Physical Sciences and Mathematics Commons^™

Electrochemical Synthesis Of Nanostructured Noble Metal Films For Biosensing, Jay Kishan Bhattarai

Dissertations

Nanostructures of noble metals (Au and Ag) are of interest because of their important intrinsic properties. Noble metals by themselves are conductive, physically robust, chemically inert, and strongly bind to thiols. However, when the nanostructures are formed, they in addition possess high surface area and unique optical properties tunable by adjusting the shape and size. All of these properties make nanostructures of noble metals suitable candidates to be used as a transducer for biosensing. Individual nanostructures might be easier to prepare but difficult to handle to be used as a transducer. Therefore, we prepared and analyzed nanostructured films/coating of noble …

Continuous Polymer Reactor Design, David Sujay Kingsley

Dissertations

Twin screw extruders can be used as continuous polymer reactors to process polymers, which are conventionally made through batch reactors. Batch processes have certain undesirable qualities such as improper mixing and the inability to precisely control the reaction, which leads to variation between batches and potential exotherms. The work presented in this dissertation investigates the use of continuous polymer reactor designs to efficiently process renewable sourced thermoplastic polyurethanes (TPU), and prepreg epoxy matrix prepolymers.

The overall goal of this research is to highlight the modularity of twin screw extruders as continuous polymer reactors to synthesize the relevant polymers. Chapter I …

Enzyme, Cosolvent, And Substrate Interactions In Ple Hydrolysis Reactions And Evaluation Of The Stability Of An Unnatural Glutathione Analogue, Maureen Elizabeth Smith

Dissertations

Prochiral diester malonates have been hydrolyzed in the presence of Pig Liver Esterase (PLE). Several of the diesters produced the respective half-ester in moderate to high enantioselectivity. A series of cosolvent assays were performed to evaluate the ability of the cosolvent to influence the enantioselective outcome of the hydrolysis reactions. Ethanol produced the largest changes in enantioselectivity of all solvents evaluated. The isoenzymes of PLE were also evaluated and provided very different enantioselective outcomes than that of crude PLE. A series of NMR titrations was performed to explore the interactions between the substrates and ethanol cosolvents.

Improvements to our previously …

Utilization Of Aqueous Raft Prepared Copolymers To Improve Anticancer Drug Efficacy, Andrew Christopher Holley

Dissertations

The advent of controlled radical polymerization (CRP) techniques, along with advancements in facile conjugation chemistry, now allow synthetic tailoring of precise, polymeric architectures necessary for drug/gene delivery. Reversible addition- fragmentation chain transfer (RAFT) polymerization and its aqueous counterpart (aRAFT) afford quantitative control over key synthetic parameters including block length, microstructure, and placement of structo-pendent and structo-terminal functionality for conjugation of active agents and targeting moieties. The relevance of water-soluble and amphiphilic (co)polymers synthesized by RAFT for in vitro delivery of therapeutics in biological fluids is an especially attractive feature. In many cases, polymerization, binding, conjugation, …

Molecular Probes For The Detection Of Zn2+ And Fe3+ Ions, Erendra Manandhar

Dissertations

A number of molecular probes have been designed and synthesized for the detection of Zn²⁺ and Fe³⁺ ions. Two types of functional groups have been incorporated into the molecular scaffolds to utilize different fluorescent mechanisms. The first class of receptors contains a pyrene moiety. These molecular probes use the excimer mechanism for the detection of Zn²⁺ ion. The probes work well in an organic solvent with a detection limit of 20 nM (one ppb). Alternatives are made to make them water soluble, but this proved to be difficult. An interesting ion-induced self-assembly system will also be discussed. …

Hybrid Meshless Method For Numerical Solution Of Partial Differential Equations, Jeanette Marie Monroe

Dissertations

A meshless method for solving partial differential equations (PDEs) which combines the method of fundamental solutions (MFS) and the method of particular solutions (MPS) is formulated and tested. The hybrid method finds a numerical approximation by solving only one system of equations as opposed to the two-stage method of fundamental solutions and method of particular solutions. This new approach, denoted MFS-MPS, one-stage MFS-MPS, or hybrid method, can be applied to a wide variety of PDEs including PDEs with variable coefficients. The MFS-MPS can simplify Helmholtz-type differential operators to Laplacian-type differential operators providing flexibility and simplification to calculating particular solutions and …

Spectroscopy And Gas-Phase Binding Of Modified Desferrioxamine B Indicator Displacement-Based Sensors, William Scott Jones

