Recently, there has been increased effort in researching methods for producing hollow nanostructures because of their potential impact in the fields of catalysis, separation processes, drug delivery, and energy storage and conversion devices. The purpose of this thesis is to describe a method for forming hollow inorganic-organic hybrid nanoboxes and nanoframes. This approach relies upon ionic liquid (1-butyl-3-methyl-imidazolium chloride) mediated auto-templating assembly of CaCO3 and chitosan to form nanoframes (two open faces) and nanoboxes (one open face). The average dimension of the nanostructures formed was 339 ± 95 x 299 ± 89 nm. Detailed structure of nanoboxes and nanoframes were obtained by 3-D electron tomography and X-ray diffraction. Chemical bonding was determined by FTIR, and the ratio of organics to inorganics in the nanostructures was determined by thermal gravimetric analysis. The chitosan to CaCO3 weigh ratio, mixing strength, temperature, and dialysis time were varied to further elucidate the method of formation. It was found that increasing the mixing power caused the equilibrium nanostructure dimension to decrease. On the other hand, varying the experimental temperature in the range of 80 to 160˚C did not affect the nanostructure dimension. The dialysis study showed that during dialysis the nanostructure core was increasingly removed. Nanoframes were observed after 72 hours of dialysis. With further dialysis, there was continued erosion of nanoframes. Results indicate that the concentration gradient and the solubility difference between the mixture components were responsible for this transformation.

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The existence of Room Temperature Ionic Liquids (RTILs) has been known for a long time, but only recently have they been pulled to the forefront of chemical research. This increase in attention can be attributed to a keen interest in their intrinsic properties for a wide variety of potential applications. RTILs have been used as alternative solvents for organic synthesis as well as catalysis, as well as supports for the purification or extraction of metals. Being ionic in nature and liquid at temperatures below 100°C, RTILs lend themselves to the electrochemist. As a result, they have been looked at for use in electrochemical systems such as high capacity batteries and supercapacitors. Due to their extremely high density of charge carriers relative to more well-known aqueous electrochemical systems, a new theoretical approach must be taken. Currently, a large gap exists between theoretical approaches and experimental results. The work contained within this thesis aims to provide insight into the interface between a RTIL and an electrified gold electrode.

Graphene has been extensively studied for possible future technical applications due to its unique electronic, transport, and mechanical properties. For practical applications, graphene often needs to be placed in a medium or on a substrate. The interfacial interaction between graphene and other materials can greatly affect the performance of graphene-based devices, but has not been well explored. My thesis research focused on developing a better understanding of the interface of pristine and chemically/mechanically modified graphene sheets with ionic liquids (ILs) as well as amorphous silica (a-SiO₂) surfaces using first principles-based atomistic modeling which combines density functional theory, classical molecular dynamics, and Metropolis Monte Carlo. The major focus of my thesis research was on investigating the interfacial structure and capacitance between graphene and ILs; graphene-based materials and ILs have been regarded as viable candidates for supercapacitor electrodes and electrolytes, respectively. Particular emphasis was placed on elucidating the relative contributions of the electric double layer (EDL) capacitance at the graphene/IL interface and the quantum capacitance of graphene-like electrodes. More specifically, we first determined the microstructure (such as orientation, packing density, cation-anion segregation) of chosen ILs near planar graphene electrodes with various surface charge densities. Based on the calculated IL microstructure for each system, the EDL capacitance was then evaluated with particular attention to the effect of cation-anion size difference. We also examined the influence of the chemical and mechanical modifications of graphene-like electrodes on the supercapacitor performance. Especially, mechanisms underlying chemical doping-induced enhancement of the total interfacial capacitance were addressed through analysis of electrode quantum capacitance changes resulting from electronic structure modifications. A part of my effort was also devoted to examining the binding interaction of graphene with a-SiO₂ (which is not yet clearly understood despite its scientific and technological importance). In particular, we attempted to evaluate quantitatively the adsorption strength of graphene on the a-SiO₂ surface, which has been under debate mainly due to the difficulty of direct measurement. / text

