Chemistry Commons^™

Template-Assisted Fabrication Of Ferromagnetic Nanomaterials, Jagnyaseni Tripathy

University of New Orleans Theses and Dissertations

Abstract

Template assisted deposition was used to produce various nanomaterials including simple nanowires, nanorods, multi-segmented metal nanowires, core-shell nanowires, alloy and polymer wires and tubes. Anodized aluminum oxide (AAO) membranes were used as templates for the growth of the various structures using an electrochemical deposition method and also by wetting the porous templates. In the electrochemical deposition method, the pore size of the templates affects the rate of synthesis and the structures of the nanomaterials while in the wetting method, the viscosity and reaction time in the polymer solution influence the structures of the nanomaterials.

A conventional two-step anodization procedure …

Production And Applications Of Formaldehyde-Free Phenolic Resins Using 5-Hydroxymethylfurfural Derived From Glucose In-Situ, Yongsheng Zhang

Electronic Thesis and Dissertation Repository

The phenol-formaldehyde (PF) resin manufacturing industry is facing a growing challenge with respect to concerns over human health, due to the use of carcinogenic formaldehyde and sustainability due to the use of petroleum-based phenol in PF resin manufacture. Glucose and its derivative, 5-hydroxymethylfurfural (5-HMF), have proven to be potential substitutes for formaldehyde in the synthesis of phenolic novolac resins.

This thesis investigated a number of glucose and 5-HMF resin systems including the curing of phenol-glucose novolac resin (PG) with a bis-phenol-A type epoxy. The curing process was modeled according to the Sestak-Berggren equation (S, B) using Málek methods. This was …

Engineering Surface Functionality Of Nanoparticles For Biological Applications, Yi-Cheun Yeh

Doctoral Dissertations

Engineering the surface functionality of nanomaterials is the key to investigate the interactions between nanomaterials and biomolecules for potent biological applications such as therapy, imaging and diagnostics. My research has been orientted to engineer both of the surface monolayers and core materials to fabricate surface-functionalized nanomaterials through the synergistic multidisciplinary approach that combine organic chemistry, materials science and biology. This thesis illustrates the design and synthesis of the surface-funcitonalized quantum dots (QDs) and gold nanoparticles (AuNPs) for the fundamental studies and practical applications. For QDs, A new class of cationic QDs with quaternary ammonium derivatives was synthesized to provide permanent …

Nanoparticle Building Blocks For Functional Structures, Youngdo Jeong

Doctoral Dissertations

A major goal in material science is achieving a desired function using structures fabricated with designed building blocks. Advanced synthetic and self-assembly techniques allow various nanomaterials to become promising building blocks, providing the control of the interaction between building blocks. The unique properties of nanomaterials can be transferred to structured systems. Among nanomaterials, inorganic nanoparticles such as gold nanoparticles (AuNPs), magnetic particles, and quantum dots (QDs) provide useful physical properties stemming from their inorganic core, large surface areas, and oriented surface functionalities. My research has focused on fabricating functional systems using gold nanoparticles (AuNPs), manipulating the interaction between AuNPs, bio-entities, …

Photochromic Molecular Materials For The Controlled Organization Of Nanoparticles, Kristen Elise Snell

Electronic Thesis and Dissertation Repository

The displacement of polystyrene nanoparticles promoted by bulk azo mass transfer using interferential light illumination will be discussed. For this a variety of different push pull small azo molecules were synthesis and characterized, changing the polarity, hydrophobicity and bulky groups around the azo moiety. These small dyes appear to orientate quicker than similarly report azo polymers, of entanglement of the azobenzene group in the polymeric backbone. These dyes were used to form surface relief grating on the thin films due to the bulk mass transfer. This mass transfer was exploited to align polystyrene nanoparticles in the crests and troughs of …

Investigation Of The Crystallization Of Dnl-6 And Ft-Raman Spectroscopic Investigation Of Guest Molecules In Mofs, Maxwell Goldman

Electronic Thesis and Dissertation Repository

Microporous solids are a widely used material in adsorption, storage and catalysis. In this thesis, the crystallization of the silcoaluminaphosphate DNL-6 was characterized using powder X-ray diffraction and solid state nuclear magnetic resonance. Two crystallization routes of the SAPO DNL-6 were studied, which are the hydrothermal method and the dry-gel conversion method. Both methods followed the same crystallization pathway and showed a layered intermediate that is then transformed into DNL-6. The reaction requires two templating agents to create the RHO topology and silicon substitutes into the framework by replacing single phosphorous atoms.

This thesis contains the conformational analysis of halocarbons …

Mass Spectrometric Characterization And Imaging Of Nanoparticles In Biological Samples, Bo Yan

Doctoral Dissertations

Nanoparticles (NPs) are being investigated widely for use in biomedical applications such as imaging, drug delivery, and cancer therapy due to their small size and readily tunable properties. The ability to accurately characterize NPs and monitor their spatial distributions is highly desirable for effective use of NPs and evaluation of their potential adverse environmental, health, and safety effects. In this dissertation, a simple, fast, and sensitive method based on laser desorption/ionization mass spectrometry (LDI-MS) to characterize and track NPs in biological systems has been developed. This method is especially well suited for characterizing core-shell structured NPs, such as quantum dots …

Molecular Engineering Strategies For The Design And Synthesis Of New Organic Photovoltaic Materials, Paul J. Homnick

Doctoral Dissertations

Dramatic improvements in organic photovoltaic device efficiency can be obtained by optimizing spectral absorbance and frontier molecular orbital (FMO) energies, increasing solid state exciton/charge mobility, and utilizing p-/n-type nanoarchitecture. Combining all of these properties into a new material presents a considerable synthetic challenge because potential commercial applications require materials that are high-performance and inexpensive. Thus, it is advantageous to design new materials using a versatile, modular synthetic approach that allows each design criterion to be engineered individually, in a synthetically efficient manner. Several strategies were successfully pursued using simple interchangeable electron donor and acceptor components as functional modules, which …

Ligand-Receptor Interactions For Supramolecular Disassembly With Applications In Screening And Drug Delivery, Diego Amado Torres

Doctoral Dissertations

Proteins have the capacity to bind specific sets of compounds known as ligands, these are small molecules with a recurrent theme in their molecular design that is a characteristic exploited here to (i) identify particular affinities of small molecules for proteins with the aim of using them as ligands, inhibitors, or targeting moieties in more complex systems by means of a methodology that screens small molecules based on protein affinity; (ii) decorate a self-assembling supramolecular system at different positions, making it responsive to a complementary protein with the aim of exploring differences in disassembly and sensitivity of the release of …

Optimization Of P-Type Czts Nanocrystal Thin Film Layers For Applications In Low Cost Photovoltaic Devices, Kyle S.B. Jeffs

Electronic Thesis and Dissertation Repository

In this thesis Cu2ZnSnS4 nanocrystal synthesis was optimized by way of photoelectrochemical measurements through tuning the stoichiometry. Formation of a Cu2ZnSnS4 light-absorbing layer was studied using multiple depositions methods. These included dropcasting, electrophoretic deposition, and use of 3-mercaptopropyl trimethoxysilane as a chemical linker. Dropcasting samples were compared according to the solvents used to suspend the nanocrystals. Photoelectrochemical measurements were used to compare dropcasting with electrophoretic deposition and use of 3-mercaptopropyl trimethoxysilane as a chemical linker. Dropcasting was shown to be the least effective method of depositing the light-absorbing layer. Samples prepared by electrophoretic deposition were optimized according to a number …

Electrogenerated Chemiluminescence Of Gold Nanoclusters, Mahdi Hesari

Electronic Thesis and Dissertation Repository

A series of monodispersed AuNCs including Au144(SR)60, Au38(SR)24 and Au25(SR)18z (z =1-, 0 and 1+, SR=2-phenylethanethiol) were prepared. All these nanoclusters showed molecule-like optical and electrochemical properties. These two features are essential for an electrogenerated chemiluminescence or electrochemiluminescence (ECL) study. The Au144(SR)60 showed a small HOMO-LUMO gap determined by electrochemistry. No ECL light was seen in the annihilation process, while NIR ECL was observed with tri-n- propylamine (TPrA) (Chapter 2). ECL was highly efficient in the Au38(SR)24/TPrA co- reactant system. This nanocluster also showed ECL emission with benzoyl peroxide (BPO), while no ECL was detected in the annihilation route (Chapter …

Synthesis And Applications Of Mutimodal Hybrid Albumin Nanoparticles For Chemotherapeutic Drug Delivery And Phototherml Therapy Platforms, Donna V. Peralta

University of New Orleans Theses and Dissertations

Progress has been made in using human serum albumin nanoparticles (HSAPs) as carrier systems for targeted treatment of cancer. Human serum albumin (HSA), the most abundant human blood protein, can form HSAPs via a desolvation and crosslinking method, with the size of the HSAPs having crucial importance for drug loading and in vivo performance. Gold nanoparticles have also gained medicinal attention due to their ability to absorb near-infrared (NIR) light. These relatively non-toxic particles offer combinational therapy via imaging and photothermal therapy (PPTT) capabilities.

