A series of substituted indoles have been synthesized by the sequential reaction of aromatic aldehydes with ethyl azidoacetate in the presence of sodium ethoxide to form the corresponding ethyl α-azido-β-arylacrylates (Knoevenagel process) followed by a solvent mediated thermolysis (Hemetsberger process). The isolated yields of the ethyl α-azido-β-arylacrylates were significantly increased when employing the sacrificial electrophile ethyl trifluoroacetate. 1H NMR and coupled 1H-13C NMR analysis of the ethyl α-azido-β-arylacrylates indicate that the condensation is stereospecific—only the Z-isomer could be detected. Solvent mediated thermal treatment of the meta-substituted ethyl α-azido-β-arylacrylates resulted in the formation of both the 5- and 7- substituted indoles—the 5-regioisomer being slightly favored over the 7-regioisomer. Analogous thermal treatment of (2Z, 2Z’)-diethyl 3,3’-(1,3-phenylene)bis(2-azidoacrylate) and (2Z, 2Z’)-diethyl 3,3’-(1,4-phenylene)bis(2-azidoacrylate) exclusively produced pyrroloindoles, diethyl 1,5-dihydropyrrolo[2,3-f]indole-2,6-dicarboxylate and diethyl 1,5-dihydropyrrolo[2,3-f]indole-2,6-dicarboxylate, respectively. Results are also reported which indicate that the α-azido-β-arylacrylates can be used in the subsequent Hemetsberger indolization process without prior purification. Organic substrates containing basic nitrogen centers have been problematic in achieving high yields in the Suzuki coupling process. The origin of this issue is attributed to the complexation of the basic nitrogen center with the palladium catalyst. As a consequence, the use of CO₂ at a variety of pressures was evaluated as a reversible protecting/activating reagent for basic nitrogen containing substrates. The following observations and conclusions were reached. (1) The use of small amounts of water significantly improves the rate and yield of Suzuki coupling reactions. (2) In the presence of aqueous CO₂, careful selection of the base is essential due to formation of bicarbonate and the associated decrease in the amount water. K3PO4 was found to be the most effective base in the presence of CO₂. (3) The yield of product in the Suzuki coupling of 4-amino-2-bromopyridine with phenylboronic acid was evaluated as a function of CO₂ pressure. Compared to reactions in the absence of CO₂, the yield of product increased at all pressures of CO₂ (6.8, 17, and 30.6 atm) - from 15% with no CO₂ to 73% with 30.6 atm of CO₂.

Electronically monitoring whether or not your car block heater is connected to a mains outlet might at first seem like an arbitrary task. A device installed in the comfort of the car seating area, which tells the user at every startup whether or not his/her car is connected to a mains outlet, could have market appeal though. But in order for it to be a worthwhile idea to pursuit, a certain requirement has to be met. It has to be able to be able to accurately detect whether or not the car is connected, through a single connection; the car ground. A certain part of the voltage in the phase of the mains will be capacitively coupled upon the safety ground. By exploiting the fact that the car ground will be connected to the mains safety ground when the block heater cable is in use, a device which can detect that coupled voltage could possibly be developed. In other words, a cable monitoring unit which in actuality detects a connection to the mains safety ground through capacitive coupling, hence the title of this dissertation. This work sets out to taking appropriate measurements to find out whether or not this proposed method of safety ground detection is valid, with heavy emphasis on whether or not it is applicable to a cable monitoring unit. According to the measurement results, an appropriate device is developed. A device which can fill the function described in the previous paragraph. Development of such a device involves; proper method of supplying power which upholds a galvanically isolated floating ground, signal processing, reliable detection mechanism, and considerations to how unintentional capacitive coupling behaves. A theoretical model of the device is put forth, as well as an actual rough prototype to in practice try to prove that the concept and method is valid. Downsides and problems with the device are discussed, such as upholding an effective detection system without making the device hard and cumbersome to use. Possible solutions to these problems are also proposed. The possible future of the concept of this device is also touched upon.

