Chemistry Commons^™

Luminescent Group 11 Metal (I) Chalcogen Clusters With A Conjugated Diphosphine Ligand, Kai Yu Jeffrey Li

Electronic Thesis and Dissertation Repository

Polynuclear Au (I) complexes exhibit rich photochemical properties and have the potential to find applications as molecular sensors, switches, or energy storage devices. Although dinuclear Au (I) complexes with bridging diphosphines have been extensively examined, most of those reported do not contain rigid-diphosphine ligands.

This thesis examines how the rigid diphosphine, 4,6-bis(diphenylphosphino)dibenzofuran (DBFDP) can be incorporated for the controlled assembly of photoluminescent gold (I) metal – chalcogenolate (chalcogenolate = RS^-, RSe^-; R = organic moiety) and gold (I) chalcogenide (chalcogenide = S^2-, Se^2-) bimetallic complexes. In these studies, the chalcogen …

Exploring The Reactivity Of Metal-Ligand Cooperative Complexes With Dioxazolones, Terminal Alkynes, And 2-Ethynylbenzyl Alcohol, Megan A. Hoffer Miss

Electronic Thesis and Dissertation Repository

N-Acyl ketenimines were attempted to be synthesized catalytically by [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ with phenylacetylene and 3-phenethynyl-1,2,4-dioxazol-5-one. Trapping agents were employed to identify the major product of the reaction, as many products were formed. [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ reacts with 3-phenethynyl-1,2,4-dioxazol-5-one generating an isocyanate via the Curtius rearrangement, confirmed by a forced Curtius rearrangement with 3-phenethynyl-1,2,4-dioxazol-5-one and 1,2,4-triazole. Rates of vinylidene formation using [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ and various terminal alkynes of different sterics and electronics were evaluated using a Hammett analysis for and simple rate comparisons. …

Hydrogen Bond Activation Of Donor Acceptor Cyclopropanes, Matthew H.J. Pamenter

Electronic Thesis and Dissertation Repository

Donor acceptor cyclopropanes (DACs) are versatile organic building blocks used in the synthesis of many pharmaceutically relevant heterocycles. The combination of a high ring strain cyclopropane core and vicinal donor and acceptor substituents cause DACs to behave like 1,3-zwitterions. Recently, DACs have been activated by a hydrogen bond donor solvent in place of a Lewis acid catalyst, allowing the elimination of heavy metals commonly used in these transformations. Hexafluoroisopropanol (HFIP) as a hydrogen bond donor cosolvent was found to cause a downfield shift of the DACs electrophilic carbon in the 13C NMR spectrum. This indicates increased electrophilicity at this position …

Experimental And Simulation Study Of Reactive Silver Ink Droplet Evaporation, Weipeng Zhang

Electronic Thesis and Dissertation Repository

The evaporation of particle-free silver ink droplets on heated substrates directly impacts the morphology of the resultant silver particles and films. In this thesis, COMSOL Multiphysics simulations of the solvent (water-ethylene glycol mixture) droplet evaporation process are used to explain the microflows, mass transfers, and heat distribution responsible for the experimental observations. The reactive ink incorporates fluoro-surfactant FS-31 and poly (acrylamide) (PAM) to suppress the coffee-ring effect that negatively impacts the electrical conductivity. Experiments show that the droplet evaporation process results in varied silver particle morphology, depending on the locations within the droplet, leading to uneven surfaces. Large particles (3 …

Protein Stability In Solution And In The Gas Phase., Yousef Haidar

Electronic Thesis and Dissertation Repository

Electrospray Ionization mass spectrometry (ESI-MS) is widely used for probing proteins, yet many aspects of this technique remain elusive. Using MS, ion mobility spectrometry (IMS), and circular dichroism (CD) spectroscopy, this thesis sheds light on the stability differences of proteins in the gas phase and solution. After a general introduction (Chapter 1), Chapter 2 scrutinizes some aspects of native ESI. Our data highlight the significance of cone voltage in maintaining a native-like fold and show the advantage of using NH₄Ac in protein experiments. Chapter 3 focuses on hydrogen/deuterium exchange (HDX)-MS. Several studies have reported that D₂O …

Synchrotron Study Of Phase Transition And Heterostructures In Metal Oxide Semiconductors, Bingyu Dong

Electronic Thesis and Dissertation Repository

Transition metal oxides, including titanium dioxide (TiO₂), zinc oxide (ZnO) and Tin dioxide (SnO₂) are widely recognized semiconducting photocatalysts. This project engages in a detailed examination of the phase transition of TiO₂ and the synthesis of heterostructured metal oxides using an eco-friendly method of ball-milling. A variety of spectroscopy and microscopy techniques have been used to analyze the products. Synchrotron-based techniques: X-ray Absorption near-edge spectroscopy (XANES), X-ray Emission Spectroscopy and X-ray excited optical luminescence (XEOL) can demonstrate the local structure and bonding. The finding highlights a phase transition in TiO₂ and the formation of …

The Effect Of Hydrogen Peroxide On The Corrosion Dynamics Of Carbon Steel, Kwang Soak Gabriel O'Donnell

Electronic Thesis and Dissertation Repository

The Used Fuel Container (UFC) is a key barrier in Canada’s nuclear fuel disposal plan. Understanding the radiation-induced corrosion of the carbon steel (CS) vessel is critical for predicting the long-term integrity of the UFC. Developing a mechanistic understanding of CS corrosion and the effect of solution parameters is essential.

This work investigates the effects of H₂O₂, the key radiolytic oxidant, on CS corrosion dynamics in small, stagnant solutions. Elementary processes are identified, corrosion rates are calculated, and the effects of H₂O₂ concentration are investigated. Corrosion was studied by quantifying the concentrations of …

Application Of Crystal Engineering In Multicomponent Pharmaceutical Crystals: A Study Of Theory And Practice, Soroush Ahmadi Nasrabadi

Electronic Thesis and Dissertation Repository

Multicomponent crystallization, a prominent strategy in crystal engineering, offers the ability to modify the physicochemical properties of crystals by introducing a secondary component to their lattice structure. Such multicomponent crystals have found widespread application in the pharmaceutical industry. This thesis explores the experimental screening, characterization, application, and theoretical prediction of multicomponent crystals of Active Pharmaceutical Ingredients (APIs).

The first case study investigates a new solvate of Dasatinib which exhibits high instability at room temperature and transforms into a different polymorph upon desolvation. The crystal structure of this compound is obtained, revealing insights into its transient nature and the potential application …

Investigating Novel Luminescent Materials Towards Applications In Light Emitting Electrochemical Cells, Kenneth Chu

Electronic Thesis and Dissertation Repository

The search for new and better luminescent materials is becoming increasingly important, as there are significant cost-savings in using luminophores that are brighter and more efficient. Carbon quantum dots (CQDs) and other luminescent materials such as Pt-Ag nanoclusters and TADF compounds are an extremely appealing alternative to existing light-emitting materials, as they are low-cost, easy to synthesize, and non-toxic.

This thesis explores the properties and performance of different luminescent materials to be used in light-emitting electrochemical cells (LECs). In this work, we focused on LECs as their low cost and ease of fabrication aligns well with the ethos of CQDs …

The Effect Of Solution Parameters On The Interfacial Chemical Dynamics Of Early-Stage Corrosion, Brianna K. Rector

Electronic Thesis and Dissertation Repository

Corrosion is a key long-term degradation process for metallic components in nuclear industry infrastructure. Accurately predicting the corrosion rate of a component in its service environment is considered a grand challenge in the corrosion community. Corrosion is a multi-step electrochemical process, with elementary steps involving mass transfer across more than one stage. Due to the multi-step, multi-phase nature of corrosion systems, predicting corrosion behaviour over time is complex. Existing corrosion models can describe electron transfer and mass transport steps independently, under narrow sets of conditions or over a specified duration but cannot account for the changes that occur over time …