DNA has been widely studied in a variety of solvents. The majority of these solvents consist of either aqueous or organic components. The presence of ions or salts in these solvents can further alter DNA properties by changing the melting point or helical structure. The size, charge, and concentration of these additional components can all affect the behaviour of DNA. A new class of solvents, known as ionic liquids have recently gained popularity. Ionic liquids are comprised of entirely of ions and can be liquid at room temperature. Due to their low volatility and ability to dissolve both polar and non-polar substances, they are generating high levels of interest as ‘green solvents’. Although the interaction between DNA and ionic liquids has been characterized, the potential of this interaction is still being studied. It was discovered that when DNA mixed with DNA intercalating dyes was added to ionic liquids, there was a large reduction in fluorescence. Although this fluorescence drop was believed to occur to removal of the dye molecule from the helix, the strength of this interaction has not been researched. In this thesis, the interaction between different intercalating dyes and different ionic liquids was evaluated. We reasoned that perhaps the difference in interaction could be used as a method of separating the DNA-dye complex, which has previously never been accomplished. For example, it has been established that both DNA and cationic dyes have an affinity for ionic liquids. The relative strength of this affinity is undetermined, as well as the comparison to normal aqueous mediums. Although ionic liquids can drastically alter the stability of the DNA duplex by either raising or decreasing the melting point depending on the ionic liquid chosen, we found that the DNA actually has a higher affinity for the aqueous phase. Conversely, intercalating dyes prefer to partition into the ionic phase. The relative affinities of the two components are strong enough for their respective phases that the complex can be split apart and each component can be extracted, allowing for separation of the two.

Since the discovery of organic semiconductors (OSCs) over four decades ago, the field of organic electronics has broken our misconceptions regarding the possibilities of modern electronics. The synthetic toolkit of organic chemistry enables the creation of a limitless number of unique OSCs that can be specifically tailored and engineered with the specific and desired properties for unique applications. The rapid adoption of modern information systems, “Internet of Things,” in which smart devices and sensors ubiquitously collect and exchange data has resulted in a need for low-cost sensors to be deployed everywhere from the monitoring of food supply chains, environmental conditions, to human health. Organic thin-film transistors (OTFTs) are a necessary component to support these technologies. However, their mass adoption will require reduction in cost and improved compatibility with low voltage generating printed batteries or flexible and ultrathin photovoltaics. This thesis is focused on the development of high performing solid state polymer electrolytes to be employed as the gating medium in OTFTs. The choice of conventional gating materials often leads to a tradeoff between high capacitance, operating speed and material softness. For example liquid electrolyte gating materials have high capacitance but low operating speed and are liquid at room temperature which is unacceptable for many electronics application. Polymer gating materials often have lower capacitance but fast operating conditions and solid at room temperature. In this thesis we establish structure property relationships which aid in the design of novel block copolymer-based gating materials which simultaneously enable the increase in capacitance and switching speed while remaining solid at room temperature. In the first study I established a styrene-based ionic liquid monomer can be using as a controlling monomer in the nitroxide mediated copolymerization of methacrylates. The second study then focuses on the integration of these materials into OTFT devices; the morphology (block vs random copolymers) effect on device performance is assessed. The last study builds on the findings of the previous study and further explores the structural elements of block copolymers on device performance. The work presented here outlines the development of advanced poly(ionic liquid) based solid electrolyte materials that enables both reduced operating voltages and fast switching. Finally, we establish structure-property relationships that relate the molecular architecture to OTFT device performance paving the way for the adoption of a new generation of high performing, printable and flexible electronics.

