Physical Sciences and Mathematics Commons^™

Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, Amir Rabiee Kenaree

Electronic Thesis and Dissertation Repository

This thesis describes the investigation of a novel strategy for the synthesis of metal-containing small molecules, polymers, and nanomaterials. In this context, a new family of air-stable, homo- and heterometallic primary, secondary, and tertiary phosphines were prepared via the radical-initiated hydrophosphination reaction of PH₃ with vinylferrocene and/or vinylruthenocene. The full characterization of the phosphines confirmed their targeted structures and proved that the properties of the starting metallocenes are reflected in those of the resulting phosphines.

To study the coordination behavior of this family of phosphines, primary, secondary, and tertiary ethylferrocene phosphines were reacted with Group 6 metal carbonyl adducts …

X-Ray Absorption And Emission Studies Of Anodic Titania Nanostructures, Jun Li

Electronic Thesis and Dissertation Repository

One-dimensional (1D) TiO₂ nanomaterials with ordered structure have been extensively applied in various fields, such as photocatalysts, solar cells, supercapacitors and rechargeable batteries, due to the unique structural and functional properties compared to the disordered nanoparticulate forms. Nevertheless, intrinsic disadvantages of TiO₂, such as its large band gap (~3 eV), fast recombination rate of photoexcited electron–hole pairs and insufficient ionic conductivity, severely limit the development of 1D TiO₂ nanomaterials for practical applications. To address the above issues, the scope of this thesis focus on the fundamental understandings of the electronic structure of highly ordered TiO_{2 …}

Creating Functional Materials With Phosphorus, Tyler John Cuthbert

Electronic Thesis and Dissertation Repository

Understanding the relationship between small molecules or polymers and how they affect the properties of materials they compose is the basis of materials science. Using unique and versatile components can impart useful and interesting properties to materials. Here, we aimed to extend this understanding to phosphorus, and the known properties it possesses. This included the production of photopolymerizable coatings containing phosphonium molecules and polymers for antifouling and antibacterial applications. The synthesis and characterization of these phosphonium components was completed and materials were produced utilizing UV curing technology. Addition of these components produced coatings that could resist bacteria attachment and efficiently …

Synthesis Of Metal-Containing Polymers And Stable Organic Radical-Containing Polymers And Their Use As Advanced Functional Materials, Joseph A. Paquette

Electronic Thesis and Dissertation Repository

The work presented in this thesis details the synthesis and characterization of two different families of multifunctional polymers. The first family involved the incorporation of stable 6-oxoverdazyl radicals into polymer scaffolds. This was originally achieved by the polymerization of the radical precursors, phenyl- and isopropyl-6-oxotetrazanes, followed by post-polymerization oxidation to afford the phenyl- and isopropyl-6-oxoverdazyl polymers. A second methodology involved the direct polymerization of isopropyl-6-oxoverdazyl radicals using ring-opening metathesis polymerization (ROMP) to afford polymers with controlled molecular weights and narrow molecular weight distributions. The polymers were characterized by the close comparison of the physical and spectroscopic properties …

Properties Of High Nitrogen Content Carbon Nitride Thin Films Prepared By A Radio Frequency Magnetron Sputtering Deposition Technique, David Pipher

Electronic Thesis and Dissertation Repository

The properties of carbon nitride (CNx) films deposited onto various substrates using a radiofrequency magnetron sputtering technique were studied as a function of deposition parameters, especially magnetron power, gas pressure and nitrogen content in the plasma. Indium tin oxide (ITO) coated glass and fluorine tin oxide (FTO) coated glass as well as metal substrates (silver and tungsten) were used. Scanning electron microscopy (SEM) was used to study the surface morphology of the prepared CNx films. Energy-dispersive X-ray spectroscopy (EDX) as well as survey X-ray photoelectron spectroscopy (XPS) spectra were used to perform the elemental analysis of the CNx films.

