Physical Sciences and Mathematics Commons^™

Studies On Molecular Sieve Crystallization And Heteroatomic Substitution, Adam R. Macintosh

Electronic Thesis and Dissertation Repository

Molecular sieves have been scientifically and industrially important materials since their inception. These porous, crystalline networks of tetrahedrally coordinated atoms bridged by oxygen are known for their extremely high surface area and low density, making them excellent systems for catalysis. The framework of the AlPO₄ family of molecular sieves is itself non-catalytic, but through heteroatomic substitution these materials can diversify into the catalytically active silicoaluminophosphate (SAPO) and metalloaluminophosphate (MAPO) families of heterogeneous acid and redox catalysts. Research into the methods by which these substitutions occur, and the effects therein on the crystallization of the sieves, is of great importance, …

Controlled Degradation Of Poly(Ester Amide)S Via Cyclization Of Pendant Functional Groups, Jose Samuel Mejia

Electronic Thesis and Dissertation Repository

Polyesters have been used for many biomedical applications ranging from sutures to drug delivery vehicles. However, their bulk degradation results in an accumulation of acidic byproducts, which is detrimental to the human body. In order to circumvent this problem, as well as to impart new properties and functions to polymers for biomedical applications, poly(ester amide)s (PEAs) have been proposed as a different class of biodegradable polymers. However, up to date, there exists no way to stimulate the degradation of these polymers.

The Gillies research group has previously incorporated self-immolative spacers into polymers and has been able to stimulate their degradation …

Studies Of Microscopic Scale Strains In Nickel Alloys Resulting From Mechanical And Chemical Forces, Jing Chao

Electronic Thesis and Dissertation Repository

The nickel-based Alloy 600, also known as Inconel 600 has been found to be susceptible to stress corrosion cracking (SCC) in high temperature aqueous environments. Despite extensive research, the mechanisms by which this process occurs remain in question. It is known that SCC results from the simultaneous effects of a chemically corrosive environment and a tensile stress. Many studies have been conducted on the microscopic chemical changes associated with SCC. There have been fewer studies of the microscopic stress/strain process. The main objective of this thesis is to use the new x-ray based diffraction technique – polychromatic x-ray microdiffraction (PXM) …

In-Capillary Reduction And Digestion Of Proteins At Nano-Liter Volume Using Capillary Electrophoresis, Thasneen Naina Nazeema

Electronic Thesis and Dissertation Repository

To analyze the proteins present in biological samples several major steps are involved. One of the crucial steps in proteomics has been sample preparation. Prior to mass spectral analysis proteins containing disulfide bonds must be reduced which is followed by digestion. In this work, a novel way of performing protein reduction and digestion at nano-liter volume using capillary electrophoresis is presented. In this work, zone passing CE technique was utilized to analyze the reduction products in CE. After the successful in-capillary reduction, digestion of protein was also performed. A pH mediated stacking was used to bring the reduced protein and …

Fundamental Studies And Bioanalytical Applications Of Nanostructured-Initiator Mass Spectrometry (Nims), Jin Li

Electronic Thesis and Dissertation Repository

Nanostructured-Initiator Mass Spectrometry (NIMS), which uses ‘initiator’ molecules trapped within a nanostructured material to assist the release and ionization of intact molecules adsorbed on that material's surface upon laser or ion irradiation, is a new soft desorption/ ionization technique with several positive attributes including extraordinarily high detection sensitivities, relatively simple sample preparation protocols, and can be initiated using photon or ion irradiation sources. As result NIMS has a great deal of potential for the ready detection of small molecules from complex biofluids including metabolites, and for tissue imaging.

In the thesis, a variety of nanostructured materials including porous silicon (pSi), …

Analysis Of Adp-Ribosylation And Protein Sample Preparation By Capillary Electrophoresis, Ming Huang

Electronic Thesis and Dissertation Repository

ADP-ribosylation is one of many biologically important protein post-translational modifications (PTMs) that received considerable research interest in the past decade. The first part of this work presents the analysis of ADP-ribosylation, with special focus on the catalytic domain of an enzyme ARTD-10. The application of capillary electrophoresis (CE) is proposed in this work to separate the in vitro enzymatic mono-ADP-ribosylated ARTD-10 catalytic domain and its unmodified form. Another exciting aspect of CE application with growing interest is the sample preparation. The effectiveness and efficiency for in-vial reaction, in-capillary mixed reaction and on-capillary-tip reaction by performing methyl esterification on phophopeptides were …