The Synthesis And Characterization Studies Of Modified Nucleobase In Pna And Dna, Gyeongsu Park

Electronic Thesis and Dissertation Repository

Nucleic acids have been extensively studied not only for their importance in biological systems as the medium of genetic information but also for their potential uses in therapeutic, diagnostic and other biological applications. As such, modified oligonucleotides and oligonucleotide analogues have drawn the attention of researchers from various disciplines. Modification of oligonucleotides can enhance their desired characteristics and engender unique properties, such as fluorescence, giving rise to a variety of applications. Peptide nucleic acid (PNA) is an oligonucleotide mimic with a pseudo-peptide backbone based on N-(2-aminoethyl)glycine that is renowned for high target binding affinity and resistance to enzyme degradation. …

Use Of Electrochemical Techniques And Statistical Analysis To Investigate The Pitting Probability Of Copper, Sina Matin

Electronic Thesis and Dissertation Repository

The development of a safe permanent disposal plan is essential for the long-term disposal of used fuel bundles. Nuclear Waste Management Organization (NWMO) has been investigating the deep geologic disposal of nuclear waste which offers the optimum passive safety system with a negligible probability of release of radionuclides into the environment.

The proposed used fuel containers (UFC) for the permanent disposal of high-level nuclear waste in Canada is comprised of a carbon steel vessel coated with a 3 mm corrosion-resistant copper layer deposited using a combination of electrodeposition and cold spray deposition. Although copper is often considered to be thermodynamically …

Investigating The Structure Of Metal-Organic Frameworks And The Behaviors Of Adsorbed Guest Molecules In Mofs Via Solid-State Nmr Spectroscopy, Yihao Shen

Electronic Thesis and Dissertation Repository

Metal-organic frameworks (MOFs) are a class of hybrid organic-inorganic microporous materials with lots of significant applications including gas capture and storage, gas separation, batteries, catalysis, ion exchange and drug delivery. MOFs based on s-block metals are important due to their many practical applications. These MOFs are also very interesting because the s-block MOFs often exhibit unpredictable behavior of coordination. In this thesis, the structures of six s-block metal (Li, Na, Cs, Mg, Ca, Sr) based MOFs involving V-shaped link, 4, 4′- sulfonyldibenzoate (SDB) are characterized by various techniques including, powder X-ray diffraction, TGA and solid-state NMR spectroscopy. ¹³C CPMAS …

Oligo [Poly(Ethylene Glycol) Fumarate] Gels With Photo-Sensitive Pendent Groups, Andrew Chung

Electronic Thesis and Dissertation Repository

Stimuli-responsive hydrogels are 3D polymeric structures that offer attractive qualities within the biomedical field due to their excellent biocompatibility and tunability to be employed in drug release, wound healing, and implants. Aliphatic polyesters are biodegradable polymers that naturally degrade by the process of simple ester hydrolysis. Oligo[poly(ethylene glycol) fumarate] (OPF) is a linear polyester containing repeating units of poly(ethylene glycol) and unsaturated fumarate. OPF naturally degrades through hydrolytic cleavage into poly(ethylene glycol) (PEG) and fumaric acid which is a naturally occurring compound found in the Kreb’s cycle. However, in some cases, it would be beneficial to activate or accelerate this …

Characterization Of Deposited Copper Oxide Films On Copper Substrates, Millicent Castillo

Electronic Thesis and Dissertation Repository

The deposition of copper oxide films on copper substrates was investigated by the electrochemical, thermal, and hydrothermal oxidation of copper. The formed oxides were characterized using various surface analytical techniques to determine the film’s morphology, composition, and thickness. The results show that by growing oxides electrochemically, a duplex layer composing of CuO and Cu₂O film was formed on the copper surface, having characteristics of being porous and possessing needle-like structures. An oxide film composed of CuO and Cu₂O, which shows minimal porosity and possess mixtures of crystalline and non-crystalline structures, is formed on the copper surface …