Ultraviolet-visible …

Polyol Induced Partitioning Of Essential Oils In Aqueous Organic Solvent Mixtures, Thomas Delmastro

Seton Hall University Dissertations and Theses (ETDs)

Polyol Induced Extraction (PIE) was developed and patented at Seton Hall University by Drs. John R. Sowa Jr., Wyatt R. Murphy, and Mithilesh Deshpande. It was originally discovered and implemented as a method to recycle and reuse waste acetonitrile during the production shortage in 2008. Through the use of PIE, a solvent mixture containing acetonitrile and water can be separated by employing a polyol mass separating agent, which induces a phase separation. The system is separated into its corresponding aqueous and organic phases, with the organic phase being a highly purified organic liquid. Based on the successful experimental results that …

Development Of An F-Element Separation Chemistry Using Solid Electrolytes, Kristian Guy Myhre

Doctoral Dissertations

The f‒elements (lanthanides and actinides) have numerous applications and are critically important to many industries, including the energy, security, and medical industries. One of the barriers to increased use and availability of the f‒elements is the difficulty in separating them from each other due to their similar chemistries. This is especially true of the trivalent f‒elements (lanthanides and minor actinides). The development of separation techniques that maximize the differences in the physicochemical properties of the f‒elements is therefore an important area of research. For these reasons, an effort was undertaken to explore the use of solid …

Role Of The Inner Shell Architecture On The Various Blinking States And Decay Dynamics Of Core-Shell And Core-Multishell Quantum Dots, Pooja Bajwa

Graduate Theses and Dissertations

Colloidal semiconductor nanocrystals (quantum dots, QDs) have received much attention in recent years due to their uniquely size-tunable properties leading to a number of promising applications. Some of their most popular applications include their use as fluorescent probes in biology, as electro-optical components and in photovoltaic devices. CdSe-based QDs are particularly important because of their ease of synthesis, high photoluminescence quantum yields (PL QYs) across the whole visible spectrum and their photostabilty. Shelling of core QDs is usually carried out to improve their optical properties, minimize outer environmental effects on their properties, and avoid toxic element exposure to the environment. …

Design And Synthesis Of Dynamic Covalent Polymer Scaffolds With Controlled Architectures, Emily Annette Hoff

Dissertations

The design and synthesis of functional, controlled polymer architectures is essential to the development of new materials with precise and tailorable properties or applications. The work described in this dissertation focuses on the development of controlled polymer architectures with dynamic linkages for the design of multifunctional materials and surfaces via robust, efficient, and stimuli-responsive strategies.

In Chapter III, a post-polymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethyl pyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds …

Electrogenerated Chemiluminescence Study Of Semiconductor Nanoparticles Towards Sensitive Detection Of Biomolecules, Yiliyasi Wusimanjiang

Dissertations

The main focus of this dissertation is to unfold the fundamental aspects of electrogenerated chemiluminescence (ECL) generation from semiconductor nanoparticles (also known as quantum dots or QDs) within different ECL systems. The ECL and photo-physical interactions between the CdTe QDs (λ_emission= ~760 nm) and the CdSe QDs (λ_emission= ~550 nm), as well as the effects of carbon nanotubes on ECL of QDs were separately investigated. Optimum experimental conditions for peptide bond formation on an electrode surface through EDC (1-ethyl-3-(-3-dimethylaminopropyl) carbodiimide hydrochloride)/NHS (N-Hydroxysulfosuccinimide) coupling were also revealed using cyclic voltammetry technique. Based on the information …

Preparation Of Aminoalcohols And Their Application For The Synthesis Of Heterocycles And As Potential Sensors For Nerve Agents, David L. Sellers

Dissertations

Oxazoles and oxazolines are important heterocyclic scaffolds commonly used in pharmaceuticals and optoelectronic materials. Traditionally these heterocyclic compounds are prepared by condensation methodology that suffers from poor reactivity when using electron deficient or sterically crowded reaction partners. Condensation methods also exhibit low tolerance of many functional groups as the reactions typically use strong acids and high temperatures. This dissertation describes an alternate strategy for the formation of these compounds by employing an epoxide opening followed by oxidation to form these heterocyclic compounds.