Dissertations

A coupling reaction has been used to successfully synthesize two novel probes utilizing coumarin derivatives as fluorophores. The structure, spectroscopy, and thermodynamics of these probes were characterized and studied. These probes, along with a classical probe using a N-methyl-anthranilate fluorophore, are used to take advantage of the ability of siderophores to coordinate Fe³⁺ ions which is coupled with the attractive phosphorescence properties of lanthanide ions. The use of lanthanide metals to create an indicator displacement assays is a novel application of these probes for the detection of Fe³⁺ ions. The use of Tb³⁺ ions as the indicator …

Investigation Of Glassy State Molecular Motions In Thermoset Polymers, Jianwei Tu

Dissertations

This dissertation presents the investigation of the glassy state molecular motions in isomeric thermoset epoxies by means of solid-state deuterium (²H) NMR spectroscopy technique. The network structure of crosslinked epoxies was altered through monomer isomerism; specifically, diglycidyl ether of bisphenol A (DGEBA) was cured with isomeric amine curatives, i.e., the meta-substituted diaminodiphenylsulfone (33DDS) and para-substituted diaminodiphenylsulfone (44DDS). The use of structural isomerism provided a path way for altering macroscopic material properties while maintaining identical chemical composition within the crosslinked networks.

The effects of structural isomerism on the glassy state molecular motions were studied using solid-state ²H …

Computational And Experimental Investigation Into Yield Behavior And Cure Rate Dependence Of Thermoset Polymers, Christopher Harold Childers

Dissertations

This dissertation is broken down into two primary sections: firstly, the development and improvement of molecular dynamics simulations of thermoset matrix polymers including their use in understanding molecular response to applied strain deformation and secondly, the discernment of a cure heating ramp rate dependence of the final molecular and macro-molecular properties of thermoset matrix polymer.

The molecular dynamics section will discuss the development of molecular dynamics simulations of thermoset epoxy/amine matrix polymers, and the implementation of this work to determine the underlying molecular level events that cause thermoset matrix polymer yield. It will report a novel method for the determination …

Tuning Responsiveness Of Polypeptide Based Block Copolymers For Drug Delivery, Ashley J. Johnson

Dissertations

The goal of this dissertation was to tune the pH response and self-assembled morphologies of amphiphilic polypeptide block copolymers for use as drug delivery vehicles. Poly(L-lysine) and poly(L-glutamtic acid) are responsive, ionizable polypeptides that undergo secondary structure transitions, from α-helix to random coil, whereby the change in conformation of the peptide chain results in changes to the global morphology of a self-assembled system. The main focus of this work was to understand how changes in the polymer composition and the local environment can lead to control over the behavior of the overall system. First, the responsive behavior of poly(L-lysine) block …

Lnference On Differences In K Means For Data With Excess Zeros And Detection Limits, Haolai Jiang

Dissertations

Many data have excess zeros or unobservable values falling below detection limit. For example, data on hospitalization costs incurred by members of a health insurance plan will have zeros for the percentage who did not get sick. Benzene exposure measurements on petroleum re nery workers have some exposures fall below the limit of detection. Traditional methods of inference like one-way ANOVA are not appropriate to analyze such data since the point mass at zero violates typical distribution assumptions.

For testing for equality of means of k distributions, we will propose a likelihood ratio test that accounts for excess zeros or …

Modular Monochromatic Colorings, Spectra And Frames In Graphs, Chira Lumduanhom

Dissertations

Abstract attached as separate document.

Probing The Unfolding And The Stability Of The Last Four Metal Binding Domains Of Wilson Disease Protein Using Circular Dichroism And Novel Spectroscopic Techniques, Ibtesam Yaseen Alja’Afreh

Dissertations

Wilson disease protein is a copper-transporting P_1B type ATPase. It has large N-terminal copper binding domain which is composed of six homologous sub-domains. Each of these six domains is ~72 residues and connected to one another by linking regions of various lengths. They all possess similar ferrodoxin fold, and metal-binding motif, MXCXXC.

The need of having six metal binding domains and the manner in which they are communicating with each other is not well understood. To better understand how the last four metal binding domains function, I pursued a detailed biophysical characterization of these domains. Using molecular biology I …

Ultrafast Interfacial Electron Transfer Across Molecule-Tio2 Nanocomposites: Towards Solar Cells And Two Photon Absorption, Edwin Mghanga

Dissertations

Interfacial charge transfer (ICT) across the molecule-TiO2 nanoparticle interface has gained enormous research attention for applications in dye sensitized solar cells (DSSC), photo-catalysis, water splitting and nonlinear optics. DSSCs are promising clean alternative energy sources. However, current DSSCs suffer from lower efficiencies and higher cost. Better understanding of the ICT processes in DSSCs can help solve these problems. We have used two strategies to understand ICT in the context of DSSCs. Firstly, we used a computationally validated anchor group, acetylacetonate (acac) to bind molecules to the semiconductor surface and facilitate charge separation. Secondly, we used natural dye sensitizers, …