Synthesis Of Ni(Ii) Complexes For Allylic C(Sp3)-H Bond Activation For Aerobic Oxidation Catalysis, Shagana Kukendran

Electronic Thesis and Dissertation Repository

Nickel is a widely abundant and inexpensive metal. Catalysts are substances that remain unconsumed and increase the rate of reactions by reducing the activation energy barrier, often by providing an alternative route. The main goal of this study is to prepare Ni(II) complexes that can promote a catalytic aerobic oxidation reaction by breaking allylic C-H bonds. Based on previous studies, allylnickel N-heterocyclic carbene complexes react with molecular oxygen to give useful carbonyl compounds with a Ni(II)-OH by-product, which undergoes dimerization. In order to achieve catalysis, dimerization of the Ni(II)-OH should be prevented and C-H activation has to be achieved to …

Synthesis And Surface Modification Of Azide Decorated Silver Nanoclusters, Alexander H. Stöckli

Electronic Thesis and Dissertation Repository

In nanocluster research, easy modification of the cluster surface while maintaining the cluster core remains a key challenge. Herein we report the synthesis, structure, and properties of four targeted Ag₂₀ nanoclusters (NCs) with surface azide moieties, two of which have 8 azide moieties, [CO₃@Ag₂₀(S^tBu)₁₀(m-N₃-C₆H₄COO)₈(DMF)₄] and [CO₃@Ag₂₀(S^tBu)₁₀(p-N₃-C₆H₄COO)₈(DMF)₄], and two of which have 6 azide moieties, [CO₃@Ag₂₀(S …

Near-Ir Laser Ablation Of Simulated Radiologically Contaminated Oxides On Carbon Steel Feeder Pipes, Thao Viet Do

Electronic Thesis and Dissertation Repository

As nuclear power plants age and retire from service, many countries face significant challenges concerning the safe long-term storage and disposal of large volumes of low and intermediate level radioactive wastes (L&ILW). The volumes of metallic waste are of particular concern, as when metal corrodes it produces hydrogen that could lead to pressure build-up in interim storage and disposal. In Canada, a significant fraction of the metallic wastes for Canada Deuterium Uranium (CANDU) nuclear reactors are out-of-core reactor components, such as carbon steel (CS) feeder pipes. The radioactive contamination is expected to be largely confined to the surface oxide layers …

Expanding The Scope Of Clickable Azide-Functionalized Nanoclusters To Include Au144, Johanna A. De Jong

Electronic Thesis and Dissertation Repository

Thiolate-protected Au₁₄₄ nanoclusters (NCs) are an intriguing member of the gold NC family. Their geometric structure, distinct electrochemical features, and susceptibility to structural rearrangement under the duress of ligand exchange have been studied. However, there are currently no established protocols for surface modification or tuning of their ligand shells post synthesis. Here, the direct synthesis of three regioisomers of azide-modified Au₁₄₄ NCs with 60 azide moieties, i.e., Au₁₄₄(SC₂H₄C₆H₄-N₃)₆₀, is reported, in which the azide functionality is located at the ortho-, meta-, or …

The Synthesis, Lewis Acidity And Catalytic Activity Of Bis(Catecholato)Germanes, Andrew T. Henry

Electronic Thesis and Dissertation Repository

Main group Lewis acids have been shown to be viable alternatives to state-of-theart transition metal catalysts. While extensive research into a variety of p-block Lewis acids have been reported, the field of germanium Lewis acid chemistry has been described as “almost non-existent”. A variety of bis(catecholato)germane derivatives have been synthesized. The Lewis acidity of these compounds was analyzed by the Gutmann-Beckett and fluoride ion affinity methods demonstrating the high Lewis acidity of these complexes. The bis(catecholato)germanes were utilized as Lewis acid catalysts for the hydrosilylation of aldehydes, the hydroboration of alkynes, Friedel-Crafts alkylation of alkenes, and the oligomerization of styrene …

Developing Carbon Quantum Dots As A Luminescent Material And Revisiting Ecl And Led Absolute Measurement Methods, Jonathan Ralph Adsetts

