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Amperometric study of microscopic band and cylinder array electrodesSeddon, Brian Jeffrey January 1989 (has links)
No description available.
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<b>Leveraging Multiphase Interfaces for Materials Synthesis</b>Thomas Bradley Clarke (19476631) 26 August 2024 (has links)
<p dir="ltr">The interface between water and oil has many unique physicochemical properties that are continuing to be explored. This dissertation demonstrates several properties of these interfaces that can be leveraged to drive unique electrochemistry at or near the location where this interface meets an electrode surface under mild applied potentials. New methods for the electrodeposition of metallic nanowires and electroprecipitation of electrocatalytic metal hydroxides are discussed. Additionally, a new method for spontaneously emulsifying water and oil phases is introduced, which can lengthen the liquid|liquid|electrode boundary to further drive the preferential electrochemical transformations just described.</p>
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Electron paramagnetic resonance studies of rhodobacter capsulatus dimethylsulfoxide reductase, model MO(V) and W(V) complexes and metallotolyporphyrinsLane, I. Unknown Date (has links)
No description available.
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Electron paramagnetic resonance studies of rhodobacter capsulatus dimethylsulfoxide reductase, model MO(V) and W(V) complexes and metallotolyporphyrinsLane, I. Unknown Date (has links)
No description available.
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Tommy_Zhang_Thesis.pdfTommy Zhang (16496298) 30 August 2023 (has links)
<p> Potassium levels in serum are used in the diagnosis of diseases involving cardiac arrhythmias, neuromuscular weakness, and chronic kidney diseases. These illnesses are becoming more prevalent, therefore, developing new potassium quantification methods would aid in advancing preventative care. Current methods of quantifying potassium mainly rely on the use of glass ion-selective electrodes which are costly, fragile, and requires frequent maintenance and recalibration. For faster and more accessible quantification of potassium, we are developing low cost, portable, and easy to fabricate electrochemical tape-and-paper-based devices. Our sensor bypasses the inconveniences of ion-selective electrodes and could ultimately serve as a point-of-care device to allow for regular monitoring or even home-use. Our sensing method relies on Prussian blue immobilized on the surface of electrodes as a potassium recognition element. Potassium ions intercalate into the Prussian blue lattice and subsequently changes the electrochemical characteristics of Prussian blue such as the redox peak potentials. These devices are highly robust, feature a limit of detection of 1.3 mM potassium and the response is linear to at least 100 mM, which contains the clinically relevant ranges required for diagnostics. Quantification was developed using cyclic voltammetry, demonstrated in Chapter 3. We observed changes in Prussian blue redox peak potentials at different concentrations of potassium and followed the expected Nernstian response. We investigated multiple methods of immobilizing Prussian blue onto the electrode surfaces to investigate stability and reproducibility in Chapter 4. Adsorption, <em>in-situ</em> synthesis, and carbon paste incorporation of Prussian blue was tested. Prussian blue-carbon paste devices had reproducibility issues and featured broad reduction peaks. <em>In-situ</em> synthesis of Prussian blue directly onto the surface of the electrodes also featured broad reduction peaks but the Prussian blue response was reproducible. The issue with <em>in-situ</em> synthesis was the stability of the Prussian blue layer, which was susceptible to degradation after repeated use of the device, which is required for evaluating the performance of the device. Although adsorption using Prussian blue in water had some reproducibility issues as well, this method led to the most stable Prussian blue layer, had distinct reduction peaks, and was simple to perform. Various solvents were used to dissolve Prussian blue in Chapter 5 to investigate methods of increasing device reproducibility when using adsorption. A few organic solvents were able to dissolve Prussian blue to form a stable solution with the goal of forming a more uniform Prussian blue layer and potentially improving consistency of the layer immobilization. While these alternative solvents were able to dissolve Prussian blue, they also damaged the graphite electrodes on the devices, which altered the electrochemical responses of the devices to the point where potassium quantification was no longer possible. Due to incompatibility between these alternative solvents and the devices, adsorption of Prussian blue in water continued to be used. Different modes of adsorption were explored and was optimized in Chapter 6. By altering the adsorption setup and allowing the Prussian blue particles to settle evenly onto a level electrode surface, device reproductivity increased substantially. To understand the applicability of the devices in real samples, interferent studies were performed in Chapter 7. Other cations such as Na+, Li+, Ca2+, Mg2+, and Ba2+ were not observed to enter the Prussian blue lattice in the cyclic voltammograms. Monovalent cations that share the same charge as K+ but have smaller ionic radius, Na+ and Li+, were able to decrease K+ sensitivity. Divalent cations that had a smaller ionic radius than K+ did not alter sensitivity. The exception was Ba2+, which also decreased K+ sensitivity. These