A novel cyclopentadienylruthenium(II) thiolato Schiff base, [Ru(SC6H4NC(H)C6H4OCH2CH2SMe)(&eta / 5-C2H5]2 was synthesized and deposited as a selfassembled monolayer (SAM) on a gold electrode. Effective electronic communication between the Ru(II) centers and the gold electrode was established by electrostatically cycling the Shiff base-doped gold electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAMmodified gold electrode (Au/SAM) exhibited quasi-reversible electrochemistry. The integrity of this electro-catalytic SAM, with respect to its ability to block and electro-catalyze certain Faradaic processes, was interrogated using Cyclic and Osteryoung Square Wave voltammetric experiments. The formal potential, E0', varied with pH to give a slope of about - 34 mV pH-1. The surface concentration, &Gamma / , of the ruthenium redox centers was found to be 1.591 x 10-11 mol cm-2. By electrostatically doping the Au/SAM/Horseradish peroxidase at an applied potential of +700 mV vs Ag/AgCl, a biosensor was produced for the amperometric analysis of hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide. The electrocatalytic-type biosensors displayed typical Michaelis-Menten kinetics with their limits of detection of 6.45 &mu / M, 6.92 &mu / M and 7.01 &mu / M for hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide respectively.

A novel cyclopentadienylruthenium(II) thiolato Schiff base,[Ru(SC6H4NC(H)C6H4OCH2CH2SMe)(η5-C2H5]2 was synthesized and deposited as a selfassembled monolayer (SAM) on a gold electrode. Effective electronic communication between the Ru(II) centers and the gold electrode was established by electrostatically cycling the Shiff base-doped gold electrode in 0.1 M NaOH from -200 mV to +600 mV. The SAMmodified gold electrode (Au/SAM) exhibited quasi-reversible electrochemistry. The integrity of this electro-catalytic SAM, with respect to its ability to block and electro-catalyze certain Faradaic processes, was interrogated using Cyclic and Osteryoung Square Wave voltammetric experiments. The formal potential, E0', varied with pH to give a slope of about - 34 mV pH-1. The surface concentration, Γ, of the ruthenium redox centers was found to be 1.591 x 10-11 mol cm-2. By electrostatically doping the Au/SAM/Horseradish peroxidase at an applied potential of +700 mV vs Ag/AgCl, a biosensor was produced for the amperometric analysis of hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide. The electrocatalytic-type biosensors displayed typical Michaelis-Menten kinetics with their limits of detection of 6.45 μM, 6.92 μM and 7.01 μM for hydrogen peroxide, cumene hydroperoxide and tert-butylhydroperoxide respectively / Magister Scientiae - MSc

All satellites need a propulsion system for orbit correction maneuvers. Electric Hall effect thrusters are an interesting technology for space applications. The big advantage compared to chemical propulsion devices is the higher specific impulse Isp, a higher ejection speed and thus a substantial gain in terms of propellant consumption. In a Hall effect thruster the ions are created and accelerated in a low pressure discharge plasma in a magnetic field. The first part of the work concerns scaling laws for Hall effect thrusters. A semi-empirical scaling model based on analytical laws and relying on simplifying assumptions is developed. This scaling model can be used to extrapolate existing thruster technologies in order to meet new mission requirements. In a second part, the influence of the channel width on the thruster performance level is investigated. It has been demonstrated that enlarging the channel width of a low power Hall effect thruster leads to an increase in thruster efficiency. Finally, electron properties are measured by means of electrostatic probes in the plume of different Hall effect thrusters. Experimental data on electron properties is of great interest for the validation of numerical plume models that are essential for the integration of the thruster on the satellite. Time-averaged and timeresolved measurements of the electron properties have been carried out for different operating conditions of the thruster. A fast-moving probe system has been developed in order to perform measurements of the electron properties close to the thruster exit plane.