Confidence Bands For Survival Curves Using Model Assisted Cox Regression, Shoubhik Mondal

Dissertations

The goal of this dissertation is to develop informative subject-specific simultaneous confidence bands (SCBs) for survival functions from right censored data. The approach is based on an extension of semiparametric random censorship models (SRCMs) to Cox regression, which produces reliable and more informative SCBs. SRCMs derive their rationale from their ability to utilize parametric ideas within the random censorship environment. Incorporating SRCMs into the existing framework produces more powerful procedures to analyze right censored data. The first part of the project focuses on proposing new estimators of Cox regression parameters and the cumulative baseline hazard function, and deriving their large …

New Directions For Remote Data Integrity Checking Of Cloud Storage, Bo Chen

Dissertations

Cloud storage services allow data owners to outsource their data, and thus reduce their workload and cost in data storage and management. However, most data owners today are still reluctant to outsource their data to the cloud storage providers (CSP), simply because they do not trust the CSPs, and have no confidence that the CSPs will secure their valuable data. This dissertation focuses on Remote Data Checking (RDC), a collection of protocols which can allow a client (data owner) to check the integrity of data outsourced at an untrusted server, and thus to audit whether the server fulfills its contractual …

Intent-Based User Segmentation With Query Enhancement, Wei Xiong

Dissertations

With the rapid advancement of the internet, accurate prediction of user's online intent underlying their search queries has received increasing attention from the online advertising community. As a rich source of information on web user's behavior, query logs have been leveraged by advertising companies to deliver personalized advertisements. However, a typical query usually contains very few terms, which only carry a small amount of information about a user's interest. The tendency of users to use short and ambiguous queries makes it difficult to fully describe and distinguish a user's intent. In addition, the query feature space is sparse, as only …

Efficient Domain Decomposition Algorithms For The Solution Of The Helmholtz Equation, Dawid Midura

Dissertations

The purpose of this thesis is to formulate and investigate new iterative methods for the solution of scattering problems based on the domain decomposition approach. This work is divided into three parts. In the first part, a new domain decomposition method for the perfectly matched layer system of equations is presented. Analysis of a simple model problem shows that the convergence of the new algorithm is guaranteed provided that a non-local, square-root transmission operator is used. For efficiency, in practical simulations such operators need to be localized. Current, state of the art domain decomposition algorithms use the localization technique based …

The Experience Of Reducing Environmental Risks In An Environmental Justice Community, Gabriela Dory

Dissertations

Research on Environmental Justice (EJ) communities has focused on quantitative assessment of environmental hazards and general physical health problems. Little is known about how individuals living in EJ communities perceive their environmental risks and how they reduce environmental risks. The purpose of the study is to explore and describe the perceived environmental risks and the experience of reducing environmental risk among individuals living in an EJ community.

A qualitative and longitudinal design with a descriptive phenomenological method is used to recruit 23 participants living in a known EJ community in the urban area of New Jersey. A total of 43 …

New Methods And Strategies For Orthogonal Oligosaccharide Synthesis, Scott James Hasty

Dissertations

Although scientists have been able to isolate certain classes of naturally occurring carbohydrates, the overall availability of pure natural isolates remains inadequate. As a result, chemical synthesis has been employed to access complex carbohydrates. Unfortunately, traditional oligosaccharide synthesis often requires laborious protecting-group manipulations that results in lower yields. Expeditious strategies effectively shorten the task of oligosaccharide assembly by minimizing the need for protecting-group manipulations between glycosylation steps, or even purification of the intermediates. Additionally, prediction of the stereoselective outcome of the coupling reaction between two sugar units is a major obstacle facing carbohydrate chemists. It is well known that 1,2-trans …

Multi-Sensory Emotion Recognition With Speech And Facial Expression, Qingmei Yao

Dissertations

Emotion plays an important role in human beings’ daily lives. Understanding emotions and recognizing how to react to others’ feelings are fundamental to engaging in successful social interactions. Currently, emotion recognition is not only significant in human beings’ daily lives, but also a hot topic in academic research, as new techniques such as emotion recognition from speech context inspires us as to how emotions are related to the content we are uttering.