results suggested that both ionic radius and charge of a species were important factors in impacting K+ intercalation into the Prussian blue lattice. Other interferents such as sulfates, phosphates, carbonates, urea, and lactic found in serum and sweat samples were tested. The presence of these interferents decreased the current intensity of the reduction peak of Prussian blue, which resulted in less definition in the peaks. For the future of this project, the effects of interferents found in serum and sweat must be investigated further. Additionally, reproducibility of the devices could be improved further if less harsh organic solvents are tested for adsorption, square wave voltammetry could be used for quantification to evaluate the viability of alternative voltametric techniques, and Prussian blue analogues could be implemented into the devices for quantification of other cations. </p>
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<b>Electrochemical Strategies for Enabling the In-field Detection and Quantification of Per- and Polyfluoroalkylsubstances (PFAS)</b>Rebecca Beth Clark (17112571) 11 October 2023 (has links)
<p dir="ltr">Per- and polyfluoroalkyl substances (PFAS), once considered to be emerging micro-pollutants, are now a very present class of pervasive and persistent micropollutant. Frequently referred to as “forever chemicals”, once they’re in the environment, they do not break down owing to the strength of their network of carbon-fluorine bonds. Their persistence is of particular concern, as they have been shown to have a plethora of negative health effects on living things including low infant birth weights, dyslipidemia, and cancer, to name a few. Due to both their persistence and negative health effects, the ability to rapidly test waters (<i>i.e.,</i> drinking water, river water, lake water, etc.) is of critical importance. The current “gold-standard” method for testing waters is the collection and transport of a sample to a centralized facility where chromatography and mass spectrometric methods can be performed for the separation, identification, and quantification of PFAS; however, this method is not able to be used for real-time analyses and is not sufficient for efficiently informing consumers or remediation efforts. An in-field detection method that is capable of providing real-time analyses is needed.</p><p dir="ltr">Electrochemistry stands well-poised to offer a suite of techniques that can be used for in-field detection. Electrochemistry is cost-effective, easy to perform and analyze, and readily portable; however, it lacks specificity and typically requires an electroactive analyte. These limitations can be overcome through the use of a surface functionalization strategy which adds specificity through the imprinting of the analyte of interest and monitors the change in signal from an alternate mediator molecule. Molecularly imprinted polymers (MIPs) are the chosen surface functionalization strategy that will be used and discussed in this work. While MIPs overcome the specificity and requirement of an electroactive analyte limitations and have been previously demonstrated for the detection of perfluorooctane sulfonate (PFOS), they traditionally require the use of added buffers and one electron mediators, which are not found in natural waters. Thus, to expand MIP-based electrochemical detection to in-field use strategies must be developed and employed to mitigate these concerns.</p><p dir="ltr">This work provides significant strides forward in enabling in-field, MIP-based electro-chemical sensing. We take advantage of ambient dioxygen present in river water to quantify one of the more harmful PFAS molecules, perfluorooctane sulfonate (PFOS), from 0 to 0.5 nM on a MIP-modified carbon substrate. Differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) generated calibration curves for PFOS in river water using oxygen as the mediator. Importantly, we show that electrochemical impedance spectroscopy is superior to voltammetric techniques: like ultramicroelectrodes, this technique can be used in low-conductivity matrices like river water with high reproducibility. Further, impedance provides a PFOS limit of detection of 3.4 pM. We also demonstrate that the common interferents humic acid and chloride do not affect the sensor signal. The use of dioxygen is predicated on the assumption that there will be consistent ambient dioxygen levels in natural waters. This is not always the case in hypoxic groundwater and at high altitudes. To overcome this challenge, and further advance the strategies that will enable in-field electroanalysis of PFAS, we demonstrate that dioxygen can be generated in solution through the hydrolysis of water. The electrogenerated dioxygen can then be used as a mediator for molecularly imprinted polymer (MIP)-based electroanalysis. We demonstrate that calibration curves can be constructed with high precision and sensitivity (LOD > 1 ppt). We also demonstrate the development and use of a universal multiplexer and electrode array, which can enable high throughput, in-field electroanalysis for a wide variety of compounds. In this work, we demonstrate it specifically for detecting PFOS from 0.05 to 0.05 nM and lead at a concentration of 1 nM.</p><p dir="ltr">Additionally, in this work, we lay the groundwork for the future direction of developing a more fundamental understanding of MIPs to be able to fine-tune their selectivity and performance. Preliminary data and experimental approaches are shown for using nanoparticle deposition and visualization, with scanning electrochemical microscopy, to characterize surface reactivity and binding site distribution, functional group studies to better understand what groups and molecular interactions affect the binding of the analyte to the MIP the most, and using cyclic voltammetry to determine the capacitance and resistance of the polymer. Further approaches are outlined to relate the conditions under which the polymer was created to the polymer’s characteristics and then the polymer’s performance. Future improvements to make the in-field use of the multiplexer more efficient are also shown. In total, this work shows the feasibility and nearness of in-field, MIP-based electrochemical detection for PFAS by advancing the strategies and hardware necessary to do so.</p>
