Physical Sciences and Mathematics Commons^™

Synthesis And Characterization Of Monolayer Protected Gold Nanoparticles And A Gold-Titanium Dioxide Nanocomposite Intended For Photocatalytic Degradation Of Environmental Pollutants, Piyadarsha Amaratunga

Dissertations

Semiconductor and metal clusters in the nanometer size regime display interesting optical, electronic and chemical properties that are size dependant. Highly monodisperse gold nanoparticles of different sizes have been synthesized and isolated by newly developed methodologies, using tiopronin as the capping ligand. Titanium dioxide nanoparticles (Ti0₂) have been used as the photocatalytic center and gold nanoparticles have been attached on Ti0₂ to make a nanocomposite. According to the findings, gold nanoparticles play a vital role in enhancing the photocatalytic activity of Ti0₂, by facilitating the charge separation. Further, the photocatalytic activity also can be tuned …

Isotropic And Anisotropic Metallic And Bimetallic Nanoparticles And Their Potential Applications In Biology, Minghong Liu

Dissertations

The development of synthetic procedures that produce nanoscale materials with controlled morphology is a significant area of investigation in nanotechnology. We have developed new synthetic procedures for fabrication of isotropic and/or anisotropic nanomaterials composed of palladium, ruthenium, nickel and alloys of palladium-ruthenium. The nanomaterials were fully characterized and were found to display unique size dependent properties. The electrochemical properties of isotropic palladium, ruthenium and palladium-ruthenium nanoparticles were investigated and the results showed that the particles were capable of charge storage and charge transfer on demand. Anisotropic palladium, ruthenium and palladium ruthenium nanoparticles were also fabricated and fully characterized. The nanoparticles …

Gold Nanoparticle - Modified Zinc Oxide Nanoparticles As Novel Photocatalytic Materials, Nayane Udawatte

Dissertations

The current study entails the construction of a novel nano-composite catalyst based on ZnO and Au nanoparticles and demonstrates its distinctive photocatalytic characteristics. Monodisperse gold nanoparticles (GNPs) passivated with monolayers of tiopronin or glutathione were synthesized via facile methods, and they were assembled on ZnO nanoparticles to form the nanocatalyst.

Steady state and time resolved photoluminescent studies on the nanocomposite revealed interesting charge transfer characteristics within the nanocomposite. Enhanced photooxidation of rhodamine 6G was observed for the nano-composite over bare ZnO, and modulation of photoactivity with the extent of GNP loading was illustrated. Photoreduction of thionine over the nanocomposite was …

Local Radial Basis Function Methods For Solving Partial Differential Equations, Guangming Yao

Dissertations

Meshless methods are relatively new numerical methods which have gained popularity in computational and engineering sciences during the last two decades. This dissertation develops two new localized meshless methods for solving a variety partial differential equations.

Recently, some localized meshless methods have been introduced in order to handle large-scale problems, or to avoid ill-conditioned problems involving global radial basis function approximations. This dissertation explains two new localized meshelss methods, each derived from the global Method of Approximate Particular Solutions (MAPS). One method, the Localized Method of Approximate Particular Solutions (LMAPS), is used for elliptic and parabolic partial differential equations (PDEs) …

Design, Synthesis, And Polymerization Of Novel Heterocyclic Monomers As Precursors For Functional Polyester, Poly(Ester Amide)S And Polyamides, Eylem Tarkin-Tas

Dissertations

The research presented in this dissertation involves the synthesis and polymerization of heterocyclic monomers which pave the way to biodegradable polyester nanocomposites, functional polyesters or poly(ester amide)s, functional polyamides and supramolecular polymers. The key monomers are ε-caprolactone, γ-acetamido-ε- caprolactone, γ-ethylene ketal-ε-caprolactam and α-amino-ε-caprolactam.

Poly(ε-caprolactone) organo-modified montmorillonite nanocomposites were prepared by in-situ polymerization using dibutyltin dimethoxide as initiator/catalyst. The montmorillonite was first modified with 1-decyl-2-methyl-3-(11-hydroxyundecyl)- imidazolium cation. The hydroxyl functionality was used for not only initiating polymer chains from the surface of the clay platelets but also for grafting polymer chains to the surface by acting as a reversible chain transfer …

Studies Of Meson Mass Spectra In The Context Of Quark-Antiquark Bound States, Mallika Dhar