Electronic Thesis and Dissertation Repository

Luminescent materials play increasingly important roles in our lives. Improvements in these materials’ quantum efficiencies (QEs), costs and toxicity can greatly reduce the power consumption, price and environmental damage to the planet, respectively. Carbon quantum dots (CQDs) and luminescent materials exhibiting thermally activated delayed fluorescence (TADF) are two interesting materials in these aspects. Furthermore, measurements on electrochemiluminescence (ECL) and electroluminescence of these luminescent materials can quickly evaluate their performance for many applications. In this thesis, controlled CQD syntheses are revealed beneficial to luminescent materials applications. Their film ECL demonstrated relatively stable anionic and cationic radicals leading to high emission at …

Conformational Dynamics And Aggregation Of Thermally Stressed Proteins Studied By Hydrogen/Deuterium Exchange Mass Spectrometry, Nastaran Nosrat Tajoddin

Electronic Thesis and Dissertation Repository

Proteins perform various biological functions, e.g., as enzymes or transporters. In addition to naturally occurring proteins, the use of protein therapeutic drugs for treating cancer and other diseases is a rapidly growing area. A thorough biophysical characterization of proteins and protein therapeutics opens the door to a more comprehensive understanding of their role in health and disease. This dissertation aims to expand the capabilities of an existing technique (Hydrogen Deuterium Exchange Mass Spectrometry, HDX-MS), which is widely used for probing protein structure and dynamics. Conventionally, HDX-MS experiments are performed as a function of labelling time. Here we aim to establish …

The Coordination Chemistry And Reactivity Of Pd Phosphine 1-Azaallyl Complexes, Kyle M. Jackman

Electronic Thesis and Dissertation Repository

Structurally responsive ligands (SRLs) are a class of ligands that change their coordination mode with a metal centre, which permits reactions that are difficult with non-SRLs, allow access to unique mechanisms, and allow isolation of unusual coordination complexes. The 1-azaallyl (1-AzA) family of SRLs are capable of isomerizing between η³-NCC and κ¹-N modes that occupy two and one coordination sites, respectively. This thesis investigates a new class of phosphine 1^AzA (P^AzA) ligands and the reactivity of their coordination complexes with palladium.

The first-generation P^AzA ligand contains a phenyl linkage between the two heteroatoms and affords a …

Characterization Of 1d And 2d Materials With Tip-Enhanced Raman Spectroscopy, María Olivia Avilés

Electronic Thesis and Dissertation Repository

Carbon-based materials, such as 1D single-walled carbon nanotubes (SWCNT) or 2D graphene, are promising materials for a variety of applications in energy storage, biosensors, and medical imaging applications. Similarly, beyond graphene, 2D transition metal dichalcogenides (TDM) that can have either a metallic or semiconducting character have gained interest for potential applications in electronics and photonics. Specifically, metallic TMDs such as vanadium disulfide (VS₂) show potential applications in optoelectronics and lithium-ion batteries. On the other hand, semiconducting TDMs like tungsten disulfide (WS₂) show a direct band gap, making them interesting for photovoltaic applications, transistors, or photodetectors. The …

Investigating The Mechanism Of Protein And Peptide Electrospray Ionization, Elnaz Aliyari

Electronic Thesis and Dissertation Repository

Electrospray ionization (ESI) mass spectrometry (MS) is widely used for the detection and characterization of various analytes. However, many fundamental aspects of the ESI process remain poorly understood. Using molecular dynamics (MD) simulations, MS, and ion mobility spectrometry (IMS), this thesis sheds light on the mechanisms whereby gaseous analyte ions are formed from highly charged ESI nanodroplets. After a general introduction (Chapter 1), Chapter 2 focuses on the ion evaporation mechanism (IEM), i.e., the ejection of analyte ions from the droplet surface. The IEM is well established for low MW compounds, but it has remained contentious whether this pathway is …