Investigations Of Zeolite Growth By Atomic Force Microscopy (Afm), Donghan Chen

Electronic Thesis and Dissertation Repository

Zeolites are microporous materials that have been used extensively in various fields. A better understanding on their crystallization process is important for their investigations. Atomic force microscopy (AFM) is a powerful tool for studying the growing traces on the crystal surface, providing information regarding the relation between surface events and framework structure. This thesis mainly focuses on the surface investigation of several zeolites and microporous materials. ZSM-11 single crystals were synthesized under hydrothermal conditions, and their crystallization process was monitored by AFM, PXRD, SEM, and SSNMR. SAPO-34 prepared under both HTS and DGC conditions showed morphological differences that are related …

Ionothermal Synthesis Of High Silica Zeolites In Deep Eutectic Solvents (Des), Zheng Sonia Lin

Electronic Thesis and Dissertation Repository

Phase-pure high silica zeolites have been synthesized using different deep eutectic solvents for the first time. ZSM-5 was made in tetrapropylammonium bromide/pentaerythritol. The reaction is affected by the amounts of seeding, water content, and organic structure-directing agent (SDA). Sodalite and ZSM-39 were prepared in tetramethylammonium chloride (TMACl)/1, 6-hexanediol by using the mineralizing agents NaOH and NH₄F, respectively. In urea/choline chloride, ZSM-5, Beta, ZSM-39, and ZSM-11 were made by using different organic SDAs in the presence of fluoride. The reaction temperature and the choice of organic SDA affect the type of structures being produced.

The crystallization of ZSM-39 in …

Scanning Electrochemical Microscopy Studies Of Nickel Surfaces And T24 Single Live Cells, Yu Sun

Electronic Thesis and Dissertation Repository

Scanning electrochemical microscopy offers a good insight into nickel surface analysis and human bladder cancer cell studies.

The surface microstructures are related with chemical reactivity by superimposing SECM, SEM and Tof-SIMS images together. Depth scans were exploited for studying chemical reactivity quantitatively by comparison with COMSOL simulation results. Simulation models are described.

Extracellular reactive oxygen species are detected by SECM. Quantitative results were demonstrated by simulation, and concentrations of H₂O₂ and O₂ were acquired. The interaction between cancer cells and vitamin C was investigated. The switch-type behaviour of vitamin C on the PMA-induced ROS burst of …

Synthesis Of Silicide Nanomaterials Using Chemical Vapour Deposition Method, Hamid Norouzi Banis

Electronic Thesis and Dissertation Repository

Recent research has evidenced that nanotechnology may bring about a material revolution which sweeps through different scientific fields and leads to dramatic changes in the use of natural resources and our everyday life. Compared to their bulk counterparts, the nanomaterials may exhibit significantly improved physical properties by shrinking their size to nanometer scale. Metal silicide are distinguished by their features of combining advantages of both metals and semiconductors which promises superior performance various fields. Despite the progress in the synthesis methods of nanomaterials, it still remains a big challenge in controlled synthesis of 1D silicide nanostructures due to the difficulties …

The Development Of Organometallic Oboc Peptide Libraries For Use In Molecular Imaging, Dana R. Cruickshank

Electronic Thesis and Dissertation Repository

The discovery of peptide-based targeted imaging agents is hindered by the required addition of a radionuclide that can affect the binding properties of the peptide. Screening of peptide libraries is problematic because they do not take into account the presence of the imaging agent. Herein the development of an organometallic OBOC peptide library that contain a rhenium (I) tricarbonyl-based imaging entity surrogate incorporated directly onto the peptide chain, is reported. Additionally, MALDI tandem mass spectrometry is reported as a method to deconvolute organometallic peptides containing four different rhenium (I) tricarbonyl chelates on the N-terminus of octapeptides. Furthermore, an organometallic OBOC …

Reactivity Of Dimethylplatinum(Ii) Complexes With Peroxides, Kyle R. Pellarin

Electronic Thesis and Dissertation Repository

This thesis describes a study of dimethylplatinum(II) complexes containing bidentate nitrogen donor ligands. This work deals with the oxidative addition of peroxides and focuses on synthesis, characterization and reaction mechanisms of these complexes.

Dimethylplatinum(II) complexes were reacted with oxidants dimethyldioxirane (DMDO), meta-chloroperbenzoic acid (m-CPBA) and phthaloyl peroxide. The use of these oxidants has allowed for the synthesis of novel platinum(IV) complexes by oxidative addition and the formation of unique supramolecular networks. The formation of both trans- and cis-oxidative addition products was controlled by the type of oxidant utilized. By varying the ligand design of the …

Reactions Of Platinum Complexes With Dimethylamine-Borane, Shawn M. Robinson

Electronic Thesis and Dissertation Repository

This thesis describes a study of the reactions of platinum complexes with dimethylamine-borane (DMAB) as models for alkane activation. It is concluded that sigma-borane complexes of platinum(II) or platinum(IV) will be difficult to synthesize or even to detect as intermediates in hydride transfer from boranes to platinum.