This study focuses on fabrication of dry adhesives mimicking gecko adhesion. We also look into the origin of the supreme adhesion of geckos, which have inspired the fabrication of fibrillar dry adhesives during the last decade or so. In principle, the superior material properties of ??-keratin (the main material comprising the fibrillar feature on gecko toe pads) along with the hierarchical high aspect-ratio fibrillar structure of geckos??? foot pad have enabled geckos to stick readily and rapidly to almost any surface in both dry and wet conditions. In this research, non-sticky fluoropolymer (Teflon AF) resembling ??-keratin rigidity and having an extremely low surface energy and dielectric constant was applied to fabricate a novel dry adhesive consisting of extremely high aspect-ratio nanopillars (200 nm in diameter) terminated with a fluffy top nanolayer. Both the nanopillars and the terminating layer were fabricated concurrently by replica-molding using a nanoporous anodic aluminum oxide membrane as the mold. In particular, upon infiltration of Teflon AF melt into the anodic aluminum oxide nanopores, the polymer melt fingered over the pore walls. The fingerlike structure formed during infiltration, subsequently collapsed after removal of the mold, developing a unique sheet-like nanostructure on top of the base nanopillars. Concurrent fabrication of the terminating nanostructure helps the fabrication of extremely high aspect-ratio (27.5???225) nanopillars which, up to an aspect-ratio of 185, neither collapse at the tip nor bundle. In order to fabricate nanopillars of different topographical properties, in our first approach, the height of the nanopillars as well as the size and density of the terminating nanostructure are carefully controlled by adjusting the processing temperature. Following that, a novel replica-molding technique for fabrication of bi-level Teflon AF nanopillars is reported. The developed technique relies on the concurrent heating and cooling of the Teflon AF melt which filled vertically-aligned alumina nanochannels. Unlike conventional polymer infiltration methods which consist of filling the mold by only heating the polymer above its glass transition temperature, in our novel method, the polymer melt is also simultaneously cooled down during the infiltration process. Concurrent cooling of the Teflon AF melt allows control over the interfacial instabilities of the polymer thin film, which forms ahead of the polymer melt upon its infiltration into the alumina nanochannels. Doing so, the geometrical properties of the subsequently developed peculiar fluffy nanostructure ??? after removal of the mold ??? on top of the extremely high aspect-ratio Teflon AF nanopillars (~25 ??m tall) are modified. In this project, we have also shown that the adhesion of the fabricated dry adhesives for the most part arises from electrostatic interactions of the applied polymer. In other words, Teflon AF, having an exceptional potential for developing electric charges at its surface upon contact with other materials via the so-called contact electrification phenomenon, can develop significant electrostatic interactions at its surface upon contact. In the current thesis, tribological results were discussed in detail to clarify the contribution of the structural properties of the fabricated dry adhesives toward their remarkable adhesion and friction forces generated via contact electrification. Nanopillars of specific geometrical properties have achieved remarkable adhesion and friction strengths, up to ~2.1 N/cm2 and 17 N/cm2, respectively (up to ~2.1 and 1.7 times larger than those of a gecko toe pad). It is commonly accepted that the adhesive performance of other synthetic bio-inspired dry adhesives is due to the formation of van der Waals interactions at the tip or side of the dry adhesives fibrils with the substrate they are brought into contact with. However, what has been usually neglected in this connection is that electrostatic interactions may also be developed at the contact between any two materials via the familiar contact electrification phenomenon. Although contact electrification is common and can have a large influence on interfacial interaction forces, its impact on adhesive properties of synthetic dry adhesives has been overlooked. Our results on adhesion of bi-level Teflon AF nanopillars, which can generate strong adhesion forces relying on electrostatic interactions arising from contact electrification, have brought to light again the idea that charging the surface of dry adhesives, specifically polymeric ones, can play a very crucial role in their adhesive behavior. From this perspective, the main reasons that have caused this lack of attention to this concept and the possible contributions of contact electrification to interfacial interactions of polymeric dry adhesives, other than bi-level Teflon AF nanopillars, are also thoroughly discussed in this thesis. Besides synthetic fibrillar dry adhesives, the possibility of the occurrence of contact electrification and its contribution to the supreme dry adhesion of geckos have also been overlooked for several decades. In this research, by the simultaneous measurement of electric charges and adhesion forces that gecko toe pads develop on two distinct substrates (a sticky and a non-sticky one), we have shown that the toe pads generate significantly large amounts of electric charge on both substrates. More importantly, we have found that there is a direct correlation between the contact electrification-driven electrostatic forces and the measured adhesion forces. Otherwise stated, we have shown that what makes the difference that geckos stick strongly to one surface and not to the other are the electrostatic interactions arising from contact electrification, and not van der Waals interactions, which have been considered as the prime source of adhesion of geckos for many years.