Epoxide opening reactions with primary aliphatic, allylic, and benzylic amines, aminolysis reactions, often achieve high yields regardless of …

Evaporation Induced Self-Assembly And Characterization Of Nanoparticulate Films: A New Route To Bulk Heterojunctions, Yipeng Yang

Doctoral Dissertations

Polymer-based semiconducting materials are promising candidates for large-scale, low-cost photovoltaic devices. To date, the efficiency of these devices has been low in part because of the challenge of optimizing molecular packing while also obtaining a bicontinuous structure with a characteristic length comparable to the exciton diffusion length of 10 to 20 nm. In this dissertation we developed an innovative evaporation-induced nanoparticle self-assembly technique, which could be an effective approach to fabricate uniform, densely packed, smooth thin films with cm-scale area from home-made P3HT nanoparticles. Unlike the previous reports of nanoparticle-based film formation, we use a mixture of two solvents so …

Cell Modulation Using Functionalized Nanoparticles, Rui Tang

Doctoral Dissertations

Monolayer functionalized ultra-small gold nanoparticles (AuNPs) provide a versatile platform for applications in cell research. Through rational design of surface ligands, the chemistry of AuNPs are precisely regulated at atomic level. In this dissertation, applications of AuNPs in cell modulation are discussed. The topics are split into two categories. In the first category, functionalized AuNPs are harnessed to generate a robust monolayer on cell culture surface for cell modulation. The proliferation and behavior of different types of cancer cells and normal cells are modulated by tuning the surface ligands of AuNPs. Fate decision of mesenchymal stem cells are also modulated …

Engineering The Nano-Bio Interface Of Gold Nanoparticles For Biomedical Applications, Ying Jiang

Doctoral Dissertations

Gold nanoparticles (AuNPs) have emerged as a promising platform for a myriad of biomedical applications, including sensing, drug delivery, and antibiotics. In this thesis, I have studied and engineered the interface of AuNPs with different biological systems, demonstrating a large variety of biomedical applications by modulation of these interfaces. My research was initially focused on systematically tuning the physicochemical properties of nanoparticles to understand nano-bio interactions at the cellular level. The results demonstrate that size and surface charge of AuNP interact in an interrelated fashion to modulate nanoparticle internalization by cells, providing an engineering strategy for designing nanomaterials for drug …

Solvothermal Preparation And Characterization Of Superstructures Of Nanoscopic Cds And Cdse, Tetyana Levchenko

Electronic Thesis and Dissertation Repository

Micrometer-sized superparticles, self-assembled from metallic or semiconducting nanoclusters, can be used as convenient building blocks for preparing functional materials, utilizing the electronic and photophysical properties resulting from the quantum confinement as well as from the coupling between individual nanoscopic constituents.

This research aimed at developing a novel approach utilizing the conversion of a cadmium phenylchalcogenolate precursor (Me₄N)₂[Cd(EPh)₄] (where E = S or Se) under solvothermal conditions for the preparation of nanoscopic CdE, including both crystalline superlattices of large discrete nanoclusters and superstructures with more complex morphology. In particular, 3D cubic superlattices of molecular CdS …

Development Of New Radiolabeling Methods And Insights On Ionizing Radiation Interactions With Nanoparticles, Travis Shaffer

Dissertations, Theses, and Capstone Projects

Nanoparticles are often combined with radionuclides for various applications, ranging from waste remediation to imaging and therapy in the medical field. The overarching aim of this body of work is two-fold. The first aim is development of new radiolabeling methods for various nanoparticles that allow stable attachment of a variety of imaging and therapeutic radionuclides. The second portion more fully describes mechanisms of interaction between ionizing radiation and nanoparticles.

The following advancements will be presented in this dissertation: i) a new radiolabeling method for silica and silica-based nanoparticles that does not require the use of specific chelators, with both radiochemical …

Sustainable Molecular Gelators: Beta-D-Glucoside Derived Structuring Agents And Their Material Application, Julian R. Silverman

Dissertations, Theses, and Capstone Projects

Though molecular gelators may by synthesized and formulated into gels following a variety of methods, it should serve that the most valued methods may utilize renewable and waste resources and follow sustainable procedures. Molecular gelators are systems capable of structuring liquids into solid-like materials and they represent a class of surfactant and amphiphilic materials which posses the capability to be not only useful in their ability to form gels, but multifunctional in the ability to respond smartly to a variety of stimuli. Thus there is an interest in the development of sustainable molecular gelators capable of being applied to applications, …

Photodynamic Killing Of Human Cancer Cells With Smart Photosensitizer Materials And An Endoscopic Implement For Singlet Oxygen Delivery, Mihaela N. Minnis

