Typescript. / Thesis (PhD)--Macquarie University (Division of Environmental & Life Sciences, Dept. of Chemistry & Biomolecular Sciences), 2005. / Includes bibliographical references. / Microelectrode voltammetry -- Experimental -- Microelectrode fabrication -- Characterisation of the carbon film surface: Surface stability - X-ray photoelectron spectroscopy - Raman spectroscopy - Capacitance - Edge plane concentration - Potential window - Surface concentration of alkenes and alkynes - Outer sphere electron transfer using hexaamineruthenium (III) chloride - Reduction of potassium hexacyanoferrate (III) - Anodic oxidation: diol to dione; dopamine and ascorbic acid - Surface oxidation - Ferrocene in a non aqueous solvent -- Selectivity: Formation of carboxylic acid groups on a carbon film surface by ferrous II sulfate complex oxidation - Ethanol modified carbon film surface - Modification of carbon film microelectrode surface using aromatic amines - Modification of carbon film surfaces to form a dual functional ascorbic acid barrier -- In vivo anti fouling properties of surface modified carbon film microelectrodes -- Conclusion. / In this thesis a procedure is presented for the fabrication of a microelectrode to monitor the neurotransmitter dopamine in vivo. The microelectrodes are fabricated by in situ pyrolysis of acetylene under a nitrogen blanket onto a quartz capillary. The carbon film was then anodically oxidised in the presence of 2,4-dinitroaniline. These microelectrodes are stable, provide the physical strength to penetrate brain tissue, have a low capacitance, are resistant to fouling in vivo and selectively suppress the endogenous ascorbic acid which oxidises at the same potential as dopamine. With such properties the carbon film microelectrode appears ideally suited for fast scanning cyclic voltammetric studies of cationic neurotransmitters such as dopamine in vivo. / xxviii, 323 p. ill

Diss. (sammanfattning) Stockholm : Karolinska institutet, 2007. / Härtill 4 uppsatser.

Thesis (Ph. D.)--University of Oregon, 2008. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 122-127). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.

This work presents microfabricated microelectrodes, capable of quantitative analysis in molten salt (MS). MSs are an electrolytic medium of growing interest, especially in the area of nuclear reprocessing. However, designing sensors for a MS-based nuclear reprocessing system is a challenge, owing to the usually corrosive nature and high operating temperatures (typically 450 - 500◦C) of MS. Microelectrodes are well placed as sensors, with numerous advantages over macro-scale electrodes. As a consequence, there have been previous attempts to utilise microelectrodes inMS. However, these have not been successful and all have suffered disadvantages inherent in traditional microelectrode manufacturing. The microelectrodes presented in this work were produced using standard microfabrication techniques and characterised in MS. An analysis of failure mechanisms guided a systematic study of material combinations. This resulted in a sensor, which is capable of delivering quantifiable electrochemistry in MS. However, the lifetime and yield of the sensor were determined to only be 46% and 1.4 hours respectively. Further investigation of the microelectrode failure mechanisms guided several layout changes to the microelectrode design. By reducing critical area, where defects or pinholes could form, these resulted in improvements in performance. This increased the yield to 65%, while the average lifetime increased up to 45 hours. Test structures were designed to investigate the causes of the continued microelectrode failures and identified shorting between the electrode metal and silicon substrate. This suggests the existence of defects in the underlying insulator are the cause of the 35% of microelectrodes which never functioned. Separate test structures suggested the lifetimes of the microelectrodes could also be improved by removing the need for a metal adhesion layer. Tantalum has been suggested as a replacement electrode metal and a proof of concept study demonstrated the feasibility of employing thin film tantalum as an electrode metal in LKE. Using this technology as a platform, several proof-of-concept microelectrode designs are also presented: liquid microelectrodes, microelectrode arrays, and a nanoelectrode. These are targeted at specific sensing applications, and provide an expanded spectrum of measurements in MS.

In this paper, I sought to identify and develop a protocol on electrode arrays as a result of rapid aging by applying rapid current over time. We, however, apply a different approach by using phosphate buffer solution (PBS) to mimic the conditions of the body. Here we have established an in vitro protocol for accelerated aging, a process that involves testing in extreme conditions such as oxygen, heat, sunlight, humidity, and vibration aimed at speeding the normal aging process of items; on commercially available shape memory polymer electrode arrays from Qualia over a period of 30 days in PBS. Two electrode arrays were placed in 37°C and 2 were placed in 57°C. Open lead electrochemical impedance spectroscopy (EIS) was conducted on the electrode arrays. Overall, the results showed there were differences in average impedance during this accelerated aging protocol. At 37°C we see that the average impedance values increased as the electrodes were aged at 1kHz from an average of 4.15E6 to 9.14E6 Ohms. At 57°C electrode arrays 4 and 5 showed strong P values well above 0.05, but average impedance increased drastically from 3.27E6 to 9.97E6 and P value of 0.04 from measurement day 24 to day 30. This indicated to us that the electrode could be experiencing some delamination. In addition, this could be because the Qualia nerve cuffs tested were "B" grade, so changes in impedance could be due to the integrity of the device. This would tell us that these electrode arrays would not be capable to withstand long – term recording for up to 240 days. As a result, rejecting the hypothesis that this protocol would show no change in impedance levels for a simulated aging period of 240 days. Although this protocol was not in a perfect setting and the quality of the electrodes were not up to standard, this gave us insight into the electrochemical properties of SMP electrodes which will be useful when we bio-fabricate our own electrodes to study gastrointestinal (GI) disorders.

Hepatocytes exhibit a regulatory volume decrease (RVD) during hypotonic shock, which comprises loss of intracellular K+ and Cl- accompanied by hyperpolarization of transmembrane potential (Vm) due to an increase in membrane K+ conductance, (GK). To examine hepatocyte K+ homeostasis during RVD, double-barrel, K+-selective microelectrodes were used to measure changes in steady-state intracellular K+ activity (aKi) and Vm during hyposmotic stress. Cell water volume change was evaluated by measuring changes in intracellular tetramethylammonium (TMA+). Liver slices were superfused with modified Krebs physiological salt solution. Hyposmolality (0.8×300 mosm) was created by a 50 m m step-decrease of external sucrose concentration. Hepatocyte Vm hyperpolarized by 19 mV from -27 ± 1 to -46 ± 1 mV and aKidecreased by 14% from 91 ± 4 to 78 ± 4 m m when slices were exposed to hyposmotic stress for 4-5 min. Both Vm and aKireturned to control level after restoring isosmotic solution. In paired measurements, hypotonic stress induced similar changes in Vm and aKiboth control and added ouabain (1 m m) conditions, and these values returned to their control level after the osmotic stress. In another paired measurement, hypotonic shock first induced an 18-mV increase in Vm and a 15% decrease in aKiin control condition. After loading hepatocytes with TMA+, the same hypotonic shock induced a 14-mV increase in Vm and a 14% decrease in aTMAi. This accounted for a 17% increase of intracellular water volume, which was identical to the cell water volume change obtained when aKiwas used as the marker. Nonetheless, hyposmotic stress-induced changes in Vm and aKiwere blocked partly by Ba2+ (2 m m). We conclude that (i) hepatocyte Vm increases and aKidecreases during hypotonic shock; (ii) the changes in hepatocyte Vm and aKiduring and after hypotonic shock are independent of the Na+-K+ pump; (iii) the decrease in aKiduring hypotonic stress results principally from hepatocyte swelling.

As the world population approaches seven billion, a greater strain is put on the resources necessary to sustain life. One of the most basic and essential resources is water and while two thirds of the earth is covered by water, the majority is either salt water (oceans and seas) or it is too contaminated to drink. The purpose of this project is to develop a portable device capable of testing whether a specific source of water (i.e. lake, river, well…) is potable. There are numerous filtration techniques that can remove contaminants and make even the dirtiest water clean enough for consumption but they are for the most part, very time consuming and immobile processes. The device is not a means of water purification but rather focuses on determining the content of the water and whether it is safe. Particles within the water are separated and trapped using a combination of a Taylor Couette fluid flow system and Dielectrophoretic electrodes. This paper explores Taylor Couette flow in a large gap and low aspect ratio system through theory and experimentation with early stage prototypes. Different inner cylinder radii, 2.12cm, 1.665cm and 1.075cm, were tested at different speeds approaching, at and passing the critical Taylor number, 3825, 4713 and 6923 respectively for each cylinder. Dielectrophoretic (DEP) electrodes were designed, fabricated, coated and tested using latex beads to determine the method of integrating them within the fluid flow system. Taylor Couette theory, in terms of the formation of vortices within the large gap, small aspect ratio system, was not validated during testing. The flow pattern generated was more akin to a chaotic circular Couette flow but still served to move the particles toward the outer wall. Fully integrated tests were run with limited success. Recommendations were made to pursue both circular Couette flow as the basis for iv particle separation and dimensional changes in the setup to allow for the formation of Taylor vortices by increasing the radius ratio but still allowing for a larger volume of fluid.

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Au cours de ce travail de thèse, je présente les résultats de travaux de recherche visant à la fabrication et au développement d'une nouvelle génération d'implants cérébraux permettant l'enregistrement stable dans le temps de signaux électrophysiologiques. L'objectif est d'offrir une solution technologique pour le développement de nouvelles applications chroniques utiles pour l'investigation du fonctionnement du cerveau (ex : dynamique des réseaux de neurones, traitement de l'information) mais aussi nécessaires pour la mise au point de nouvelles technologies, de type Brain Computer Interface (BCI), qui devraient, à terme, permettre d'augmenter l'autonomie des patients atteints de troubles moteurs ou victimes d'accident ayant conduit à un handicap physique.Nous rapportons, à travers diverses études expérimentales, des arguments soutenant l'utilisation de matériaux nanostructurés et en particulier les nanotubes de carbone, pour permettre d'améliorer les performances électriques et pour diminuer leur impact sur la réponse immunitaire du cerveau induite par l'implantation d'un corps étranger. Ceci représente la principale limitation à l'utilisation d'implants de mesure sur de longues périodes.Notre étude couvre ainsi l'ensemble des problématiques relatives aux implants cérébraux, en abordant les techniques de fabrication, le protocole de caractérisation électrique et enfinl'évaluation biologique in vitro et in vivo.Dans un premier temps, nous avons développé une matrice de microélectrodes nanostructurées en utilisant les techniques de microfabrication. Ceci a permis de mettre en avant la diminution de l'impédance interfaciale des électrodes liée à l'augmentation de leurs surfaces développées et, par conséquent, l'amélioration de la qualité du signal due à la réduction du niveau de bruit de la mesure. Une analyse électrochimique complémentaire, nous a dans le même temps, permis d'établir un modèle qualitatif représentant les différents phénomènes mis en jeu et soulignant l'importance des phénomènes diffusifs lors de la mesure et leurs éventuelles conséquences in vivo.Cette première génération d'électrodes nous a également permis de mener une campagne de tests in vitro pour évaluer la cytotoxicité des nanotubes à partir de différents modèles cellulaires: cultures de lignées neuronales (NG108-15) et cellules primaires (cellules gliales7et neurones du cortex ou de l'hippocampe). Suite à ces expériences, aucune forme de toxicité n'a été décelée. Bien au contraire, l'évolution des cellules gliales pendant la culture tend à défendre l'idée que les nanotubes de carbone ont le potentiel de réduire la réaction immunitaire du cerveau. Nous avons testé ce phénomène in vivo grâce à l'analyse histologique de cerveaux de rats après une implantation sous-durale d'un mois avec des échantillons en nitrure de titane (TiN) avec ou sans nanotubes de carbone. Nos résultats confirment une réduction significative de la cicatrice gliale lors d'implantations avec des échantillons nanostructurés.Ces résultats suggèrent un possible impact des nanotubes de carbone sur la stabilité de la mesure dans le temps, autrement dit sur sa « biostabilité ». Nous avons donc implanté un macaque Fascicularis avec un système comportant 16 électrodes en TiN et 16 électrodes nanostructurées de 1mm², amincies à 25μm et montées sur un substrat en polyimide flexible.L'étude qui se situe dans le cadre du projet Neurolink (financé par l'ANR/PNANO),représente la première validation expérimentale sur une longue période et démontre les avantages tant électriques que biologiques de l'utilisation des nanotubes de carbone comme interface entre l'électrode et les neurones. / During this work of thesis, I present the results of research works aiming at the manufacturing and to the development of a new generation of intellectual implants allowing the stable recording in the time of signals électrophysiologiques. The objective is to offer a technological solution for the development of new useful chronic applications for the investigation of the functioning of the brain (ex: dynamics of the networks of neurones, data processing) but also necessities for the development of new technologies, Brain Computer Interface ( BCI), which should, eventually, allow to increase the autonomy of the patients reached(affected) by driving disorders(confusions) or the victims of accident having led(driven) to a physical handicap. [résumé incomplet]