Development And Application To Hunterdon County, New Jersey, Florencio C. Ballesteros Jr.

Dissertations

This dissertation is to develop a parcel-based spatial land use change prediction model by coupling various machine learning and interpretation algorithms such as cellular automata (CA) and decision tree (DT). CA is a collection of cells that evolves through a number of discrete time steps according to a set of transition rules based on the state of each cell and the characteristics of its neighboring cells. DT is a data mining and machine learning tool that extracts the patterns of decision process from observed cell behaviors and their affecting factors. In this dissertation, CA is used to predict the future …

Roles Of Gap Junctions In Neuronal Networks, Joon Ha

Dissertations

This dissertation studies the roles of gap junctions in the dynamics of neuronal networks in three distinct problems. First, we study the circumstances under which a network of excitable cells coupled by gap junctions exhibits sustained activity. We investigate how network connectivity and refractory length affect the sustainment of activity in an abstract network. Second, we build a mathematical model for gap junctionally coupled cables to understand the voltage response along the cables as a function of cable diameter. For the coupled cables, as cable diameter increases, the electrotonic distance decreases, which cause the voltage to attenuate less, but the …

Synthesis And Characterization Of Plasma Enhanced Chemically Vapor Deposited Tantalum Films, Weizhong Chen

Dissertations

A low temperature inorganic plasma-enhanced chemical vapor deposition (PECVD) process has been developed for the growth of Ta using tantalum pentachloride (TaC15) as the preferred precursor and hydrogen as the reactant gas. Ta coatings were deposited at substrate temperature of 370-400 °C, reactor working pressures of 0.7-2 Ton, hydrogen carrier flow rate of 10-20 sccm, hydrogen reactant flow rates of 500 sccm, and plasma power ranging from 60 to 100W. Ta coatings were characterized with respect to their chemical, structural, and morphological properties by Auger electron spectroscopy (AES), x-ray diffraction (XRD), atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS), scanning …