Dissertations, Theses, and Capstone Projects

The thesis describes progress on probe tips for a microoptic device for the precise delivery of the components necessary for photodynamic therapy (PDT) in a highly localized and controllable fashion. The thesis also summarizes results of a photosensitized oxidation study. The work focused on i) developing a photoactive fluoropolymer surface that will release sensitizer drug molecule for use in PDT, ii) designing new probe tips surfaces for use as sensitizer support for a microoptic PDT device, iii) exploring strategies for covalent attachment of sensitizers and model compounds to Teflon/PVA surfaces with the aim of being coupled with our microoptic device, …

Probing The Structure And Photophysics Of Porphyrinoid Systems For Functional Materials, Christopher D. Farley

Dissertations, Theses, and Capstone Projects

Porphyrins (Pors) and their many cousins, including phthalocyanines (Pcs), corroles (Cors), subphthalocyanines (SubPcs), porphyrazines (Pzs), and naphthalocyanines (NPcs), play amazingly diverse roles in biological and non-biological systems because of their unique and tunable physical and chemical properties. These compounds, collectively known as porphyrinoids, can be employed in any number of functional devices that have the potential to address the challenges of modern society. Their incorporation into such devices, however, depends on many structural factors that must be well understood and carefully controlled in order to achieve the desired behavior. Self-assembly and self-organization are key processes for developing these new technologies, …

Nanostructured Air Electrodes And Electrochemical Reaction Mechanism Studies For Sodium-Oxygen Batteries, Hossein Yadegari

Electronic Thesis and Dissertation Repository

Alkali metal-O₂ batteries, i.e. Li- and Na-O₂, are considered as the next generation of energy saving technologies with potential application in electric transportation. The high theoretical energy density in these cells is related to the use of high energy alkali metals as negative and oxygen as the positive electrode materials. The performance of alkali metal-O₂ cells is highly dependent on the positive electrode material, where oxygen reduction and evolution reactions take place. Besides, the primary products of oxygen reduction reaction in these cells are typically metal oxides, which are insoluble in nonaqueous electrolytes, resulting in accumulation …

Fabricating And Characterizing Chalcogenide Thin Films As Light Absorbing Layers In Solar Cells, Daniel Vaccarello

Electronic Thesis and Dissertation Repository

Solar cell development has been a focus in energy research, with light-absorbing layers as the key theme. Copper indium disulphide (CuInS₂) and copper zinc tin sulphide (Cu₂ZnSnS₄ or CZTS) have energy band gaps that are optimal for solar energy conversion. New preparation methods have been developed with practicality, safety, and low costs in mind. The one-pot method developed in this thesis group has been utilized to create nanocrystals that can be used to absorb light and generate current. The use of low temperatures and minimalistic reaction conditions has led to the production of CIS and …

A Comparison Of Solvent And Water-Borne Alkyd Coatings And The History Of Voc Regulations In The United States, Molly Elise Burns

Master's Theses

A Comparison of Solvent and Water-Borne Alkyd Coatings Abstract

Conventional solvent based alkyd coatings have gone out of favor due to concerns over volatile organic compound (VOC) content. However, due to recent focus on renewable raw materials, alkyds are making a comeback in waterborne form. Water based alkyd coatings are known to have poor shelf stability and corrosion resistance, as well as other problems during the formulation process. This project focused on comparing solvent borne to two types of water-borne alkyds, water reducible alkyds and alkyds emulsions. The purpose was to understand the differences between the three types of alkyds …

Development Of Novel Anode Materials For Lithium Ion Batteries, Mike A. Nieradko

Electronic Thesis and Dissertation Repository

This thesis focuses on the development of new anodes for Li ion batteries. Aluminium has been long considered as promising anode material for Li ion batteries because of its low cost, abundance, and low toxicity. Aluminium undergoes alloying with lithium through intermetallic LiAl formation which offers a relatively high theoretical capacity of 993 mAh/g compared to 372 mAh/g for graphite that is currently the principal anode material in commercial Li ion batteries. However, despite intensive research, all aluminium-based anodes tested so far suffered from rapid capacity fading and failure within first few cycles. Furthermore, there is insufficient understanding of the …

Engineering Nanoarchitectures From Nanosheets, Nanoscrolls, And Nanoparticles, Taha Rostamzadeh

