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Electric propulsion thrusters are considered to be candidates for microsatellites; ion engines are among the most scalable. Miniaturizing the ion engine will require novel concepts for the ionizer. MEMS, nanotechnology and other new technologies are expected to impact here. This thesis explores the use of these technologies to enable a new design for ion-thruster propellant ionization. An ideal approach, using expensive fabrication processes, is first described. This approach could prove to be a good method for testing and for the collection of precise data. A cost effective approach, on which our testing is based, is then discussed in detailed. After assembling a facility which uses existing vacuum systems and available instrumentation, we manufactured and tested miniature discharge geometries consisting of commercial 2â x2â copper-clad wafers. Three nominal insulator thicknessâ were used, 0.005,â 0.010â and 0.115.â The wafers were each drilled with 9 equal wholes of diameters 300, 400, and 500 m. A total of 12 wafers were tested (including 3 widths without wholes for a baseline) for the breakdown voltage as a function of argon pressure in the range of 10 to 1000 mTorr. Results indicate that argon breakdown may occur in the holes consistent with the classical Paschen curves.

Micro-satellites often require the adaptation of existing propulsion systems. Electric propulsion thrusters are perhaps the best candidates to meet these needs and ion engines are among the most scalable. Miniaturizing the ion engine will require novel concepts for the ionizer with perhaps novel propellants. MEMS, nanotechnology and other technological advances are expected to impact on new designs. Our work shows that the ionization of Argon, which is an alternate fuel to Xenon, can be achieved at low voltages by utilizing Micro-Structured Electrode (MSE) Arrays. Copper-clad sheets separated by a dielectric material (fiberglass laminate epoxy resin system combined with a glass fabric substrate) of varying thickness (0.1 mm to 0.4 mm) form the discharge electrodes in the MSE arrays The wafers are drilled with an array of holes and this geometry serves to concentrate the electric field between electrodes enhancing electron emission at the cathode. Minimum breakdown voltages between 240 and 280 Volts at pressures of around 100 mTorr (0.133N/m2) were consistently obtained with arrays of hole diameter ranging from 300 to 500um. These results are consistent with conventional Paschen-curves with two empirical constants that arise from our unconventional geometrical arrangements and from the different material properties.

Le processus de vieillissement des accumulateurs lithium-ion est un facteur déterminant lors de leur utilisation pour des applications spatiales. Les couches de passivation présentes à la surface des électrodes, composées de différents sels et polymères, ont une grande influence sur les performances des batteries, en particulier en termes de cyclage et de durée de vie. La compréhension des phénomènes de dissolution et de précipitation des espèces présentes aux électrodes est donc essentielle pour appréhender le vieillissement des batteries. Dans un premier temps, les propriétés de solubilisation et de transport de ces espèces dans l’électrolyte ont été étudiées afin d’analyser leur comportement en solution. Les investigations ont ensuite porté sur l’influence de ces composés sur le cyclage des accumulateurs lithium-ion. Les résultats obtenus ont permis d’identifier les constituants des couches de passivation ayant un impact critique sur le fonctionnement des batteries, en vue d’optimiser les performances en vieillissement des systèmes existants. / The ageing process of lithium-ion batteries is a key issue for their use in space applications. The passivation layers deposited on the electrode surface are composed of various salts and of polymers, and hence, have a great impact on battery performances or on cycle life. The understanding of dissolution and precipitation phenomena of species deposited at the electrode surface is therefore essential to enlighten the ageing process in batteries. At first, solubilization and transport properties of organic or mineral lithium salts in the electrolyte were determined. Using solubility data, investigations were then carried out to study the effect of these compounds on cycling properties. It has been shown that if some lithium salts have a critical impact on the battery efficiency, others do not have any detrimental effect on battery capacity or faradic yield. As a conclusion, the dissolution with time of compounds belonging to the solid electrolyte interphase is an important parameter to take into account when studying battery ageing.