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Eletrodos modificados por óxido de tungstênio: Métodos de preparação e aplicações analíticas / Modified Electrodes with Tungsten Oxide: Preparation Methods and Analytic ApplicationsRocha, José Roberto Caetano da 23 January 2006 (has links)
Neste trabalho são apresentados resultados da eletrodeposição de MoOx e de WOx em eletrodos de carbono vítreo e em eletrodos de ouro. A estabilidade de filmes de WOx foi investigada em diferentes valores de pH utilizando voltametria cíclica e microbalança eletroquímica de cristal de quartzo e observou-se que estes filmes são estáveis em soluções com valores de pH inferiores a 3. O processo eletrocatalítico envolvendo a redução de IO3- em superfícies recobertas com WOx foi comparado com aquele observado em eletrodo modificado com MoOx, observando-se as vantagens deste processo em superfícies modificadas com WOx. Discutiram-se ainda os resultados obtidos do processo da oxidação de óxido nítrico na superfície eletródica polida e modificada com WOx. Também são apresentados resultados de estudos comparativos sobre a redução do IO3-, BrO3- e ClO3- na superfície modificada, concluindo-se que no caso do IO3- obtêm-se maiores valores de corrente devido à maior polarizabilidade do átomo de iodo em relação aos outros dois halogênios. Estudos envolvendo a permeabilidade de íons IO3- e Fe(CN)63- em filmes de WOx foram realizados por voltametria com eletrodos rotativos percebendo-se que filmes mais espessos apresentam pouca permeabilidade. Eletrodos recobertos por filmes de WOx foram utilizados como sensores amperométricos para iodato. Para tanto, desenvolveu-se método em fluxo para IO3- em uma faixa de concentração de 5 a 5000 mmol/L, com limite de detecção estimado em 210 nmol/L. A repetibilidade do método para 41 injeções de solução 80 mmol/L de IO3- foi de 98,3 %. Também foram realizados ensaios para determinar o analito em amostras de sal de cozinha e os dados obtidos foram concordantes com os resultados oriundos do uso de método oficial. / Thin films of non-stoichiometric tungsten oxides have been deposited onto glassy carbon surfaces by electrodeposition from acidic W (VI) solutions. At these modified surfaces, rotating disc electrode voltammetric experiments indicated that iodate is electrocatalytically reduced in a mass-transport controlled process. The influence of the film thickness on the response to iodate was investigated and the results suggested a reaction occurring at the film/solution interface. The modified electrode was employed successfully as an amperometric sensor for iodate in a flow injection apparatus. The linear response of the developed method is extended from a 5 mmol L-1 to 5 mmol L-1 iodate with a limit of detection (signal-to-noise = 3) of 210 nmol L-1. The repeatability of the method for 41 injections of an 80 mmol L-1 iodate solution was 98,3 % and the throughput was determined as 123 injections h-1. Interference from other oxidant anions such as nitrate and nitrite was not noticeable, whereas bromate and chlorate interfere at slight levels. The method was used in the determination of the iodate content in commercial salt samples.
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Creating mesophorous materials by liquid crystal templating of readily available materialsMankelow, Rowena, Chemistry, Faculty of Science, UNSW January 2003 (has links)
No description available.
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A fill and flow channel enzyme biosensorZhao, Min, Chemistry, Faculty of Science, UNSW January 2004 (has links)
No description available.
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Cyclic BiamperometryRahimi, Mohammad Mehdi 05 August 2009 (has links)
In this thesis, cyclic biamperometry (CB) as a new method in electrochemistry,
has been introduced and investigated. The hallmark of this method is the absence
of a reference electrode which potentially allows simplification and miniaturization
of the measurement apparatus. Similarities and differences of this method and
cyclic voltammetry (CV) have been studied and it was shown that under conditions
of using standard electrodes, CB has a better sensitivity and a lower detection
limit than CV. A new equivalent circuit model for the cell has been proposed and
parameters affecting the sensitivity of CB, such as keeping the concentration of
one redox species in excess and having a larger W2 electrode, have been described.
The redox cycling effect in biamperometric systems has been investigated and it
is shown that improvements of at least two orders of magnitude in sensitivity can
be achieved by using interdigitated electrodes (IDEs). In addition, an example
for applications of this method, including biamperometric dead-stop titration of
1-naphthol with ferricyanide, has been presented and possible fields in which CB can
be incorporated (e.g. monitoring the activity of alkaline phosphatase) have been
illustrated. Finally, a few suggestions for future studies and further improvements
have been outlined.
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