The complex [PtMe(O₂CCF₃)(bpy)] reacts with DMAB to form an intermediate [PtMeH(bpy)] complex, which undergoes reductive elimination of methane with further degradation to give platinum(0) and free 2,2’-bipyridine. The addition of methyl acrylate to the reaction allowed the trapping of the platinum-hydride, producing [PtCl(CHMeCO₂Me)(bpy)] and [Pt(CHMeCO₂Me) …

Migration Behaviour Of Discontinuous Buffers In Capillary Electrophoresis During Protein Enrichment, Ting Li

Electronic Thesis and Dissertation Repository

To enrich protein at sub-microliter sample volumes, our group has developed a discontinuous buffer system which consists of an acid and a base inside a capillary. Upon voltage application, the protein moves towards and stacks at the pH junction. Prior to this work, we only focused on the protein enrichment and have not investigated the migration behaviour of various ions in this system. However, it is important to understand the mechanism of the migration of these ions, because the pH junction formation and further the protein enrichment are based on it. In this work, the ion migration patterns at the …

The Multicomponent Synthesis Of Pyrroles From Cylcopropane S Using A One Pot Pd(0) Catalyzed Dehydrocarbonylation Protocol, William J. Humenny

Electronic Thesis and Dissertation Repository

Previous work done by the Kerr group has shown that tetrahydro-1,2-oxazines can be efficiently synthesized using a three component coupling reaction between a hydroxylamine, aldehyde and cyclopropane diester. This affords the desired heterocycle efficiently with a wide variety of substitution. When one esters bears an allyl group a Tsuji dehydrocarbonylation reaction may take place resulting in the formation of a 4,5-dihydro-1,2-oxazine. This motif contains a vinylogously acidic proton which is extremely labile and easily deprotonated. Under basic conditions this proton is removed and consequently the N-O bond is cleaved and subsequent condensation occurs forming a pyrrole. Using a sequence of …

X-Ray Absorption Fine Structure And X-Ray Excited Optical Luminescence Studies Of One-Dimensional Nanomaterials, Lijia Liu

Electronic Thesis and Dissertation Repository

One dimensional nanomaterials have attracted extensive attention in recent years due to their superior electrical, optical, mechanical and chemical properties compared to their bulk counterparts. In this thesis, electronic structure and optical properties of three types of nanomaterials are investigated using synchrotron based X-ray absorption spectroscopy: X-ray absorption fine structure (XAFS) and X-ray excited optical luminescence (XEOL).

Si nanowire arrays are synthesized using electroless chemical etching, and coated with platinum and gold nanoparticles. The interaction between metal nanoparticles and the nanowire substrate is investigated using X-ray absorption near-edge structure (XANES). The luminescence properties of thermally oxidized Si nanostructures, such as …

High-Pressure Study Of Molecular Solids And 1d Nanostructures By Vibrational Spectroscopy And Synchrotron X-Ray Diffraction, Zhaohui Dong

Electronic Thesis and Dissertation Repository

Pressure plays a critical role in regulating the structures and properties of materials. Since Percy Bridgeman was recognized by the 1946 Nobel Prize for his contribution to high-pressure physics, high-pressure research as an interdisciplinary area has attracted extensive attentions. Nowadays, the high-pressure research involves broad frontier areas, such as chemistry, physics, biology, material and earth science. For instance, brand new classes of inorganic materials of unusual stoichiometries and crystal structures, with wide range of optical, mechanical, electronic and magnetic properties, have been produced at high pressure. Pressure-induced structural transformations between crystalline and amorphous materials, as well as among insulators, conductors …

The Synthesis And Reactivity Of New Pnictogen(Iii) Cations, Allison L. Brazeau

Electronic Thesis and Dissertation Repository

Chelating nitrogen based ligands are well known for their use with transition metals while their chemistry with p-block elements has been relatively underdeveloped. This thesis examines the structure, bonding and reactivity of group 15 elements supported by a pyridyl tethered 1,2-bis(imino)acenaphthene (“clamshell”) and various homo- and heteroleptic guanidinate frameworks.

The unique “clamshell” ligand contains a pendant Lewis base and has been used to support N-heterocyclic phosphenium and arsenium cations. Reactivity studies with the phosphorus analogue demonstrate the ability of the ligand to act as a Lewis base, while the phosphorus centre provides a Lewis acidic site, showing the amphoteric …

Complementary And Self-Complementary Hydrogen Bond Double Helical Complexes, Bhanu P. Mudraboyina

Electronic Thesis and Dissertation Repository

The design of artificial or synthetic strands that self-assemble to form double-helical complexes have been of great interest to chemists and researchers since the discovery of the double helical DNA structure in 1953 by Watson and Crick. Most of the complexes were self-complementary double-helical homodimers and while few heterodimer complexes are also known. The present thesis describes the design, synthesis and characterization of complementary and self-complementary hydrogen bond arrays built from heterocycles such as pyridine, thiazine dioxide and indole connected in different sequences. The sequence-based stabilities, insolubility issues, substitution and preorganization effects in these arrays have been studied in detail. …

Electrohydrodynamic Enhancement Of Heat Transfer And Mass Transport In Gaseous Media, Bulk Dielectric Liquids And Dielectric Thin Liquid Films, Seyed Reza Mahmoudi

Electronic Thesis and Dissertation Repository

Controlling transport phenomena in liquid and gaseous media through electrostatic forces has brought new important scientific and industrial applications. Although numerous EHD applications have been explored and extensively studied so far, the fast-growing technologies, mainly in the semiconductor industry, introduce new challenges and demands. These challenges require enhancement of heat transfer and mass transport in small scales (sometimes in molecular scales) to remove highly concentrated heat fluxes from reduced size devices. Electric field induced flows, or electrohydrodynamics (EHD), have shown promise in both macro and micro-scale devices.

Several existing problems in EHD heat transfer enhancements were investigated in this thesis. …

Heme Binding And Transfer In The Isd Heme Scavenging Pathway Of Staphylococcus Aureus, Michael T. Tiedemann

Electronic Thesis and Dissertation Repository

The antibiotic resistant bacterium Staphylococcus aureus is a significant problem in hospitals and communities worldwide. Survival of the bacterium in the host is reliant on iron scavenging. Staphylococcus aureus has adopted specialized mechanisms for scavenging iron from the host. The cell wall and membrane-associated iron regulated surface determinant (Isd) proteins allow Staphylococcus aureus to scavenge iron from the heme in hemoglobin. There are nine Isd proteins (IsdH, IsdB, IsdA, IsdC, IsdE, IsdD, IsdF, IsdG and IsdI) located at different depths in the cell wall and membrane. Magnetic circular dichroism (MCD) spectroscopy and electrospray ionization mass spectrometry (ESI-MS) have been used …

Kinetics Of O2 Reduction On Oxide-Covered Ni-Cr-Mo Alloys, Xiangrong (Sarah) Zhang

Electronic Thesis and Dissertation Repository

Ni-Cr-Mo alloys exhibit exceptional corrosion resistance and are widely used in chemical processing industries. The reliable performance of these alloys under extreme industrial conditions, are generally attributed to the presence of a passive film on the alloy surface. O₂ reduction is the most likely cathodic process able to sustain metal oxidation (corrosion) in industrial environments. However, the kinetics of O₂ reduction on these oxide-covered alloys has hardly been studied, despite the possibility it may be the rate controlling process for corrosion, especially localized corrosion. The objectives of this research are to characterize the properties of the oxide film …

Structural Motifs Of Novel Metallothionein Proteins, Duncan E K Sutherland

Electronic Thesis and Dissertation Repository

Metallothioneins (MT) are a family of small cysteine rich proteins, which have been implicated in toxic metal detoxification, protection against oxidative stress, and as a metallochaperone. The most well studied member of the family is the mammalian MT, which consists of two domains: a β-domain with 9 cysteine residues, which sequesters 3 Cd²⁺/Zn²⁺, and an α-domain with 11 cysteine residues, which sequesters 4 Cd²⁺/Zn²⁺. The exact functions of MT are unknown but must relate to its metalation status. Several areas that could lead to the assignment of function include 1) the determination …

Solid-State Nuclear Magnetic Resonance Spectroscopy Of Unreceptive Quadrupolar Nuclei In Inorganic Materials, Andre Sutrisno

Electronic Thesis and Dissertation Repository

Preparation and characterization of inorganic materials is a crucial practice because understanding the relationship between structure and property is important for improving current performance and developing novel materials. Many metal centers in technologically and industrially important materials are unreceptive low-γ quadrupolar nuclei (i.e., possessing low natural abundance, low NMR frequencies and large quadrupole moments) and they usually give rise to very broad NMR resonances and low signal-to-noise ratios, making it difficult to acquire their solid-state NMR spectra. This thesis focuses on the characterization of inorganic materials using solid-state NMR (SSNMR) spectroscopy at very high magnetic field of …