The demand and importance of emotion recognition have highly increased in many applications in recent years, such as video games, human computer interaction, cognitive computing, and affective computing. …

Development And Applications Of The Expanded Equivalent Fluid Method, Bharath Kumar Kandula

Dissertations

Ocean acoustics is the study of sound in the oceans. Electromagnetic waves attenuate rapidly in the water medium. Sound is the best means to transmit information underwater. Computational numerical simulations play an important role in ocean acoustics. Simulations of acoustic propagation in the oceans are challenging due to the complexities involved in the ocean environment. Different methods have been developed to simulate underwater sound propagation. The Parabolic-Equation (PE) method is the best choice in several ocean acoustic problems. In shallow water acoustic experiments, sound loses some of its energy when it interacts with the bottom. An equivalent fluid technique was …

The Experiences Of Women In Post Graduate Physics And Astronomy Programs: The Roles Of Support, Career Goals, And Gendered Experiences, Ramón S. Barthelemy

Dissertations

In physics and astronomy the low representation of women is obvious at every stage of the educational pathway from undergraduate students to full professors. These low numbers perpetuate themselves by failing to create new mentors to foster the next generation of women. Women and men also have different experiences as they traverse into physics and astronomy careers. Women often experience chilly climates, discrimination, and challenges coordinating the demands of young families with their careers. In the literature exploring this topic, little focus is put on the experiences of women graduate students in physics and no focus is put on women …

Comparison Of Hazard, Odds And Risk Ratio In The Two-Sample Survival Problem, Benedict P. Dormitorio

Dissertations

Cox proportional hazards is the standard method for analyzing treatment efficacy when time-to-event data is available. In the absence of time-to-event, investigators may use logistic regression which only requires relative frequencies of events, or Poisson regression which requires only interval-summarized frequency tables of time-to-event. When event frequencies are used instead of time-to-events, does it always result in a loss in power?

We investigate the relative performance of the three methods. In particular, we compare the power of tests based on the respective effect-size estimates (1)hazard ratio (HR), (2)odds ratio (OR), and (3)risk ratio (RR). We use a variety of survival …

Design And Synthesis Of Chelating Compounds And Solid-Supported Chelators For Metal Depleted Solutions, Surendra Dawadi

Dissertations

Metals are essential to life, yet they can be toxic for biological systems when present in excessive amounts. The major source of metal overload in humans is diet; and in some cases, intravenous feeding. Thus the removal of toxic metal ions from contaminated clinical products such as total parenteral nutrition (TPN) solutions, and drinking and waste water is extremely important. The use of chelating resins, which are polymeric solids containing covalently immobilized chelating compounds, for the selective removal of metal ions from contaminated solutions has been conceptualized long ago. Herein, the design and synthesis of metal specific chelating compounds and …

Chemistry And Thermochemistry Of Selected Fatty Acids Using Correlation Gas Chromatography, Joe A. Wilson

Dissertations

Correlation gas chromatography (c-GC) is a special application of the gas chromatography technique and is used for the evaluation of both vaporization enthalpy and vapor pressures of organic compounds. Its use in measuring vaporization enthalpies has been extensively documented. This method is useful for measurements of both liquids and solids. For substances that are solids, since each analyte is dilutely adsorbed on the condensed phase of the gas chromatographic column, it is not crystalline. The vapor pressure that it exhibits behaves as an excellent model of the sub-cooled liquid as demonstrated by various thermochemical cycles. Thermochemical measurements are important to …

Nanoporous Gold Characterization, Structural Modification And Use As A Solid Support For Biomolecule Immobilization, Abeera Sharma

Dissertations

Nanoporous gold (NPG) has immense technological applications owing to a plethora of properties like large surface area to volume ratio, plasmonic properties, stable gold-thiolate bond formation and a wide range of pore sizes. The surface morphology of nanoporous gold has been altered previously by dealloying and thermal annealing to increase/decrease the pore size and change the surface area. We provide a novel electrochemical annealing technique for post dealloying modification wherein electrochemical sweep cycles in different electrolytes at positive potentials leads to a subsequent increase in pore sizes of nanoporous gold as studied using scanning electron microscopy. Tailoring the surface of …

Lie Loops Associated With Gl(ℋ), ℋ A Separable Infinite Dimensional Hilbert Space, Alper Bulut

Dissertations

Abstract attached as separate file.

On Eulerian Irregularity And Decompositions In Graphs, Eric Andrews

Dissertations

Abstract attached as separate file.

Biophysical Characterization Of The First Four Metal-Binding Domains Of Human Wilson Disease Protein, Alia V.H. Hinz

Dissertations

Wilson disease protein (WLNP) is a P_1b-type ATPase crucial for maintaining copper homeostasis in humans. Mutations in this protein result in the autosomal recessive disorder Wilson disease, a condition characterized by copper accumulation in the liver and brain. WLNP provides copper for incorporation into cuproproteins and exports excess copper into the bile for excretion. There are six metal-binding domains (MBDs) in WLNP, found within the first 650 amino acids of this 1,465 amino acid protein. Though each MBD has a different amino acid sequence, all MBDs possess a similar ferredoxin fold with a conserved hydrophobic core and a …