This thesis comprises three parts united by a single theme: development of flexible ditopic receptors. In part 1, two bis(crown ether)s were synthesized and their binding selectivities with alkali, alkaline earth and α,ω-primaryalkylidenediammonium cations were studied by electrospray ionization mass spectrometry (ESI-MS). First, we confirmed that the ion intensities of complexes in the gas phase are linearly related to the concentrations of complexes in solution for single crown ether dicarboxylic acid. Binding selectivities of complex bis(crown ether)s with mixtures of alkali cations and with mixtures of alkaline earth cations were then determined directly from ESI-MS spectra. The results from ESIMS are consistent with literature data if ions of like charge and similar type are compared (e. g., among the alkali metals). The stoichiometries of complexes in solution were also probed. Complexes with up to two K⁺ per crown ether were detected by ESI-MS. The research shows that ESI-MS provides an effective tool to study complexation by structurally complex molecules in solution. From the ESI-MS results, bis(crown ether) bolaamphiphiles were designed and synthesized as cation-recognition based membrane-disruption agents. Three bis(crown ether)s were obtained by capping an 18-crown-6 dicarboxylate anhydride with different lengthes of α,ω-alkanedicarboxylic acids extended as the 3-amino-1-propyl esters. Their membrane disrupting activities were explored using vesicle encapsulated 5(6)- carboxyfluorescein (CF) by a fluorescence self-quenching (FSQ) method. The membrane disrupting activity is significantly and specifically enhanced specifically by the addition Sr²⁺ or Ba²⁺ in solution. The membrane-disrupting activity is also enhanced with a increased aliphatic loop length of the starting α,ω-alkanedicarboxylic acid. Based on the mechanism studies of Regen and work conducted in this thesis, we propose that the active form for membrane-disruption is created by a U-shaped sandwich complex between Ba²⁺ and the bis(crown ether) bolaamphiphiles which interacts only with the outer leaflet of the vesicle bilayer. In part 3, a photoswitchable bis(crown ether) based on thioindigo was designed and synthesized as a cation- and photo-regulated membrane-disruption agent. The bis(crown ether) was prepared by capping an 18-crown-6 dicarboxylate anhydride with 7,7’-thioindigo dicarboxylic acid extended as the 8-amino-1-octanyl esters. There is significant difference in the membrane-disrupting activities of the cis- (U-shape) and trans- (S-shape) isomers using the vesicle entrapped CF (FSQ) method. Alkaline earth cations suppress the cis-to-trans thermal isomerization and stabilize the cis-isomers of the 7,7’- thioindigo bis(crown ether) in organic solvent. The results confirm the mechanism proposed, namely, that a U-shaped conformation is required for membrane disruption, that the bis(crown ether)s form sandwich complexes with alkaline earth metal ions. / Graduate

Voltage-gated potassium channels are primary determinants of cellular excitability in the mammalian nervous system. The localization of these channels to distinct cellular compartments influences components of neuronal function, including resting membrane potential, action potential characteristics and neurotransmitter release. Thus, understanding the mechanistic basis of ion channel localization can provide fundamental insight into human physiology. The overall goal of this dissertation was to elucidate the regulatory mechanisms governing localization and function of the Kv1.3 voltage-gated potassium channel. The sympathetic branch of the autonomic nervous system innervates many organ systems including the kidneys, heart and blood vessels and was used as a model to study endogenous Kv1.3. We found that postganglionic sympathetic neurons express Kv1.3 and that the channel exhibits a striking pattern of localization to the Golgi apparatus in the soma of these cells. Kv1.3 ionic current was also isolated from the soma of these neurons, indicating the channel is a determinant of the electrophysiological properties of sympathetic neurons. In addition, the specific inhibition of Kv1.3 with margatoxin was found to depolarize neuronal resting membrane potential, decrease the latency to action potential firing and increase nicotinic agonist-induced neurotransmitter release. Collectively, these findings demonstrate that Kv1.3 influences the function of postganglionic sympathetic neurons and led to the hypothesis that regulating channel localization may be a mechanism for modulating the activity of these cells. In this dissertation, we propose that the observed Golgi retention of Kv1.3 may be a trafficking-dependent mechanism of channel regulation. To test this hypothesis, we used HEK293 cells as our model system. Our data show that the degree of Kv1.3 Golgi localization is inversely correlated with the amount of channel at the plasma membrane. In addition, the amplitude of Kv1.3 ionic current measured in cells with low Kv1.3 Golgi localization was significantly greater than the current measured in cells with high Kv1.3 Golgi localization. One mechanism for localizing ion channels to the Golgi apparatus involves the Class I PDZ-binding motif (X-S/T-X-Φ). Deletion of the C-terminal PDZbinding motif of Kv1.3 decreased the intracellular Golgi localization of the channel and increased channel localization at the cell surface. Disrupting this canonical binding motif also increased the amplitude of Kv1.3 ionic current. These findings indicate that regulated subcellular distribution of the channel may be a determinant of Kv1.3 surface expression and function.

This thesis is concerned with ion-ion and ion-polymer interactions over a wide concentration range in polymer electrolytes with a view to shedding new light on the mechanism of ion migration. Additionally, the electrochemical stability window of these electrolytes on platinum and vitreous carbon electrodes has been thoroughly investigated. The final part of this thesis is concerned with determining the feasibility of polymer electrolytes as electrolytes in a new type of energy storage device, a double layer capacitor which incorporates activated carbon cloth electrodes. Conductivities and viscosities of solutions of Li, Na and K thiocyanates in low-molecular-weight, non-crystallizable liquid copolymers of ethylene oxide (EO) and propylene oxide (PO) have been measured. The curves of molar conductance versus sqrt c show well-defined maxima and minima. The conductivity is independent of copolymer molecular-weight but is enhanced by raising the EO content of the copolymer. The results are interpreted in terms of a model for ion migration in which ion association and redissociation effects play an important role. It is proposed that the characteristic properties of liquid polymer electrolytes can only be satisfactorily explained if the current is largely anionic. The electrochemical stability window of these electrolytes on platinum is dominated by the presence of a water reduction peak starting at approximately -1.0V which limits the overall stability to approximately 2V. The onset of water reduction is displaced to more negative potentials (-3.0V), thus increasing the stability window, on vitreous carbon electrodes. The value of the double layer capacitance on vitreous carbon electrodes (15-30muF cm-2) agrees well with published data. The double layer capacitance of activated carbon cloth electrodes is lower than anticipated. The importance of faradaic charging and discharging currents to the successful operation of double layer capacitors is indicated but no problems relating to the specific use of polymer electrolytes in such devices were found.