Dissertations

This dissertation deals with the computation of meson mass spectra in the context of quarkantiquark (q ¯ q) bound-state. Traditionally the q ¯ q bound-state problem is treated by solving the non-relativistic Schrödinger equation in position representation with a linear confining potential and a Coulomb-like attractive potential. For high energy, relativistic kinematics is necessary. It is well known that relativistic kinematics cannot be treated properly in position representation, but it can easily be handled in momentum representation. On the other hand, the linear potential and Coulomb-like potential have singularities in momentum-space and complicated subtraction procedure is necessary to treat the …

Inhibition Studies Of Serine Hydrolases By Cyclic Phosphates And Phosphonates, Supratik Dutta

Dissertations

The serine hydrolase superfamily is one of the largest known enzyme families comprising approximately 1% of the predicted protein product in human genome. This family of enzymes contains a catalytic triad that is mainly consists of serine, aspartic acid/glutamic acid and histidine residues in their active sites. It has been proposed that the potential drug targets for Alzheimer’s disease and diabetes type 2 are enzymes that belong to this enzyme family. Acetylcholinesterase is an enzyme that catalyses the breakdown of acetylcholine, a neurotransmitter that helps transport information from one nerve cell to another. Breakdown of acetylcholine in Alzheimer’s disease patients …

The Nature Of The O-2/O-5 Cooperative Effect And Its Role In Chemical Glycosylation, Laurel Kathryn Mydock

Dissertations

Since carbohydrates were first discovered, understanding the structure, reactivity, and function of these bioorganic compounds has remained of great priority. However, as the appreciation for the biological roles of carbohydrates intensifies, a growing demand for efficient and scalable methods towards the synthesis of these challenging molecules has become even more imperative. While modern synthetic techniques have allowed us to readily achieve most glycosidic linkages, it is the inability to effectively predict and control the stereoselectivity of the glycosylation reaction that has remained the synthetic hurdle. Herein, much effort has been placed in the investigation of “mixed-patterned” glycosyl donors as they …

Glaciotectonic Deformation Along The Valparaiso Upland In Southwest Michigan, Usa, Brian C. Bird

Dissertations

Glaciotectonic deformation has been observed and analyzed across parts of the Valparaiso, Kendall, and Inner Kalamazoo Moraines in southwest Michigan, USA. Deformation structures such as folds and faults have been analyzed using techniques typically used by structural geologist along with the fabric of elongated clasts in the surficial diamicton. The structures are consistent with simple shear, horizontal compressional stresses, and pure shear. A series of drumlin fields exist along the western boundary of the study area. Direct investigation of the deformed sediments was conducted at a gravel pit in one of these drumlins. Lacustrine derived sediments interbedded with coarse sand …

Variance Reduction Techniques For Estimating Quantiles And Value-At-Risk, Fang Chu

Dissertations

Quantiles, as a performance measure, arise in many practical contexts. In finance, quantiles are called values-at-risk (VARs), and they are widely used in the financial industry to measure portfolio risk. When the cumulative distribution function is unknown, the quantile can not be computed exactly and must be estimated. In addition to computing a point estimate for the quantile, it is important to also provide a confidence interval for the quantile as a way of indicating the error in the estimate. A problem with crude Monte Carlo is that the resulting confidence interval may be large, which is often the case …

New Data Structures, Models, And Algorithms For Real-Time Resource Management, Xinfa Hu

Dissertations

Real-time resource management is the core and critical task in real-time systems. This dissertation explores new data structures, models, and algorithms for real-time resource management.

At first, novel data structures, i.e., a class of Testing Interval Trees (TITs), are proposed to help build efficient scheduling modules in real-time systems. With a general data structure, i.e., the TIT* tree, the average costs of the schedulability tests in a wide variety of real-time systems can be reduced. With the Testing Interval Tree for Vacancy analysis (TIT-V), the complexities of the schedulability tests in a class of parallel/distributed real-time systems can be effectively …

Modeling With Bivariate Geometric Distributions, Jing Li

Dissertations

This dissertation studied systems with several components which were subject to different types of failures. Systems with two components having frequency counts in the domain of positive integers, and the survival time of each component following geometric or mixture geometric distribution can be classified into this category. Examples of such systems include twin engines of an airplane and the paired organs in a human body. It was found that such a system, using conditional arguments, can be characterized as multivariate geometric distributions. It was proved that these characterizations of the geometric models can be achieved using conditional probabilities, conditional failure …

Effect Of Anions On The Iron Release Pathways Of Human Serum Transferrin, Rashmi Subhash Chander Sharma

Dissertations

Transferrin, the serum iron transport protein in humans, is used to transport 30-40 mg of iron per day through blood. The accessibility of transferrin makes it an attractive target for iron cheating therapeutic agents used in the treatment of iron overload. There is an ongoing search for ligands which can accelerate the rate of iron release, as the currently approved drug DFO has a very slow rate for iron removal. Previous studies have shown that anions can accelerate the rate of iron release. Studies on the effect of anions on the rates of iron release from C-terminal monoferric transferrin at …