University of New Orleans Theses and Dissertations

The ability to encapsulate/insert different kinds of nanoparticles (NPs) in scrolled nanosheets (NSs) may lead to the formation of new nanocomposite materials that yield novel properties. These nanostructures resemble “peapods” that consist of NPs chains (“peas”) located in a hollow space of desired nanoscrolls (“pods”). Depending on different combinations of “peas” and “pods” diverse families of nanopeapods (NPPs) can be synthesized which may exhibit interesting properties not accessible from the individual components. Though there exist various synthetic methods for the formation of NPPs, more development in terms of simplicity, flexibility, and productivity of synthetic approaches are needed so that different …

Correlation Of Polymer Performance And Hansen Solubility Parameters, Daniel Jobse Mania

Master's Theses

Ready-to-use (RTU) grout is becoming more important to the finish and remodeling construction industry. Market research shows it is a fast-growing product that not only is creating its own space, but is beginning to supplant existing technology.

The original intent of this research was to investigate formulation parameters and how they affect grout performance. It was learned that particle size and oil absorption (OA) value are important filler properties that affect performance as much as adequate packing density and optimal pigment volume concentration (PVC) without going beyond critical PVC (CPVC).

Polymer architecture was also determined to be extremely important, but …

Development Of Instrumentation For The Analysis Of Photoconductivity In Functional Materials, Brandon L. Chapman 9741174

Chancellor’s Honors Program Projects

No abstract provided.

Development And Optimization Of Solid Polymer Electrolyte For Lithium Ion Batteries, Ladan Eskandarian

Electronic Thesis and Dissertation Repository

This thesis focuses on the development of new poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) in order to enhance their ionic conductivity at ambient temperature and fabricate the prototypes of novel Li ion batteries using these SPEs. Different types of SPEs have been developed: (i) blends of high molecular weight PEO and low molecular weight poly(vinyl acetate) (PVAc); (ii) composites of high molecular weight PEO and titanium dioxide (TiO₂)nanoparticles; and (iii) blend-based composite electrolytes consisting of PEO and PVAc with dispersed TiO₂. The SPEs were characterized by scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and …

Synthesis And Characterization Of Polymeric Anion Exchange Membranes, Wenxu Zhang

Doctoral Dissertations

As alkaline anion exchange membrane fuel cells (AAEMFC) are regarded as promising and important energy devices, the development of high performance anion exchange membranes are in urgent need, as well as fundamental investigation on the structure-property relationship, which are the motivation of this dissertation. Three different polymer systems are presented and focused on polymer synthesis, material morphology, and ion transport phenomena. Crosslinked membranes are promising as practical materials, however, the understanding and further improvement of its performance is hindered by the lack of an ordered morphology or well-defined chemical structure. In Chapter 2, a series of crosslinked membranes were design …

Magnetic Doping Of Semiconductor Molecular Models And Colloidal Nanocrystals, Swamy Pittala

Doctoral Dissertations

Spin-based electronics use the spins of electrons in addition to their charges and have potential applications to create a next generation of quantum computers, capable of storing vast amounts of data in an energy-efficient way. Diluted magnetic semiconductor quantum dots (DMS-QDs) have shown great promise as ideal materials for application in spin-based electronics. However, doping impurities into quantum confined colloidal nanocrystals (NCs) has been a great challenge due to the lack of control over the dopant reactivity during the specific stages of nucleation and growth. The mechanism of dopant incorporation into nanocrystals is complex and well-defined and atomically precise molecular …

Design, Synthesis, And Applications Of Nano-Assemblies Based On Amphiphilic Macromolecules, Hui Wang

Doctoral Dissertations

Recent progress in nanotechnology has been significantly impacting a variety of areas such as utilization in microelectronics, multiphase catalysis, sensing and therapeutics. Our interests are to develop new nanomaterials to understand their structure-property relationships and to utilize them for various applications. In this thesis, we discuss our findings on the design, synthesis and applications of nanomaterials formed by self-assembly of amphiphilic molecules. Micelles are self-assembled nanostructures formed by amphiphilic molecules. They are capable of sequestering hydrophobic guest molecules in an aqueous environment. Other than surfactants, micelles can also be formed by amphiphilic polymers or dendrimers, which are macromolecular surfactants in …