This dissertation presents chemical sensors that are based on an emerging optical fiber sensing technology for the determination of the presence and concentration of hydrogen peroxide (H2O2) at low concentrations. The motivation to determine hydrogen peroxide lies on the fact that this chemical species is generated as a by-product of the operation of hydrogen-based polymer electrolyte membrane fuel cells (PEMFCs), and the presence and formation of this peroxide has been associated with the chemical degradation that results in low durability of PEMFCs. Currently, there are no techniques that allow the hydrogen peroxide to be determined in situ in PEMFCs in a reliable manner, since the only report of this type of measurement was performed using electrochemical techniques, which can be affected by the environmental conditions and that can alter the proper operation of the PEMFCs. The sensors presented in this dissertation are designed to detect the presence and quantify hydrogen peroxide in solution at the conditions at which PEMFCs operate. Since they are made using fused silica optical fibers and are based on a spectroscopic technique to perform the detection of H2O2 , they are not affected by the electromagnetic fields or the harsh chemical environment inside PEMFCs. In addition, they are able to still detect the presence of H2O2 at the operating temperatures. The construction of the sensing film on the tip of an optical fiber and its small size (125 µm diameter), make the sensors here developed an ideal solution for being deployed in situ in PEMFCs, ensuring that they would be minimally invasive and that the operation of the fuel cell would not be compromised by the presence of the sensor. The sensors developed in this dissertation not only present design characteristics that are applicable to PEMFCs, they are also suitable for applications in other fields such as environmental, defense, and biological processes. / Graduate / 0548 / 0756 / 0791 / jfbotero@gmail.com

This dissertation presents chemical sensors that are based on an emerging optical fiber sensing technology for the determination of the presence and concentration of hydrogen peroxide (H2O2) at low concentrations. The motivation to determine hydrogen peroxide lies on the fact that this chemical species is generated as a by-product of the operation of hydrogen-based polymer electrolyte membrane fuel cells (PEMFCs), and the presence and formation of this peroxide has been associated with the chemical degradation that results in low durability of PEMFCs. Currently, there are no techniques that allow the hydrogen peroxide to be determined in situ in PEMFCs in a reliable manner, since the only report of this type of measurement was performed using electrochemical techniques, which can be affected by the environmental conditions and that can alter the proper operation of the PEMFCs. The sensors presented in this dissertation are designed to detect the presence and quantify hydrogen peroxide in solution at the conditions at which PEMFCs operate. Since they are made using fused silica optical fibers and are based on a spectroscopic technique to perform the detection of H2O2 , they are not affected by the electromagnetic fields or the harsh chemical environment inside PEMFCs. In addition, they are able to still detect the presence of H2O2 at the operating temperatures. The construction of the sensing film on the tip of an optical fiber and its small size (125 µm diameter), make the sensors here developed an ideal solution for being deployed in situ in PEMFCs, ensuring that they would be minimally invasive and that the operation of the fuel cell would not be compromised by the presence of the sensor. The sensors developed in this dissertation not only present design characteristics that are applicable to PEMFCs, they are also suitable for applications in other fields such as environmental, defense, and biological processes. / Graduate / 0548 / 0756 / 0791 / jfbotero@gmail.com

The aim of this study was to investigate the molecular interactions of the anti-cancer drug Doxorubicin (DOX) with poly(methacrylic acid) grafted starch nanoparticles (PMAA-g-St). In order to fully understand the DOX/PMAA-g-St system, we conducted in-depth studies on DOX dimer dissociation and DOX/PMAA-g-St binding interactions using various techniques such as isothermal titration calorimetry (ITC), dynamic light scattering (DLS), and fluorescence and absorption spectroscopy. Based on our experimental results, we developed a quantitative thermodynamic model with relevant parameters such as dissociation constant, Kd, as well as enthalpy of binding, ΔH, in order to explain DOX/PMAA-g-St interactions. In addition, we also studied the effect of environmental factors such as pH and NaCl on DOX self-association and DOX/PMAA-g-St complex formation. In conclusion, the combination of results obtained from various techniques as well as the multispecies equilibrium model, enables us to interpret quantitatively the data of drug loading onto and release from polymeric nanoparticles.

An electrostatic actuator driven by conventional voltage control and charge control requires high actuation voltage and suffers from the pull-in phenomenon that limits its operation range, much less than its entire gap. To provide effective solutions to these problems, we present complete analytical and numerical models of various electrostatic actuators coupled with resonant drive circuits that are able to drive electrostatic actuators at much lower input voltage than that of conventional actuation methods and to extend their operation range beyond their conventional pull-in points in the presence of high parasitic capacitance. Moreover, in order to validate the analytical and numerical models of various electrostatic actuators coupled with the resonant drive circuits, we perform the experiment on the microplate and the micromirror coupled with the resonant drive circuit. For instance, using a high voltage amplifier, we manage to rotate the micromirror with sidewall electrodes by 6 ° at 180 V. However, using the resonant drive circuit, we are able to rotate the same micromirror by 6 ° at much lower input voltage, 8.5 V. In addition, the presented work also facilitates the stability analysis of electrostatic actuators coupled with the resonant drive circuits and provides how the effect of the parasitic capacitance can be minimized. For example, the resonant drive circuit placed within a positive feedback loop of a variable gain amplifier is able to extend the operation range much further even in the presence of very high parasitic capacitance. The resonant drive circuit with the proposed feedback controllers is also able to minimize the detrimental effects of the parasitic capacitance and to displace a parallel-plate actuator over its entire gap without the saddle-node bifurcation. Finally, we present a new displacement measurement method of electrostatic actuators coupled with the resonant drive circuits by sensing the phase delay of an actuation voltage with respect to an input voltage. This new measurement method allows us to easily implement feedback control into existent systems employing an electrostatic actuator without any modification or alteration to the electrostatic actuator itself. Hence, this research work presents the feasibility of electrostatic actuators coupled with the resonant drive circuit in various industrial and medical applications, in which the advantages of miniaturization, low supply voltage, and low power consumption are greatly appreciated.

The objective of the work presented in this thesis is to implement high-Q silicon capacitive micromechanical resonators operating in the HF, VHF and UHF frequency bands. Several variations of a fully silicon-based bulk micromachining fabrication process referred to as HARPSS have been developed, characterized and optimized to overcome most of the challenges facing application of such devices as manufacturable electronic components. Several micromechanical structures for implementation of high performance capacitive silicon resonators covering various frequency ranges have been developed under this work. Design criteria and electromechanical modeling of such devices is presented. Under this work, HF and VHF resonators with quality factors in the tens of thousands and RF-compatible equivalent electrical impedances have been implemented successfully. Resonance frequencies in the GHz range with quality factors of a few thousands and lowest motional impedances reported for capacitive resonators to date have been achieved. Several resonator coupling techniques for implementation of higher order resonant systems with possibility of extension to highly selective bandpass filters have been investigated and practically demonstrated. Finally, a wafer-level vacuum sealing technique applicable to such resonators has been developed and its reliability and hermeticity is characterized.

Over the last 20 years "composite" insulators have been increasingly used in high voltage applications as an alternative traditional materials. More recently, polydimethylsiloxane (PDMS) have been used as weather sheds on these composite insulators. The main attraction with PDMS is that the surface hydrophobicity can be recovered following pollution or surface discharges. Among the possible mechanisms for recovery the most likely is the migration of low molecular weight silicone oil (LMWS) from the bulk to the surface encapsulating pollutant particles. Although it is widely recognised that the migration of LMWS is the cause of this recovery of hydrophobicity, the mechanism of what actually occurs is not well understood. It is also not known for how long this process will continue. The main objective of this study program was to gain improved understanding of the surface hydrophobic recovery process that is unique to polydimethlysiloxane high-voltage insulators. Fundamental knowledge of this mechanism has been increased through the development of the Contact Angle DRIFT Electrostatic Deposition (CADED) novel analytical technique. This technique enabled study of the degradation of silicone elastomers subjected to high voltage environments by closely following LMWS migration from the bulk material to the surface and linking it to the contact angle measurements. The migration rate data showed that the aged material recovered faster that the virgin material. Differences in the rate and maximum surface levels of silicone were seen between materials from different manufacturers. This has significant implications for the life-time of these materials A model system has been developed to examine LMWS diffusion through the bulk material and into the interface of surface and pollutant. This was achieved by examining theoretical and empirically derived equations and using existing experimental data to better understand the mechanism of recovery. This diffusion was Fickian in the initial stages of recovery. X-ray photoelectron spectroscopy (XPS) and contact angle measurements were used to substantiate the degree of degradation in in-field silicone insulators by quantifying the levels of the major degradation products: silica and silica-like material and alumina.