A desolvation and crosslinking approach was employed to encapsulate gold nanoparticles (AuNPs), hollow gold nanoshells (AuNSs), …

Dynamics Of Polyelectrolyte Adsorption On Surfaces: Applications In The Detection Of Iron In Water, Madhira N. Gammana

Electronic Theses and Dissertations

Layer by layer (LbL) self assembly is a simple multilayer thin (nanometer scale) film fabricating technique. The mechanism of film growth remains a topic of much controversy. For example, several models have been proposed to explain the origin of linear and exponential film growth that are attributed to differences in the dynamic processes that occur at the molecular level during film formation. The problem is that there are no methods that directly measure the dynamics of polymer formation during LbL film formation. In this thesis, I describe the essential elements of an ATR-IR spectroscopic method that was developed to enable …

Structural Dynamics And Charge Transport In Room Temperature Ionic Liquids, Philip James Griffin

Doctoral Dissertations

Room temperature ionic liquids are an important class of materials due to their chemical tunability and numerous advantageous physicochemical properties. As a result, ionic liquids are currently being investigated for use in a wide array of chemical and electrochemical applications. Despite their great potential, however, the relationship between the chemical structure and physicochemical properties of ionic liquids is not well understood.

To this end, this dissertation presents experimental studies of the reorientational structural dynamics and charge transport properties of a variety of room temperature ionic liquids using quasielastic light scattering spectroscopy and broadband dielectric spectroscopy.

Studies of a series of …

The Influence Of Microstructure On The Corrosion Of Magnesium Alloys, Robert M. Asmussen

Electronic Thesis and Dissertation Repository

This thesis reports a series of investigations into the influence of microstructure on the corrosion of Mg alloys. Mg alloys are prime candidates for the light-weighting of automobiles however any extensive applications are limited by their high corrosion rates. The corrosion resistance is further hindered by the susceptibility of Mg alloys to microgalvanic coupling occurring between the Mg matrix and the secondary microstructures in the alloys. This process and the individual contributions to it must be understood to improve Mg alloy design for automotive applications, develop methods for extending the lifetime of Mg alloys and developing models to successfully predict …

An Investigation Of Poly(N-Isopropylacrylamide) For Applications With Microfluidic Paper-Based Analytical Devices, Haydn Thomas Mitchell

Master's Theses

N,N′-methylenebisacrylamide-crosslinked poly(N-isopropylacrylamide), also known as P(NIPAM), was developed as a fluid delivery system for use with microfluidic paper-based analytical devices (microPADs). MicroPADs are postage-stamp-sized devices made out of paper that can be used as platforms for low-cost, simple-to-use point-of-care diagnostic assays. P(NIPAM) is a thermally responsive polymer that absorbs aqueous solutions at room temperature and will expel the solutions to microPADs when heated. The fluid delivery characteristics of P(NIPAM) were assessed, and P(NIPAM) was able to deliver multiple solutions to microPADs in specific sequences or simultaneously in a laminar-flow configuration. P(NIPAM) was then shown to be suitable …

Improving Hybrid Solar Cells: Overcoming Charge Extraction Issues In Bulk Mixtures Of Polythiophenes And Zinc Oxide Nanostructures, Grant T. Olson

Master's Theses

Organic photovoltaics (OPVs) have received a great deal of focus in recent years as a possible alternative to expensive silicon based solar technology. Current challenges for organic photovoltaics are centered around improving their lifetimes and increasing their power conversion efficiencies. One approach to improving the lifetime of such devices has been the inclusion of inorganic metal oxide layers, but interaction between the metal oxides and common conjugated polymers is not favorable. Here we present two methods by which the interactions between polythiophenes and nanostructured ZnO can be made to be more favorable. Using the first method, direct side on attachment …

Ab Initio Studies Of Proton Transport In Proton Exchange Membranes, Jeffrey Keith Clark

Doctoral Dissertations

A molecular-level understanding of the factors that contribute to transport properties of proton exchange membranes (PEMs) for fuel cell applications is needed to aid in the development of superior membrane materials. Ab initio electronic structure calculations were undertaken on various PEM ionomer fragments to explore the effects of local hydration, side chain connectivity, protogenic group separation, and specific side chain chemistry on proton dissociation and transfer at low hydration. Cooperative interactions between both intra- and inter-molecular acidic groups and hydrogen bond connectivity were found to enhance proton dissociation at very low degrees of hydration. The energetics associated with proton transfer …

Methods For Quantitative Local Structure Analysis Of Crystalline Materials Employing High Performance Computing, Tara Marie Michels-Clark

Doctoral Dissertations

A fundamental computational methodology was investigated to extract quantitative local structure information from single crystal diffuse scattering data. The principles of a highly efficient, parallelizable local structure analysis using massively parallel computing resources at Oak Ridge National Laboratory (ORNL) are demonstrated on an organic hydrocarbon compound containing stacking faults, Tris(bicyclo[2.1.1]hexeno)benzene. A probabilistic model of the stacking variations with a five layer interaction depth was developed. The final model structure motif statistics are verified using the steady state distribution of Markov matrix representing the four to five layer transitions. The computations revealed that highly parallelizable “structure-clones” could replace less computationally efficient …

Understanding The Plasmonic Properties Of Metallic Nanostructures With Correlated Photon- And Electron-Driven Excitations, Vighter Ozezinimize Iberi

Doctoral Dissertations

The collective oscillation of the conduction band electrons in metal nanostructures, known as plasmons, can be used to manipulate light on length scales that are smaller than the diffraction limit of visible light. In this dissertation, a correlated approach is used to probe localized surface plasmon resonances (LSPRs) in metallic nanostructures, and their application to surface-enhanced spectroscopy. This correlated approach involves the measurement of LSPRs with dark-field optical microscopy (resonance-Rayleigh scattering), and electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Structural parameters of the exact same nanostructures obtained from the STEM are subsequently used in performing fully …

Porphyrin Cross-Linkers For Generating Soluble Molecularly Imprinted Polymers From Polyethyleneimine, Mohammed R. Elshaer

Seton Hall University Dissertations and Theses (ETDs)

Molecular recognition is vital to many biochemical processes and is at the heart of promising bio-medically related technologies. Molecular imprinting has a long-standing history as a successful method for mimicking the molecular recognition phenomena exhibited by nature, whereby artificial receptors are prepared for a given target molecule based on synthetic polymers. The molecularly imprinted polymer (MIP) contains a three dimensional network with a memorized cavity specific to the shape and functionality of the templated target molecule. The utility of traditional MIPs has been limited due to an inherent lack of solubility. We have worked toward developing a system that allows …

Tip-Enhances Raman Spectroscopy, Enabling Spectroscopy At The Nanoscale, Nastaran Kazemi Zanjani

Electronic Thesis and Dissertation Repository

The knowledge on the chemical and the structural properties of substances benefits strongly from characterization methods that can provide access to the sample’s nanoscale building blocks. Not only should the sensitivity of these methods approach a high detection limit up to single molecule, but also the accessible spatial resolution must enable chemical imaging of individual nanoscale features of the substances. High resolution imaging is often provided by electron microscopes through methods such as transmission electron microscopy (TEM) and scanning electron microscopy (STM), nevertheless, these methods lack offering chemical information. Surface-enhanced spectroscopy was developed to improve the sensitivity of the chemical …

The Electrochemistry Of Hydrogen Peroxide On Uranium Dioxide And The Modelling Of Used Nuclear Fuel Corrosion Under Permanent Disposal Conditions, Linda Wu

Electronic Thesis and Dissertation Repository

This thesis reports a series of investigations examining the corrosion process of used nuclear fuel under permanent disposal conditions. The motivation of the project is that the safety assessment of deep geological disposal of spent nuclear fuel requires a fundamental understanding of the processes controlling fuel corrosion which could lead to the release of radionuclides to the geosphere from a failed container.

One primary objective of this project was to develop a computational model in order to simulate fuel corrosion under the disposal conditions. A series of simulations based on COMSOL were designed and developed to determine the influence of …

Self-Assembly Of Block Copolymers For The Fabrication Of Functional Nanomaterials, Li Yao

Doctoral Dissertations

This dissertation explores the use of block copolymers which can self-assemble into different morphologies as templates to fabricate nanostructured materials. The first section (Chapters 2-4) reports the formation of mesoporous silica films with spherical, cylindrical and bicontinuous pores up to 40 nm in diameter through replicating the morphologies of the solid block copolymer (BCP) templates, polystyrene-b-poly(tert-butyl acrylate) (PS-b-PtBA), via phase selective condensation of tetraethylorthosilicate in supercritical CO2. Next, directed self-assembly was used to control the orientation of cylindrical domains in PS-b-PtBA templates. Large-area aligned mesochannels in silica films with diameters tunable between …

Synthesis, Characterization And Potential Applications Of Palladium And Ruthenium Nanostructures, Clara Patrice Adams

Dissertations

Controlling the size and shape of metal nanostructures is important for tuning the intrinsic chemical and physical properties of materials, and consequently their potential technological applications. Modulating the morphology of metal nanostructures is essential to understanding the structure-function relationship (for example, optical, magnetic, catalytic, and electronic properties) under various environmental conditions. Our work describes the development of new procedures for the synthesis of well-defined isotropic and anisotropic nanoparticles consisting of palladium (Pd) and ruthenium (Ru). Characterization of the nanostructures was carried out using transmission electron microscopy (TEM), high resolution-TEM (HRTEM), powder x-ray diffraction (XRD), selected area electron diffraction (SAED) and …

Size-Dependent Interactions Of Metal Nanoparticles With Fluorophores And Semiconductors, Liyana A. Wajira Ariyadasa

Dissertations

In recent years, nanoscale metallic particles have gained considerable interest due to their potential applications in advanced technology. Despite such interest, synthetic procedures that produce gram-scale, well-defined metallic nanoparticles with controlled size and shape, especially with diameters less than 5 nm remains a challenge. Our work has focused on developing synthetic procedures that produce well-defined platinum and palladium metal nanoparticles in the 1-5 nm size range. Thioether ligands were used as stabilizers and resulted in metal nanoparticles with controlled size. The nanoparticles were characterized using transmission electron microscopy (TEM), x-ray diffraction (XRD), selected area electron diffraction (SAED), x-ray photoelectron spectroscopy …

Surface Functionalization And Bioconjugation Of Nanoparticles For Biomedical Applications, Longyan Chen

Electronic Thesis and Dissertation Repository

Colloidal inorganic nanoparticles (NPs) have been attracting considerable interest in biomedicine, from drug and gene delivery to imaging, sensing and diagnostics. It is essential to modify the surface of nanoparticles to have enhanced biocompatibility and functionality for the in vitro and in vivo applications, especially in delivering locally and recognizing biomolecules. Herein, the goal of this research work is to develop advanced NPs with well-tailored surface functionalities and/or bio-functionality for the applications in cell tracking and analytes detection.

In the first project, quantum dots incorporating with gelatin nanoparticles (QDs-GNPs) have been developed for bioimaging applications. Two different approaches have been …

Degradation Of High Voltage Glass Fiber-Reinforced Polymer Matrix Composites By Aggressive Environmental Conditions, Tianyi Lu

Electronic Theses and Dissertations

Polymer matrix composites reinforced with either E glass or ECR glass fibers-reinforced are used in a variety of high voltage electrical applications because of their advantages like lower weight and cost. However, they can be damaged by aggressive in-service conditions such as high temperature, ultraviolet radiation, moisture, ozone and corrosive environments. Different degradation mechanisms can develop in high voltage PMCs under those extreme environments, which, in turn, can affect the long term structural durability of the composites. A set of PMCs reinforced with ECR-glass and E-glass fibers embedded in four different resins has been investigated in this study. In addition, …

Functional Properties Of Whey Protein And Its Application In Nanocomposite Materials And Functional Foods, Helen Walsh

Graduate College Dissertations and Theses

Whey is a byproduct of cheese making; whey proteins are globular proteins which can be modified and polymerized to add functional benefits, these benefits can be both nutritional and structural in foods. Modified proteins can be used in non-foods, being of particular interest in polymer films and coatings. Food packaging materials, including plastics, can linings, interior coatings of paper containers, and beverage cap sealing materials, are generally made of synthetic petroleum based compounds. These synthetic materials may pose a potential human health risk due to presence of certain chemicals such as Bisphenol A (BPA). They also add to environmental pollution, …

Synthesis And Characterization Of Sugar Based Low Molecular Weight Gelators And The Preparation Of Chiral Sulfinamides, Hari Prasad Reddy Mangunuru

Chemistry & Biochemistry Theses & Dissertations

Low molecular weight gelators (LMWGs) have received considerable attention in the field of chemistry from last few decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and forms gel, because of the self-assembly phenomenon and their demonstrated potential uses in a variety of areas, ranging from environmental to medicinal applications.

Sugars are good starting materials to synthesize the new class of LMWG's, because these are different from some expensive materials, these are natural products. We have synthesized and characterized the LMGS's based on D-glucose and D …