Weak Shear Study Of Galaxy Clusters By Simulated Gravitational Lensing, David Raymond Coss

Dissertations

Gravitational lensing has been simulated for numerical galaxy clusters in order to characterize the effects of substructure and shape variations of dark matter halos on the weak lensing properties of clusters. In order to analyze realistic galaxy clusters, 6 high-resolution Adaptive Refinement Tree N-body simulations of clusters with hydrodynamics are used, in addition to a simulation of one group undergoing a merger. For each cluster, the three-dimensional particle distribution is projected perpendicular to three orthogonal lines of sight, providing 21 projected mass density maps. The clusters have representative concentration and mass values for clusters in the concordance cosmology. Two gravitational …

Investigation Of Novel Quasiliving Polyisobutylene Chain-End Functionalization (Quenching) Methods, David Lee Morgan

Dissertations

This volume recounts efforts toward the development and understanding of chain functionalization techniques involving the direct addition of nucleophiles to quasiliving polyisobutylene (PIB). Nucleophiles included in the study were sterically hindered organic bases, (di)sulfides, N-substituted pyrroles, and alkoxybenzenes. A kinetic investigation of the end-quenching of TiCl4-catalyzed quasiliving PIB with sterically hindered amines was used to determine the mode of interaction with TiCl4 and the active species responsible for -proton abstraction. 2,5-disubstituted-N-hydropyrroles formed pyrrole-TiCl3 adducts that were active in formation of exo-olefin chain ends; whereas, with other sterically hindered amines, only an equilibrium fraction of the amine that did not complex …

A Study Of The Effective Interfacial Tension Between Miscible Fluids By Spinning Drop Tensiometer And Microfluidics, Gloria Dollie Viner

Dissertations

A miscible system is a system in which two fluids can completely dissolve in one another. A sharp concentration gradient can be observed in miscible systems. We studied the concentration gradient or miscible interface between IBA (isobutyric acid) and water, a miscible system near a consulate point (close to the system’s upper critical solution temperature [UCST]). The original hypothesis was that the sharp concentration gradient of IBA/water was due to barodiffusion, a diffusion effect driven by pressure. We tested this hypothesis by studying IBA/water at five different rotation rates and three different temperatures. At 20 oC, increasing rotation acceleration from …

Synthesis Of Functional Copolymers Via Aqueous Raft Polymerization For Bioconjugation And Targeted Delivery Of Small Interfering Rna, Adam Wesley York

Dissertations

The versatility of reversible addition-fragmentation chain transfer (RAFT) polymerization has moved this controlled radical technique to the forefront of copolymer construction for bioapplications including polymeric drug/gene delivery vehicles. Strengths of the RAFT process include the capacity to control the polymerization of a wide variety of vinyl monomers under mild conditions, its tolerance to numerous chemical groups that allow the preparation of functional copolymers for facile modification, and the range of copolymer architectures with predetermined end group functionalities which may be synthesized. Given these strengths, RAFT polymerization was utilized in this research to synthesize functional/reactive copolymers for bioconjugation and targeted delivery …

Polyisobutylene Chain End Transformations: Block Copolymer Synthesis And Click Chemistry Functionalizations, Andrew Jackson David Magenau

Dissertations

The primary objectives of this research were twofold: (1) development of synthetic procedures for combining quasiliving carbocationic polymerization (QLCCP) of isobutylene (IB) and reversible addition fragmentation chain transfer (RAFT) polymerization for block copolymer synthesis; (2) utilization of efficient, robust, and modular chemistries for facile functionalization of polyisobutylene (PIB). Two site transformation strategies were employed to create block copolymers effectively linking PIB with either poly(methylmethacrylate) (PMMA), polystyrene (PS), and poly(Nisopropylacrylamide) (PNIPAM) block segments. Functionalization of PIB was accomplished by utilizing two click chemistries, the azide-alkyne 1,3-dipolar cyclo addition and the thiol-ene hydrothiolation reaction, and by efficient transformation of the thiol functional …

The Lipid Acyl-Chain Dynamics In Giant Liposomes And Characterization Of Domain 4 Of The Wilson Disease Protein, Wilson Okumu

Dissertations

Steady-state and nanosecond time-resolved fluorescence of the nitro-2, 1, 3- benzoxadiazol-4-yl (NBD) probe and line tension force were determined in phospholipids acyl-chain dynamics in giant liposomes made from a homologous series of phosphatidylcholines (PC). The fluorescence spectroscopy of a NBD probe attached to the headgroup (NBD PE) or the tail (NBD PC) of the phospholipid were used to determine the rate of dithionite quenching in a homologous series of phospholipids. Similar experiments were performed in the gel and the fluid phases of the l,2-dimyristoyl-s«-glycero-3-phosphocholine (DMPC ). Nanosecond time scale lifetimes and anisotropy measurements were obtained by a 470 nm LED …

On Robustification Of Some Procedures Used In Analysis Of Covariance, Kuanwong Watcharotone

Dissertations

This study discusses robust procedures for the analysis of covariance (ANCOVA) models. These methods are based on rank-based (R) fitting procedures, which are quite analogous to the traditional ANCOVA methods based on least squares fits. Our initial empirical results show that the validity of R procedures is similar to the least squares procedures. In terms of power, there is a small loss in efficiency to least squares methods when the random errors have a normal distribution but the rank-based procedures are much more powerful for the heavy-tailed error distributions in our study.

Rank-based analogs are also developed for pick-a-point, adjusted …

Designing Molecular And Nanoscale Materials For Environmental Chemistry Processes, Wen Guo

Dissertations

This dissertation focuses on fundamental studies to identify materials that detect and degrade common organic environmental pollutants. Chapter 1 represents the overview of two widespread ground water contaminants: organohalides and organophosphorous compounds. Due to continuous usage of these compounds as well as their toxicity, reliable and sensitive methods for their detection and degradation are urgently needed. In Chapter 2 a description of molecular sensors designed with high sensitivity and selectivity to detect and distinguish between three organophosphorus (OP) pesticides are described. These sensors provide dual optical and electrochemical signals for detection, which minimizes false-positives. The signal transduction occurs in real …

Characterization Of The N-Terminal Domains And Disease-Causing Mutations Of The Human Wilson Protein, Joshua Mutambuki Muia

Dissertations

The Wilson protein (ATP7B) is a copper transporting ATPase that is involved in copper trafficking and homeostasis. Unlike the other known P-type ATPases, it possesses six homologous metal binding domains at the N-terminal end. Several mutations in the gene coding for this protein lead to Wilson disease, a hepatic disorder characterized by impaired excretion of copper in the bile, and accumulation of copper in body organs such as the liver, brain, kidney, and eye cornea. Characterization of various regions of expressed and purified ATP7B has been hampered by its low stability, aggregation and degradation.

In this research, novel methods were …

Self-Assembly And Gold Nanoparticle Cross-Linking Of Stimuliresponsive Block Copolymers Synthesized Bt Reversible Addition-Fragmentation Chain Transfer Polymerization, Adam Eugene Smith

Dissertations

The ability of amphiphilic block copolymers to self-assemble into various morphologies in aqueous solution in response to specific stimuli has attracted widespread interest for potential applications as targeted drug delivery and diagnostic vehicles. Stimuli-responsive block copolymers afford a facile method for tuning the hydrophilic mass fraction to provide access to various solution morphologies. Reversible additionfragmentation chain transfer (RAFT) polymerization provides the ability to prepare stimuli-responsive block copolymers while maintaining precise control over the macromolecular characteristics (molecular weight, copolymer composition, functionality, etc.) that dictate nanostructure morphology.

This work may be divided into four sections. In the first section the synthesis and …

Assessing The Impact Of A Computer-Based College Algebra Course, Ningjun Ye

Dissertations

USM piloted the Math Zone in Spring 2007, a computer-based program in teaching MAT 101and MAT 099 in order to improve student performance. This research determined the effect of the re-design of MAT 101 on student achievements in comparison to a traditional approach to the same course. Meanwhile, the study investigated possible effects of the Math Zone program on students’ attitude toward studying mathematics.

This study shows that there was no statistically significant difference on MAT101 final exam scores between the Math Zone students and the Classroom students in Fall 2007, Spring 2008 and Fall 2008. At the same time, …

Towards Multiplexed Electrogenerated Chemiluminescent Detection, Shijun Wang

Dissertations

The main objective of this dissertation is to understand and study the principle of electrogenerated chemiluminescence (ECL) and its applications to detect biomolecules simultaneously. Four aspects of ECL were studied. In order to carry out multiplexed ECL detection, both classical and several novel ECL systems have been investigated.

In the first aspect, significant effect of chloride ions on the ECL behavior of the tris(2,2′-bipyridyl) ruthenium(II) (Ru(bpy)3 2+)/tri-n-propylamine (TPrA) system at Au electrode was investigated. At low concentrations (e.g., [Cl-] < 5 mM), the ECL was enhanced; at relatively high concentrations, however, the ECL intensity decreased with the increase of the [Cl-]. At [Cl-] = 90 mM, ~ 50% and 100% ECL inhibition was observed for the first and the second ECL wave, respectively. The electrogenerated chloroaurate anions (AuCl2 - and AuCl4 -) which were verified using an electrochemical quartz-crystal microbalance (EQCM) method were found to be responsible for the ECL inhibition. This study suggests that care must be taken when Au working electrode is used for ECL studies in chloride-containing buffer solutions (widely used in DNA probes) and/or with the commonly used chloride-containing reference electrodes since in these cases the ECL behavior may significantly disagree with that obtained using other electrodes and reaction media.

In the second aspect, the electrochemical behavior of a trinuclear ruthenium(II)- containing complex, [((phen)2Ru(dpp))2RhCl2]5+ (where phen = 1,10-phenanthroline, dpp = 2,3-bis-2-pyridylpyrazine), …

Rational Design Of Self-Assembled Nanostructures Based On Polymers Synthesized Via Aqueous Reversible Addition-Fragmentation Chain Transfer Polymerization, Stacey Kirkland York

Dissertations

Recent advances in reversible addition-fragmentation chain transfer (RAFT) polymerization have allowed the rational, bottom-up design of biorelevant assemblies. Utilizing foresight, polymers can be tailored to self-assemble into nano-, micro-, and macroscopic structures. Given the size scale on which rationally-designed polymers can be tailored, they hold significant promise in the biomedical field. For example, nanoscale materials can be designed to carry small-molecule and gene therapeutics while macroscopic structures can be tailored for cell growth scaffolds. The design process begins by selecting monomers, chain transfer agents, and reaction conditions which will yield the desired polymer architecture and composition.

The work herein builds …

Developing A Biosensor For The Detection Of Bacteria: A Comparison Of Methods For Isolating Bacteria-Specific Antibodies, Scott Allen Walper

Dissertations

The antigen-antibody interaction is known to be a high affinity and highly specific interaction that can readily be used for the detection and identification of biological and chemical agents. These studies were conducted to develop an efficient and cost-effective method of obtaining bacteria-specific antibody molecules for integration into a fielddeployable biosensor. Antigen-binding molecules were obtained both as full-length IgG molecules from a hybridoma cell line and as recombinant single-chain Fv (scFv) antibodies isolated from naïve and immunize libraries. Monoclonal and recombinant antibody systems were compared on the effectiveness of producing new, target-specific molecules; the efficiency of production and purification of …

Guppie: A Coordination Framework For Parallel Processing Using Shared Memory Featuring A Master-Worker Relationship, Sean Christopher Mccarthy

Dissertations

Most programs can be parallelized to some extent. The processing power available in computers today makes parallel computing more desirable and attainable than ever before. Many machines today have multiple processors or multiple processing cores making parallel computing more available locally, as well as over a network. In order for parallel applications to be written, they require a computing language, such as C++, and a coordination language (or library), such as Linda. This research involves the creation and implementation of a coordination framework, Guppie, which is easy to use, similar to Linda, but provides more efficiency when dealing with large …

Synthesis, Characterization, And Deuterium Labeling Of Polyamides Studied By Nuclear Magnetic Resonance Spectroscopy, Christopher Allen Lange

Dissertations

The synthesis, characterization, and deuterium labeling of polyamides have been investigated. In Chapter II, selective deuterium labeling of various polyamides was demonstrated via a facile method which does not require organic solvent or catalyst. Quantitative solution-state NMR analysis showed deuterium incorporation at the carbon alpha to the carbonyl ranged from 20-75%. Incorporation in ε-caprolactam increased with repeated treatments. Isotopic shift effects for the deuterated materials were additive for all sites within experimental error.

In Chapter III, the effect of stoichiometric imbalances on the polymerization of poly(dodecamethylene terephthalamide)was investigated. Molecular weight was varied by polymerizing the monomer salt with excess diaminododecane, …

Structure-Property Relationships In The Formation Of Polyphenylsulfone Molecular Composites And Nanocomposites, Paul Joseph Jones

Dissertations

As the constituent phases in a polymer composite approach the molecular level, specific phenomena occur that can lead to significant changes in material properties when only minimal quantities of the additive are incorporated into the polymer matrix. Molecular composite and nanocomposites are state-of-the-art polymeric materials that contain nanostructured additives effectively dispersed within polymer matrices. The properties of molecular composites and nanocomposites are directly related to the interactions of the nanostructured additive and the polymer matrix. Subtle changes to the nanostructured additive can have profound effects on the ultimate properties of the composite material. Therefore, understanding the structure-property relationships in these …