This study explores the question of how educational bureaucracies impact school efficacy, from the perspectives of senior administrators, a group made up of superintendents and assistant superintendents. The literature review defines the terms educational bureaucracy and systems coupling, which provide a theoretical framework for the study and serve as a lens through which the data, anecdotal reports contextualized by real-life experiences, are analyzed and the theme of school efficacy is explored. Understanding the unique perspective of the senior administrator’s role with regards to educational bureaucracy and its impact will provide a basis from which the structure of school systems is explored more deeply, and the ways in which systems coupling and elements of bureaucratic structures might be used as tools to improve school efficacy. The aim of this study is to better understand the specific functions of educational bureaucracies that have a perceived and/or measured effect on school efficacy. Rather than using a uniform measure of school efficacy, which could serve to limit the experiences shared by participants, the secondary aim of this study is to develop possible definitions/conceptualizations of school efficacy based on the anecdotal reports provided by participants, through the application of grounded theory. The findings of this study and the implications for practice will be of interest to those studying the sociological foundations of education and to stakeholders who wish to know more about the functioning of educational bureaucracies at the systemic level, and how they impact school efficacy.

A Global Positioning System (GPS) can be used to estimate an objects position,given that the object has a GPS antenna. However, the system requires informationfrom at least four independent satellites in order to be able to give a positionestimate. If two GPS antennas and a carrier-phase GPS measurement unit is usedan estimate of the objects heading can be calculated by determine the baselinebetween the two antennas. The method is called GPS Attitude Determination(GPSAD) and requires that an Integer Ambiguity Problem (IAP) is solved. Thismethod is cheaper than more traditional methods to calculate the heading butis dependent on undisturbed GPS-reception. Through support from an InertialMeasurement Unit (IMU), containing accelerometers and gyroscopes, the systemcan be enhanced. In Thorstenson [2012] data from GPS, GPSAD and IMU wasintegrated in an Extended Kalman Filter (EKF) to enhance the performance. Thisthesis is an extension on Thorstensons work and is divided into two separate problems:enhancement of positioning when less than four satellites are available andthe possibility to integrate the EKF with the search of the correct integers for theIAP in order to enhance the estimation of attitude. For both problems an implementationhas been made and the performance has been enhanced for simulateddata. For the first problem it has been possible to enhance the performance onreal data while that has not been possible for the second problem. A number ofproposals is given on how to enhance the performance for the second problemusing real data.

This thesis is a study of solid halogenated organic compounds by Nuclear Magnetic Resonance Spectroscopy (NMR) in an attempt to extract previously inaccessible information. The first part of the thesis is concerned with three fluorinated steroids, studied by observing (^1)H, (^13)C and (^19)F nuclei. A number of experimental techniques are employed to verify solution-state and solid-state spectral assignments, and spectral anomalies are discussed. Both proton-coupled and proton-decoupled (^19)F solid-state spectra, recorded using specially designed spectrometer hardware, are presented. The huge gain in resolution afforded by the implementation of proton decoupling allows static and MAS spectra to yield previously inaccessible information pertaining to various NMR parameters of the fluorine nuclei. Advantages of (^1)H→(^19)F cross-polarisation experiments over single-pulse experiments are explained and rotational resonance, dipolar dephasing, T(_1), measurement and spin-exchange experiments are presented from which information regarding phenomena such as spin diffusion and polymorphism is gleaned. The second part of the thesis focusses on the topic of residual dipolar coupling, the transfer of quadrupolar effects to spin-1/2 nuclei via dipolar coupling and/or anisotropy m indhect coupling. Unexpected, field-dependent, multiplicities for signals in spectra of spin-1/2 nuclei are observed, which can be used to evaluate certain fundamental NMR parameters including the quadrupolar coupling constant and, m favourable cases, anisotropy in indirect coupling. The phenomenon is comprehensively studied for the (^13)C, (^35,37)Cl and (^13)C, (^79,81)Br spin-pairs in a range of solid halogenated compounds. Coupling to more than one halogen nucleus and long- range (non-bonded) coupling are considered. First-order perturbation, inverse first- order and "exact" theories, that allow the multiplet line positions to be predicted, are introduced and their results are subsequently compared to the experimentally observed the positions. Rapid molecular motion is shown to negate the effects of residual dipolar coupling and the phenomenon is analysed with the aid of NQR measurements.

In this thesis, the 2×2 MIMO performance of several low mutual coupling antennas has been investigated in indoor and hallway scenarios. Three compact antennas intended for mobile applications with low mutual coupling between the input ports are presented in this thesis. To gauge the performances of the three designed antennas, two reference antennas are also used. Channel capacity measurements were conducted in Bahen Center Antenna Lab room 8175 and the Bahen Center 8th floor hallway by using the five antennas as receivers. The antenna spatial location, orientation, line-of-sight and non-line-of-sight situation and richness of multipath effect were considered in the measurements. By averaging the results, it is found that in an indoor environment, low mutual coupling antennas can outperform the reference high mutual coupling antennas especially in higher SNR scenarios. In the hallway environment, low mutual coupling antennas always outperform the reference high mutual coupling antennas due to pattern diversity.