Enhancing Raman And Fluorescence Spectroscopies With Nanosphere Lithography Platforms, Shabila Fayyaz

Electronic Thesis and Dissertation Repository

Localized surface plasmon resonance (LSPR) is of particular interest to enhance the limit of detection for spectroscopic techniques such as Raman and fluorescence via a surface enhancement from metallic nanostructures. In this study, using nanosphere lithography (NSL) technique, a series of gold nanostructures over glass surfaces are prepared. These nanostructures are used to record the surface enhanced Raman scattering (SERS) spectrum of benzenethiol and azobenzene thiol and the vibrational modes are compared to literature. Once protected with an ultrathin layer of SiO₂, the gold nanostructures are investigated using scanning confocal fluorescence microscopy to detect the fluorescence from a …

Synthesis Of Self-Immolative Monomers And Their Applications In Polymeric Materials, Matthew A. Dewit

Electronic Thesis and Dissertation Repository

Self-immolative spacers are a unique class of molecules employed in a variety of applications, particularly in the biomedical field. Most commonly, they are molecules containing two reactive termini with a capping group at one terminus and a substrate of interest at the other. Upon removal of the capping group, the spacer undergoes an intramolecular reaction that results in its removal from the molecule and liberation of the substrate. These spacers have been extensively studied in monomeric form within prodrugs, as well as to form dendrimers that have been used for applications such as signal amplification, molecular logic gates and amplified …

Progress Towards The Total Synthesis Of Amphidinolide C, Nicholas A. Morra

Electronic Thesis and Dissertation Repository

A second generation catalyst for the Mukaiyama oxidative cyclization for the formation of trans-THF rings is described. Co(nmp)₂, displays increased stability to the reaction conditions, resulting in lower catalyst loadings, lower reaction temperatures, and significantly higher purity and yields of the products. Three procedures have been developed with this new water-soluble catalyst that greatly simplifies the post-reaction purification, making this procedure the premier method of forming trans-THF rings.

This new catalyst has been applied towards the total synthesis of the potently bioactive macrocycle, Amphidinolide C. Herein we report the successful synthesis of several fragments of the …

Synthesis Of (±)-Quebrachamine, Tetrahydroisoquinocarbazoles, And Progress Towards Biselide A And E, Barbora Morra

Electronic Thesis and Dissertation Repository

A variety of methodologies developed in our research group have inspired the three separate projects reported. First, the total synthesis of (±)-quebrachamine was performed in 13 steps and 17.8% overall yield. Highlights of the synthesis include an efficient preparation of a functionalized indole core via a [3+2] annulation cycloaddition reaction between a functionalized nitrile and donor-acceptor cyclopropane and a photo induced 9-membered ring closure.

Secondly, we have reported the most efficent and highest yielding route to several tetrahydroisoquinocarbazoles, where the core was prepared in six steps from tryptophol in 51% overall yield. This work highlights for the first time the …

Scanning Probe Microscopy Studies Of The Properties Of Conducting Polymers, Kevin D. O'Neil

Electronic Thesis and Dissertation Repository

Electronically conducting polymers (ECPs) have been growing in interest as important materials for a variety of different applications such as charge storage devices and photovoltaics. However, in all of these applications, the performance of conducting polymers are strongly dependent upon their local properties such as morphology, local conductivity and carrier mobility, local chemical composition, etc. All polymer materials feature a distribution of these parameters and therefore, they are considered heterogeneous. In this work, we use atomic force microscopy (AFM) and its related techniques such as current-sensing AFM (CS-AFM), Kelvin probe force microscopy (KFM) and phase imaging (PI-AFM) to directly investigate …

Miniaturized Fractionation And Purification Of Analytes Of Interest In Complex Mixtures: Protein Enrichment And Purification With Capillary Electrophoresis And Identification Of Pesticide Chemicals In Bio-Oils, Christina J. Booker

Electronic Thesis and Dissertation Repository

The ability to isolate and detect an analyte of interest is vital for many different facets of life today, from disease detection to environmental safety. The goal of the method development discussed within this thesis is to isolate and identify unique analytes from complex matrices and to do so in a scaled down approach. Removal of an analyte from a diverse background of molecules is often required for successful detection and determination of analyte properties. As well, many samples are only available at low volumes and at trace levels so miniaturized techniques that only require small sample volumes are designed …