This dissertation presents the synthesis of a series of well-defined multiresponsive hydrophilic ABA linear triblock copolymers and the study of their aqueous micellar gels. By incorporating a small amount of stimuli-responsive groups into thermosensitive outer blocks of ABA triblock copolymers, the lower critical solution temperatures (LCST) of thermosensitive blocks can be modified by external stimuli. Consequently, the sol-gel transition temperatures (Tsol-gel) of their aqueous solutions can be altered. Chapter 1 describes the synthesis and solution behavior of a series of thermo- and light-sensitive triblock copolymers, poly(ethoxytri(ethylene glycol) acrylate-co-o-nitrobenzyl acrylate)-b-poly(ethylene oxide)-b-poly(ethoxytri(ethylene glycol) acrylate-co-o-nitrobenzyl acrylate), with different contents of light-responsive o-nitrobenzyl groups. Aqueous solutions of these block copolymers with a 10.0 wt% concentration exhibited thermo-induced sol-gel transitions. Upon UV irradiation, the hydrophobic o-nitrobenzyl groups were cleaved, resulting in an increase in the LCST and consequently gel-to-sol transitions. The UV-irradiated solutions again underwent temperature-induced sol-gel transitions but at higher temperatures. The change of Tsol-gel was, in general, larger for the copolymer with a higher o-nitrobenzyl content after UV irradiation. Chapter 2 presents the synthesis of thermo- and enzyme-responsive ABA triblock copolymers, poly(ethoxydi(ethylene glycol) acrylate-co-4-((dihydroxyphosphoryl)oxy)butyl acrylate)-b-poly(ethylene oxide)-b-poly(ethoxydi(ethylene glycol) acrylate-co-4-((dihydroxyphosphoryl)oxy)butyl acrylate), and the enzyme-induced formation of thermoreversible micellar gels from their moderately concentrated aqueous solutions at 37 °C. The dephosphorylation by acid phosphatase decreased the LCST of thermosensitive outer blocks from above to below 37 °C. The enzyme-induced gelation of 7.9 wt % aqueous polymer solutions at pH 4.4 was monitored by rheological measurements. The Tsol-gel decreased and the gel strength increased with the increase of reaction time. The gels formed were thermoreversible. Chapter 3 presents the synthesis of two thermo- and pH-sensitive tertiary amine-containing ABA triblock copolymers and the sol-gel transitions of their aqueous solutions with a 10 wt% concentration at different pH values. Chapter 4 describes the use of reversible addition-fragmentation chain transfer (RAFT) polymerization for the synthesis of well-defined thermosensitive polymethacrylates and polyacrylates. Eight chain transfer agents were synthesized. The RAFT polymerizations of alkoxyoligo(ethylene glycol) (meth)acrylates using these chain transfer agents were well controlled, producing well-defined polymers. A summary of this dissertation research and future work are presented in Chapter 5.

Competitive-Consecutive and Competitive-Parallel reactions are both mixing sensitive reactions; the yield of desired product from these reactions depends on how fast the reactants are brought together. Recent experimental results have suggested that the mixing effect may depend strongly on the stoichiometry of the reactions. To investigate this, a 1-D, non-dimensional, reaction-diffusion model at the micro-mixing scale has been developed. Assuming constant mass concentration and diffusivities, systems of PDEs have been derived on a mass fraction basis for both types of reactions. A single general Damkhler number and specific dimensionless reaction rate ratios were derived for both reaction schemes. The resulting dimensionless equations were simulated to investigate the effects of mixing, reaction rate ratio and stoichiometry of the reactions. It was found that decreasing the striation thickness and the dimensionless rate ratio maximizes yield for both types of reactions and that the stoichiometry has a considerable effect on yield. All three variables were found to interact strongly. Phase plots showing the interactions between the three variables were developed.

Phenelzine (PLZ) is a monoamine oxidase (MAO) inhibitor that also inhibits the activity of GABA-transaminase (GABA-T), causing significant and long-lasting increases in brain GABA levels. Inhibition of MAO prior to PLZ administration has been shown to prevent the GABAergic effects of the drug, strongly suggesting that a metabolite of PLZ formed by the action of MAO is responsible for the GABAergic effects. While PLZ has been used clinically for decades for its antidepressant and antipanic effects, it has more recently been shown to be neuroprotective in an animal model of ischemia. The aim of the experiments described in this thesis was to identify the active metabolite of PLZ, and to determine the neurochemical mechanisms by which PLZ and this metabolite exert their neuroprotective effects (with a particular focus on degenerative mechanisms observed in cerebral ischemia and Alzheimers disease (AD)). The development of an analytical assay for -phenylethylidenehydrazine (PEH) was a major breakthrough in this project and permitted the positive identification of this compound as the active metabolite of PLZ. Further experiments demonstrated that PLZ and PEH could be neuroprotective in cerebral ischemia and AD not only by reducing excitotoxicity via increased GABAergic transmission, but also by (a) increasing brain ornithine, which could potentially lead to a decrease in glutamate synthesis and/or a decrease in polyamines (whose metabolism produces toxic aldehydes); (b) inhibiting the activity of human semicarbazide-sensitive amine oxidase (SSAO), an enzyme whose activity is increased in AD producing excessive amounts of the toxic aldehyde formaldehyde (FA); (c) by sequestering FA in vitro, forming a non-reactive hydrazone product. Since PEH appears to mediate or share the neurochemical effects of PLZ, two propargylated analogs of PEH were synthesized and tested for their potential as PEH prodrugs. Surprisingly these analogs were not particularly effective prodrugs in vivo, but they possessed an interesting neurochemical properties on their own (the ability to elevate brain levels of glycine), and warrant further investigation as potential antipsychotic agents. Together, these results suggest that PLZ and its active metabolite, PEH, should be further investigated for their neuroprotective potential in cerebral ischemia and in AD. / Neurochemistry

In this study, the film-cooling effectiveness in different regions of gas turbine blades was investigated with various film hole/slot configurations and mainstream flow conditions. The study consisted of three parts: 1) turbine blade span film-cooling, 2) turbine platform film-cooling, and 3) blade tip film-cooling. Pressure sensitive paint (PSP) technique was used to get the conduction-free film-cooling effectiveness distribution. Film-cooling effectiveness is assessed in terms of cooling hole geometry, blowing ratio, freestream turbulence, and coolant-to-mainstream density ratio. Blade span film-cooling test shows that the compound angle shaped holes offer better film effectiveness than the axial shaped holes. Greater coolant-to-mainstream density ratio prevents coolant to lift-off. Higher freestream turbulence causes effectiveness to drop everywhere except in the region downstream of suction side. Results are also correlated with momentum flux, compound shaped hole has the greatest optimum momentum flux ratio, and then followed by axial shaped hole, compound cylindrical hole, and axial cylindrical hole. For platform purge flow cooling, the stator-rotor gap was simulated by a typical labyrinth-like seal. Two different film-cooling hole geometries, three blowing ratios and density ratios, and two freestream turbulence are examined. Results showed that the shaped holes present higher film-cooling effectiveness and wider film coverage than the cylindrical holes, particularly at higher blowing ratios. Moreover, the platform film-cooling effectiveness increases with density ratio but decreases with turbulence intensity. The blade tip study was performed in a blow-down flow loop. Results show that a blowing ratio of 2.0 is found to give best results on the tip floor. Lift-off of the coolant jet can be observed for the holes closer to the leading edge as blowing ratio increases from 1.5 to 2.0. A stator vane suction side heat transfer study was conducted in a partial annular cascade. The heat transfer coefficients were measured by using the transient liquid crystal technique. At X/L=0.15, a low heat transfer region where transition occurs. The heat transfer coefficients increase toward the trailing edge as flow accelerates; a spanwise variation can be found at neat tip and hub portions due to passage and horseshoe vortices.

The provision of water, wastewater and stormwater infrastructure is an essential ingredient of cities. However, questions are being raised about the type and form of urban infrastructure, for economic and environmental reasons. Traditionally these techologies have offered linear solutions, drawing increasing volumes of water into cities and discharging waste at ever increasing levels, causing escalating stress on the environment. In addition the costs of water infrastructure provision and replacement, both in the developing and developed world, is becoming prohibitive. In response, a new paradigm has been called for and new solutions are emerging that have been labelled as Integrated Urban Water Management (IUWM). This concept can be considered to consist of both technical and philosophical dimensions, and represents a new form of professional praxis. However, the adoption of these techniques and concepts is constrained by the inertia of the existing urban water systems. It is therefore argued that the introduction of any change must occur across a number of dimensions of the technoeconomic system of the city. These dimensions-artefacts and technical systems (i.e. the technology and knowledge systems), professional praxis and socio-political context (i.e. institutions, culture and politics) and biophysical realities and world views (i.e. the environment and underlying values) - provide a framework for analysis of the change process - both how it is occurring and how it needs to occur. This framework is used to illustrate the link between environment values and the process of technological innovation, and points to the need for the emerging values and innovations to be institutionalised into the professional praxis and socio-political context of society. Specifically, it is argued that a new form of transdisciplinary professional praxis is emerging and needs to be cultivated. A broad review of the literature, an evaluation of selected emerging technologies and three case studies are used to illustrate and argue this position. These examples show the potential economic, social and environmental benefits of IUWM and provide some insight into the potential which this approach has to influence the form and structure of the city and at the same time highlighting the institutional arrangements required to manage urban water systems.

The work presented in this thesis discusses various formalisms for representing the addition of order-controlling and order-relaxing mechanisms to existing formal language models. An immediate example is shuffle expressions, which can represent not only all regular languages (a regular expression is a shuffle expression), but also features additional operations that generate arbitrary interleavings of its argument strings. This defines a language class which, on the one hand, does not contain all context-free languages, but, on the other hand contains an infinite number of languages that are not context-free. Shuffle expressions are, however, not themselves the main interest of this thesis. Instead we consider several formalisms that share many of their properties, where some are direct generalisations of shuffle expressions, while others feature very different methods of controlling order. Notably all formalisms that are studied here have a semi-linear Parikh image, are structured so that each derivation step generates at most a constant number of symbols (as opposed to the parallel derivations in for example Lindenmayer systems), feature interesting ordering characteristics, created either by derivation steps that may generate symbols in multiple places at once, or by multiple generating processes that produce output independently in an interleaved fashion, and are all limited enough to make the question of efficient parsing an interesting and reasonable goal. This vague description already hints towards the formalisms considered; the different classes of mildly context-sensitive devices and concurrent finite-state automata. This thesis will first explain and discuss these formalisms, and will then primarily focus on the associated membership problem (or parsing problem). Several parsing results are discussed here, and the papers in the appendix give a more complete picture of these problems and some related ones.

abstract: K-Nearest-Neighbors (KNN) search is a fundamental problem in many application domains such as database and data mining, information retrieval, machine learning, pattern recognition and plagiarism detection. Locality sensitive hash (LSH) is so far the most practical approximate KNN search algorithm for high dimensional data. Algorithms such as Multi-Probe LSH and LSH-Forest improve upon the basic LSH algorithm by varying hash bucket size dynamically at query time, so these two algorithms can answer different KNN queries adaptively. However, these two algorithms need a data access post-processing step after candidates' collection in order to get the final answer to the KNN query. In this thesis, Multi-Probe LSH with data access post-processing (Multi-Probe LSH with DAPP) algorithm and LSH-Forest with data access post-processing (LSH-Forest with DAPP) algorithm are improved by replacing the costly data access post-processing (DAPP) step with a much faster histogram-based post-processing (HBPP). Two HBPP algorithms: LSH-Forest with HBPP and Multi- Probe LSH with HBPP are presented in this thesis, both of them achieve the three goals for KNN search in large scale high dimensional data set: high search quality, high time efficiency, high space efficiency. None of the previous KNN algorithms can achieve all three goals. More specifically, it is shown that HBPP algorithms can always achieve high search quality (as good as LSH-Forest with DAPP and Multi-Probe LSH with DAPP) with much less time cost (one to several orders of magnitude speedup) and same memory usage. It is also shown that with almost same time cost and memory usage, HBPP algorithms can always achieve better search quality than LSH-Forest with random pick (LSH-Forest with RP) and Multi-Probe LSH with random pick (Multi-Probe LSH with RP). Moreover, to achieve a very high search quality, Multi-Probe with HBPP is always a better choice than LSH-Forest with HBPP, regardless of the distribution, size and dimension number of the data set. / Dissertation/Thesis / M.S. Computer Science 2011

abstract: Most of the sunlight powering natural photosynthesis is absorbed by antenna arrays that transfer, and regulate the delivery of excitation energy to reaction centers in the chloroplast where photosynthesis takes place. Under intense sunlight the plants and certain organisms cannot fully utilize all of the sunlight received by antennas and excess redox species are formed which could potentially harm them. To prevent this, excess energy is dissipated by antennas before it reaches to the reaction centers to initiate electron transfer needed in the next steps of photosynthesis. This phenomenon is called non-photochemical quenching (NPQ). The mechanism of NPQ is not fully understood, but the process is believed to be initiated by a drop in the pH in thylakoid lumen in cells. This causes changes in otherwise nonresponsive energy acceptors which accept the excess energy, preventing oversensitization of the reaction center. To mimic this phenomenon and get insight into the mechanism of NPQ, a novel pH sensitive dye 3'6'-indolinorhodamine was designed and synthesized which in a neutral solution stays in a closed (colorless) form and does not absorb light while at low pH it opens (colored) and absorbs light. The absorption of the dye overlaps porphyrin emission, thus making energy transfer from the porphyrin to the dye thermodynamically possible. Several self-regulating molecular model systems were designed and synthesized consisting of this dye and zinc porphyrins organized on a hexaphenylbenzene framework to functionally mimic the role of the antenna in NPQ. When a dye-zinc porphyrin dyad is dissolved in an organic solvent, the zinc porphyrin antenna absorbs and emits light by normal photophysical processes. Time resolved fluorescence experiments using the single-photon-timing method with excitation at 425 nm and emission at 600 nm yielded a lifetime of 2.09 ns for the porphyrin first excited singlet state. When acetic acid is added to the solution of the dyad, the pH sensitive dye opens and quenches the zinc porphyrin emission decreasing the lifetime of the porphyrin first excited singlet state to 23 ps, and converting the excitation energy to heat. Under similar experimental conditions in a neutral solution, a model hexad containing the dye and five zinc porphyrins organized on a hexaphenylbenzene core decays exponentially with a time constant of 2.1 ns, which is essentially the same lifetime as observed for related monomeric zinc porphyrins. When a solution of the hexad is acidified, the dye opens and quenches all porphyrin first excited singlet states to <40 ps. This converts the excitation energy to heat and renders the porphyrins kinetically incompetent to readily donate electrons by photoinduced electron transfer, thereby mimicking the role of the antenna in photosynthetic photoprotection. / Dissertation/Thesis / Ph.D. Chemistry 2012

Doctor of Philosophy / Department of Geography / John A. Harrington Jr / The climate of the Middle East is warming and extreme hot temperature events are becoming more common, as observed by the significant upward trends in mean and extreme temperatures during the last few decades. Climate modeling studies suggest that the frequency, intensity, and duration of extreme temperature events are expected to increase as the global and local climate continues to warm. Existing literature about heat waves (HWs) in Saudi Arabia provides information about HW duration using a single index, without considering the observed effects of climate change and the subtropical arid climate. With that in mind, this dissertation provides a series of three stand-alone papers evaluating temporal, geographic, and atmospheric aspects of the character of warm season (May-September) HWs in Saudi Arabia for 1985 to 2014. Chapter 2 examines the temporal behavior(s) of the frequency, duration, and intensity of HWs under the observed recent climate change. Several issues are addressed including the identification of some improved methodological practices for HW indices. A time-sensitive approach to define and detect HWs is proposed and assessed. HW events and their duration are considered as count data; thus, different Poisson models were used for trend detection. Chapter 3 addresses the spatio-temporal patterns of the frequency and intensity of hot days and nights, and HWs. The chapter reemphasizes the importance of considering the on-goings effects of climate warming and applies a novel time-series clustering approach to recognize hot temperature event behavior through time and space. Chapter 4 explores the atmospheric circulation conditions that are associated with warm season HW event occurrence and how different HWs aspects are related to different circulation types. Further, possible teleconnections between HWs and sea surface temperature (SST) anomalies of nearby large bodies are examined. Results from Chapters 2 and 3 detected systematic upward trends in maximum and minimum temperatures at most of the 25 stations, suggesting an on-going change in the climatology of the upper-tail of the frequency distribution. The analysis demonstrated the value of using a time-sensitive approach in studying extreme thermal events. Different patterns were observed over time and space not only across stations but also among extreme temperature events (i.e., hot days and nights, and HWs). The overall results suggest that not only local and regional factors, such as elevation, latitude, land cover, atmospheric humidity, and distance from a large body of water, but also large-scale factors such as atmospheric circulation patterns are responsible for the observed temporal and spatial patterns. Chapter 4 confirmed that as the Indian Summer Monsoon Trough and the Arabian heat low were key atmospheric features related to HW days. SST anomalies seemed to be a more important factor for HWs intensity. Extreme thermal events in Saudi Arabia tended to occur during regional warming due to atmospheric circulation conditions and SSTs teleconnections. This study documents the value of a time-sensitive approach and should initiate further research as some of temporal and spatial variabilities were not fully explained

Este estudo busca dar visibilidade ao estar-junto-dançando nas Danças Circulares Sagradas, aos encontros e sentidos construídos pelos Corpos Dançantes na convivência do grupo e fora dele. Através dos depoimentos e falas de nove Dançantes do grupo de Danças Circulares Sagradas do Centro Comunitário George Black da Secretaria Municipal de Esportes, Recreação e Lazer, partícipes deste estudo, foi possível identificar o exercício do olhar e da escuta sensíveis. Além da prática da presença e do ritmo, da percepção do erro, da dúvida, como processo inerente do dançar-junto no círculo. Para a constituição de um espaço reflexivo no grupo, utilizei as Cartas de Caminho(Apêndice B), que representam as emoções e sentimentos advindos desse dinâmico, complexo e multidimensional contato dos Corpos Dançantes com o vitalismo manifestado por esse estar-junto-dançando. No entanto, para a realização desse caminho, foi necessário mergulhar nas trilhas e mestres das Danças Circulares Sagradas, suas relações com o Sagrado, seus Mitos e Símbolos, estabelecendo um paralelo com minha história pessoal e os caminhos que me levaram à pesquisa. Busquei teoricamente o apoio de Michel Maffesoli, na perspectiva de um estar-junto sensível e solidário, na visão de complexidade de Edgar Morin e na concepção de corpo próprio de Merleau-Ponty. Muitos outros autores contribuíram para o adensamento reflexivo, mas foram os depoimentos e falas dos Dançantes que me possibilitaram ir além, com vistas a uma Pedagogia do Sensível, onde o ritmo, o olhar e a escuta sensíveis estavam presentes. / This study seeks to give visibility to the being-together-dancing in the Sacred Circle Dances, meetings and meanings constructed by Dancing Bodies in the living of the group and outside it. Through interviews and speeches of nine Dancing group Sacred Circle Dances George Black Community Center of the Municipal Secretary of Sports Recreation and Leisure, participants in this study, we observed the exercise of looking and listening sensitive. In the practice of the presence and rhythm, the perception of error, definitely as a process inherent in dance-along in the circle. To form a reflective space in the group, used the Letters of Way, representing the emotions and feelings arising from this dynamic, complex and multidimensional contact Dancing Bodies with vitalism expressed by this being-together-dancing. However to achieve this way, it was necessary to dive into the tracks and masters of the Sacred Circle Dances, their relations with the Sacred, its Myths and Symbols, drawing a parallel with my personal history and the paths that led me to research. To do so, I sought the support of Maffesoli theoretically, from the perspective of a being-together-sensitive and supportive, in view of the complexity of Morin and designing its own body of Merleau-Ponty. Many others have contributed to the reflective density, but it was the testimony and statements of Dancing that allowed me to go further with a view to the sensitive pedagogy, where the pace, look and listen sensitive were present.