Pressure-Induced Modifications To The Structural And Optoelectronic Properties Of 2d Hybrid Organic-Inorganic Perovskites, Jesse Ratte

Electronic Thesis and Dissertation Repository

Recently, 2D hybrid organic-inorganic perovskites (HOIP) have garnered lots of research interest for their applications in optoelectronic devices, especially in solar cells. The optoelectronic properties of 2D HOIPs have yet to be optimized for these applications. High external pressure is well known to induce structural modifications to 2D HOIPs, and thus modify their optoelectronic properties. Herein, we report a study of the effects of high pressure (HP) on the structures and optoelectronic properties of cyclohexane methylamine (CMA) lead iodide (CMA2PbI4) and the structures of N,N-dimethylphenylene-p-diammonium (DPDA) lead iodide (DPDAPbI4).

High pressure measurements of CMA2PbI4 were performed using Raman spectroscopy, Fourier-transform …

Natural Product Discovery And Mycotoxin Analysis Of Agricultural Endophytes And Pathogens, Jacob P. Walsh

Electronic Thesis and Dissertation Repository

This thesis focuses on the application of fungal natural product chemistry for the use of agriculture fungal pathogenesis research. The research in this work uses many analytical chemistry techniques and instruments such as HPLC, LC-MS/MS and NMR. In Chapter 2, a diagnostic fragmentation module was developed for the identification of compound classes in crude fungal extracts. This module identified the classes cytochalasins and chaetoglobosins from extracts of Penicillium, Chaetomium, and Xylaria. From these extracts a new chaetoglobosin was discovered and the module was implemented into the open-source software package MZmine 2.0. Chapter 3 discusses analytical chemistry techniques with the …

Analyzing Enhanced Electrochemiluminescence Of Novel Materials, Liuqing Yang

Electronic Thesis and Dissertation Repository

As a powerful analytical technique, electrochemiluminescence (ECL) has found wide applications in the fields of bioanalysis and light-emitting devices. However, many ECL materials sustain the shortcomings of low ECL efficiencies. To better design novel materials with ECL enhancement, it is essential to investigate and the enhanced ECL mechanisms. In this thesis, ECL enhancements of various novel materials were analyzed utilizing ECL-voltage curves, potential pulsing experiments, ECL and photoluminescence spectroscopies, and other characterization methods. Specifically, two graphene quantum dots (GQDs) with different heteroatom doping were designed and synthesized. Structural characterizations and spectroscopies demonstrated that the heteroatom doping could change the surface …

Design And Surface Modification Of Noble Metal-Based Nanocatalysts, Xuchun Wang

Electronic Thesis and Dissertation Repository

This thesis investigates approaches to modifying the surface structure of noble metal-based nanocatalysts. Noble metal-based nanocatalysts, such as Pt and Pd, play a significant role in heterogeneous catalysis due to their capabilities in activating the cleavage or formation of chemical bonds, but still suffer from the high-cost issue and unsatisfied catalytic performance due to too strong or too weak adsorption of intermediates. Considering the surface specificity of heterogeneous catalysis, Bi, a cheap metal, was used to modify the surface of Pt- and Pd-based nanocatalysts. This thesis aims to unveil the role of Bi in improving their catalytic performance from both …

Oxygen Speciation In Potassium Silicate And Potassium Aluminosilicate Glasses: Insights From X-Ray Photoelectron Spectroscopy, Ryan Sawyer

Electronic Thesis and Dissertation Repository

In a geological context, glasses are useful analogues for silicate melts as they are more readily studied in the laboratory using a wide range of techniques that are impractical for molten liquids. Understanding the structure of binary silicate glasses can help us understand more about the magmatic processes that affect terrestrial planetary bodies.

Potassium silicate glasses ranging in composition from 10 mol% to 35 mol% K₂O were studied using X-ray Photoelectron Spectroscopy (XPS). From high resolution O 1s XPS spectra, Bridging Oxygen (BO) mole fractions were calculated and compared with those of previous ²⁹Si MAS NMR studies. …