The current environmental situation, with respect to global warming and the ever– approaching depletion of fossil fuel sources, places significance on the development of green fuel and platform chemical production methods. In this context, processes that utilise biomass sources as feedstock, are of great interest. Cellulose, which is the most abundant biopolymer in nature, is a renewable low–cost carbon resource derived from harvest residues and sources like wood and straw. Glucose generation from cellulose requires a saccharide conversion, whereby the β-(1,4)-glycosidic bond linkages in the cellobiose polymer repeating units are cleaved. Problems arise in the hydrolysis of cellulose as experimental and theoretical studies have shown cellulose to have very low solubility in water and most other general molecular solvents. This results in the use of harsh pretreatments at high temperatures and pressures to extract cellulose from lignocellulosic material and strong acids catalysts (pKa < −3.2). Room temperature ionic liquids (RTILs) provide potentially environmentally friendly alternative. It has been shown that ILs can dissolve cellulose under relatively benign conditions and can possibly be adapted into a one-pot-like process of hydrolysis using acid-functionalised IL catalysts. This dissertation investigated the effect of various ionic liquids on the thermodynamics of cellobiose acid hydrolysis, as both a catalyst and as a solvent, using computational means. An appropriate thermodynamic cycle protocol, a DLPNO-CCSD(T)/ccpVTZ//TPSS/def2-TZVP [M05-2X/6-31+G** (SMD)] proton exchange cycle, was established through benchmarking for the prediction of Brønsted acid-functionalised ionic liquid pKa values in ionic liquids. The sulfonyl-functionalised acidic IL was shown to be the most acidic IL resulting in a lower protonation free energy. Solvation in ionic liquids resulted in higher protonation and barrier height free energies relative to solvation in water. The current environmental situation, with respect to global warming and the ever– approaching depletion of fossil fuel sources, places significance on the development of green fuel and platform chemical production methods. In this context, processes that utilise biomass sources as feedstock, are of great interest. Cellulose, which is the most abundant biopolymer in nature, is a renewable low–cost carbon resource derived from harvest residues and sources like wood and straw. Glucose generation from cellulose requires a saccharide conversion, whereby the β-(1,4)-glycosidic bond linkages in the cellobiose polymer repeating units are cleaved. Problems arise in the hydrolysis of cellulose as experimental and theoretical studies have shown cellulose to have very low solubility in water and most other general molecular solvents. This results in the use of harsh pretreatments at high temperatures and pressures to extract cellulose from lignocellulosic material and strong acids catalysts (pKa < −3.2). Room temperature ionic liquids (RTILs) provide potentially environmentally friendly alternative. It has been shown that ILs can dissolve cellulose under relatively benign conditions and can possibly be adapted into a one-pot-like process of hydrolysis using acid-functionalised IL catalysts. This dissertation investigated the effect of various ionic liquids on the thermodynamics of cellobiose acid hydrolysis, as both a catalyst and as a solvent, using computational means. An appropriate thermodynamic cycle protocol, a DLPNO-CCSD(T)/ccpVTZ//TPSS/def2-TZVP [M05-2X/6-31+G** (SMD)] proton exchange cycle, was established through benchmarking for the prediction of Brønsted acid-functionalised ionic liquid pKa values in ionic liquids. The sulfonyl-functionalised acidic IL was shown to be the most acidic IL resulting in a lower protonation free energy. Solvation in ionic liquids resulted in higher protonation and barrier height free energies relative to solvation in water.

Yes / A series of novel nopyl-derived chiral phosphonium ionic liquids have been successfully synthesised and characterised. Analysis of each novel ionic liquid was conducted in order to confirm structure, purity and thermal stability. / The full-text of this article will be released for public view at the end of the publisher embargo on 19 Jul 2021.

A survey of substitution reactions conducted in a phosphonium bistriflimide ionic liquid is presented. The results demonstrate high selectivity favoring substitution over typically competitive elimination and solvolytic processes even when challenging secondary and tertiary electrophiles are employed. The first reports of Kornblum substitution reactions in an ionic liquid are described that proceed with very high chemoselectivity in favor of nitro over nitroso products and elimination side products. The structure-reactivity study indicates that these reactions proceed through a narrow spectrum of pathways ranging from straight SN2 to a preassociation pathway along a saddle point that approaches the SN1 limit. The lack of any basic entity in the phosphonium bistriflimide ionic liquid appears to prevent any potential base-mediated elimination reactions, which makes this a highly selective medium for use in general substitution reactions. A general, high yielding procedure is described for the esterification of carboxylic acids through carboxylate alkylation in phosphonium salt ionic liquid. The product ester can be readily isolated using a standard extraction protocol or by direct solvent freedistillation allowing ionic liquid re-use. The reaction takes place at relatively low temperature in comparison to other processes reported in ionic liquids. Biologically important BZE (benzoate) esters were synthesized and a proposed solvolysis mechanism investigated in ionic liquids. The Pd-mediated Buchwald-Hartwig amination reaction of aryl halides in phosphonium salt ionic liquid consisting of a trihexyl(tetradecyl)phosphonium cation with a range of anions has been investigated. A pronounced anionic effect was uncovered with the reaction proceeding readily with weakly nucleophilic diarylamines only in the presence of non-coordinating anions. A mechanism is postulated to explain these results involving a rate limiting ligand exchange step that proceeds through a dissociative pathway. A novel non solvated crystal structure of tris(dibenzylideneacetone) palladium(0) in phosphonium salt ionic liquids is reported. This research provided insights concerning the use of ionic liquids in palladium catalyzed Buchwald-Hartwig amination reaction. New synthetic methods were developed for the preparation of trialkyl (methyl) phosphonium ionic liquids, with this novel "green" protocol, the use of iodomethane is eliminated and oxidation of trialkyl phosphines can be reduced. / Thesis / Doctor of Philosophy (PhD)

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