In this thesis, the 2×2 MIMO performance of several low mutual coupling antennas has been investigated in indoor and hallway scenarios. Three compact antennas intended for mobile applications with low mutual coupling between the input ports are presented in this thesis. To gauge the performances of the three designed antennas, two reference antennas are also used. Channel capacity measurements were conducted in Bahen Center Antenna Lab room 8175 and the Bahen Center 8th floor hallway by using the five antennas as receivers. The antenna spatial location, orientation, line-of-sight and non-line-of-sight situation and richness of multipath effect were considered in the measurements. By averaging the results, it is found that in an indoor environment, low mutual coupling antennas can outperform the reference high mutual coupling antennas especially in higher SNR scenarios. In the hallway environment, low mutual coupling antennas always outperform the reference high mutual coupling antennas due to pattern diversity.

Nanomaterials have been studied extensively in the last decade in the context of many applications such as polymer composites, energy harvesting systems, sensors, ‘transparent’-like materials, field-effect transistors (FETs), spintronic devices, gas sensors and biomedical applications. Graphene, a recently discovered two-dimensional form of carbon has captured the interest of material scientists, and physicists alike due to its excellent electrical, mechanical and thermal properties. Graphene has also kindled a tremendous interest among chemists and cell biologists to create cellular-electronic interface in the context of bio-electronic devices as it can enable fabricating devices with enhanced potential as compared to conventional bio-electronics. Graphene’s unique electronic properties and sizes comparable with biological structures involved in cellular communication makes it a promising nanostructure for establishing active interfaces with biological systems. In the recent past Field effect transistors (FETs) have been successfully fabricated using carbon nanotubes (CNTs) and nanowires (NWs) and electrical characterization of these FETs were done by interfacing them with various cell cultures, tissues and muscle cells. In these cases, exceptionally high surface area to thickness ratio of FETs provides high percentage of collectible signals and the cells that are used for the study are typically placed on the FET. In this thesis, we examine a different approach towards forming bio-electronic interfaces by covering the graphene oxide (reduced) sheets on the yeast cells. Graphene oxide and reduced graphene oxide sheets as two-dimensional electronic materials have very high charge carrier mobility, extremely high surface area to thickness ratio, mechanical modulus and elasticity. We report the synthesis of graphene oxide using wet chemistry method, reduction of graphene oxide using different reducing agents and electrical characterization of graphene oxide’s conductivity. Micro-meter sized graphene sheets are used to encapsulate the yeast cells with the aid of calcium and gold nanoparticle chains. We also demonstrate that graphene sheets form electrically conductive layers on the yeast cells and developing an electromechanical coupling with the cell. The mechanical and electrical characteristics of graphene sheets are highly dependent on the cell volume and structure which are in turn related to the environment around the cell. Furthermore, using the same principle of electromechanical coupling we study the dynamics of cell surface stresses and cell volume modification, which are of importance in processes such as cell growth, division, and response to physiological factors such as osmotic stresses.

Consider the problem of designing capacity-achieving codes for multi-terminal communication scenarios. For point-to-point communication problems, one can optimize a single code to approach capacity, but for multi-terminal problems this translates to optimizing a single code to perform well over the entire region of channel parameters. A coding scheme is called universal if it allows reliable communication over the entire achievable region promised by information theory. It was recently shown that terminated low-density parity-check convolutional codes (also known as spatially-coupled low-density parity-check ensembles) have belief-propagation thresholds that approach their maximum a-posteriori thresholds. This phenomenon, called "threshold saturation via spatial-coupling," was proven for binary erasure channels and then for binary memoryless symmetric channels. This approach provides us with a new paradigm for constructing capacity approaching codes. It was also conjectured that the principle of spatial coupling is very general and that the phenomenon of threshold saturation applies to a very broad class of graphical models. In this work, we consider a noisy Slepian-Wolf problem (with erasure and binary symmetric channel correlation models) and the binary-input Gaussian multiple access channel, which deal with correlation between sources and interference at the receiver respectively. We derive an area theorem for the joint decoder and empirically show that threshold saturation occurs for these multi-user scenarios. We also show that the outer bound derived using the area theorem is tight for the erasure Slepian-Wolf problem and that this bound is universal for regular LDPC codes with large left degrees. As a result, we demonstrate near-universal performance for these problems using spatially-coupled coding systems.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23910号 / 工博第4997号 / 新制||工||1780(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 中尾 佳亮, 教授 松原 誠二郎, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM