Traditional state estimation whereby the state of the system is assessed based on a limited number of measurements is a well established tool for steady-state situations where the frequency of the system is 50 Hz. Previous contributions have looked at extending this concept to the power quality area. This area of research is called Power Quality State Estimation (PQSE) and represents a class of techniques. Under the umbrella of PQSE, the main contribution of this work is taking Transient State Estimation (TSE) on step further. A new three-phase formulation for TSE using the Numerical Integrator Substitution (NIS) will be detailed. NIS approach, also known as Dommel's method, gives a numerical solution to describe the transient behaviour of a dynamic system at discrete time points. The new transient state estimator is implemented and verified by applying the proposed algorithm to a real distribution test system. It's performance and accuracy are investigated in presence of measurement noise, background harmonics, multiple faults, etc. The conducted study has shown this technique has a great potential.

<p> 1,1-Bis(4-(trifluoromethyl)phenyl)germacyclobutane and 1,1-bis(3,5-bis(trifluoromethyl)phenyl)germacyclobutane have been prepared, and their photochemistry studied by steady state and nanosecond laser flash photolysis (NLFP) techniques. Photolysis of the two compounds in the presence of methanol leads to the formation of products resulting from reaction of the alcohol with two germanium-containing reactive intermediates, the germenes and germylenes.</p> <p> The reactivities of the two germenes with nucleophiles such as alcohols, carboxylic acids, and amines have been examined by NLFP techniques, and the results are compared to analogous data for 1,1-diphenylgermene and 1,1-diphenylsilene. Germene reactivity is shown to increase with increasing electron-withdrawing power of the substituents, consistent with a mechanism initiated by nucleophilic attack at germanium. The increased electrophilicity of the substituted 1,1-diarylgermenes results in kinetic behavior indistinguishable from that of 1,1-diphenylsilene, indicating that germenes and silenes form a mechanistic continuum in their reactions with nucleophiles.</p> / Thesis / Master of Science (MSc)

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This thesis describes the algorithms and techniques developed for harmonic state estimation and transient state estimation, which can be used to identify the location of disturbance sources in an electrical power system. The previous harmonic state estimation algorithm is extended to include the estimation of time-varying harmonics using an adaptive Kalman filter. The proposed method utilises two covariance noise models to overcome the divergence problem in traditional Kalman filters. Moreover, it does not require an optimal covariance noise matrix of the Kalman filter to be used. The common problems faced in harmonic state estimation applications due to the influence of measurement bad data associated with measurements and the lack of measurement points, hence the system being partially observable, are investigated with reference to the Lower South Island of the New Zealand system. The state estimation technique is also extended to transient state estimation. Two formulation methods are outlined and the development of the proposed methodology is presented. Fault scenarios with reference to the Lower South Island of the New Zealand system are simulated to demonstrate the ability of transient state estimation in estimating the voltages and currents of the unmeasured locations, and applying the estimated results to search for the fault location. The estimation results are compared with PSCAD/EMTDC simulations to justify their accuracy.

Protein arginine methyltransferase 1 (PRMT1) is a key posttranslational modification enzyme that catalyzes the methylation of specific arginine residues in histone and nonhistone protein substrates, regulating diverse cellular processes such as transcriptional initiation, RNA splicing, DNA repair, and signal transduction. Recently the essential roles of PRMT1 in cancer and cardiovascular complications have intrigued much attention. Developing effective PRMT inhibitors therefore is of significant therapeutic value. The research on PRMT inhibitor development however is greatly hindered by poor understanding of the biochemical basis of protein arginine methylation and lack of effective assays for PRMT1 inhibitor screening. Herein, we report our effort in the kinetic mechanism study as well as the fluorescent probe and inhibitor development for PRMT1. New fluorescent reporters were designed and applied to perform single-step analysis of substrate binding and methylation of PRMT1. Using these reporters, we performed transient-state fluorescence measurements to dissect the rate constants along the PRMT1 catalytic coordinate. The data give evidence that the chemistry of methyl transfer is the major rate-limiting step, and that binding of the cofactor SAM or SAH affects the association and dissociation of H4 with PRMT1. Importantly, we identified a critical kinetic step suggesting a precatalytic conformational transition induced by substrate binding. On the other hand, we discovered a type of naphthyl-sulfo (NS) compounds that block PRMT1- mediated arginine methylation at micromolar potency through a unique mechanism: they directly target the substrates but not PRMT enzymes for the observed inhibition. We also found that suramin, an anti-parasite and anti-cancer drug bearing similar functional groups, effectively inhibited PRMT1 mediated methylation. These findings about novel PRMT inhibitors and their unique inhibition mechanism provide a new way for chemical regulation of protein arginine methylation. Addionally, to dissect the interplaying relationship between different histone modification marks, we investigated how individual lysine acetylations and their different combinations at the H4 tail affect Arg-3 methylation in cis. Our data reveal that the effect of lysine acetylation on arginine methylation depends on the site of acetylation and the type of methylation. While certain acetylations present a repressive impact on PRMT-1 mediated methylation (type I methylation), lysine acetylation generally is correlated with enhanced methylation by PRMT5 (type II dimethylation). In particular, Lys-5 acetylation decreases activity of PRMT1 but increases that of PRMT5. Furthermore, hyperacetylation increases the content of ordered secondary structures of H4 tail. These findings provide new insights into the regulatory mechanism of Arg-3 methylation by H4 acetylation, and unravel that complex intercommunications exist between different posttranslational marks in cis.

Maintenance and rehabilitation of existing masonry and reinforced concrete structures are of great importance in the field of civil engineering. Due to deterioration and severe environment, numerous structures fail to meet functional or safety requirements, and as a result, they should be strengthened. Several methods have been utilized to repair the structures, including steel plate bonding, cable post-tensioning, and section enlargement. However, these methods bring disadvantages, such as significant added dead load and high labour cost. Therefore, externally bonding with composite materials has attracted considerable attention recently. Externally bonded fibre-reinforced polymer (FRP) sheets have been widely used to strengthen reinforced concrete and masonry structures. FRP has been a common method to provide a higher service life for structures for several decades. However, strengthening structural members with FRP introduces certain drawbacks, such as their poor performance in fire scenarios caused by the rapid softening of the polymer-based resin. An alternative strengthening system known as a fabric-reinforced cementitious matrix (FRCM) has been developed to address this issue by replacing resin-based material with an inorganic cementitious-based matrix. Nonetheless, the performance of FRCM at high temperatures has not been investigated sufficiently so far. Hence, this research focused on the mechanical behaviour of FRCM at high temperatures. This experimental research investigates the tensile performance of carbon FRCM at high temperatures. First, the temperature distribution within the specimens during heating was studied using nine specimens with one, two, or three layers to reveal the required time for the inner fabric to reach a steady temperature. Then, the tension and stiffness degradation of FRCM coupons were studied at different temperatures. A total of 84 FRCM coupons were fabricated and tested in tension; 60 of the tests were conducted at steady-state conditions in which temperature was held constant and load increased, and 24 specimens were carried out in transient-state tests, in which load was constant, and temperature grew. In order to provide a more comprehensive knowledge concerning the FRCM composite, some key variables were included in this research. These parameters are the number of layers (1, 2, 3) leading to different thicknesses (20, 30, 40 mm), the orientation of the fabric layer (unidirectional and bidirectional), target temperature (ambient, 100, 200, 300, 400°C), and heating condition (steady-state, transient state). These tests aimed to reveal the primary mechanical characteristics such as ultimate strength and cracked elastic modulus at different temperatures and compare them with control specimens tested at room temperature. With the increase in the number of fabric grids from one to two and three, the stress at failure decreased by about 11 and 18%, respectively. With regards to cracked elastic modulus two and three-layered specimens showed 18 and 20% reduction in value. It is also noteworthy to mention that overall load capacity of specimens rose with the increase in number of layers; however, due to the more significant increase in area, the stress was reduced. The same decreases in the cracked elastic modulus and ultimate strength were observed as the target temperature increased. Increasing the temperature to 400°C led to a decrease in ultimate strength and cracked elastic modulus of approximately 60 to 70%. Furthermore, the bidirectional specimens showed a better behaviour than unidirectional specimens in terms of ultimate strength; however, their cracked elastic moduli were almost the same. With regards to the transient-state tests, as the material became thicker, the failure temperature increased considerably. For instance, a 20-mm specimen failed at 467°C with a 20% sustained load, while a 30-mm specimen failed at 558°C. Another vital parameter studied in transient-state tests was the decrease in temperature with the increase in sustained load. An example of this is the 20-mm specimens which failed at 352 and 258°C, while they were preloaded to 40 and 60% of their capacities. The conclusions of this study suggest that FRCM materials do retain a non-negligible strength capacity at high temperatures. However, further investigations to reveal FRCM bond behaviour and retrofitted structural members at high temperatures are still required to provide comprehensive knowledge.

Fluorescent molecules commonly shift to transient dark states, induced bylight or triggered by chemical reactions. The transient dark states can beused as probes of the local environment surrounding the fluorescent molecules,and are therefore attractive for use in biomolecular applications. Thisthesis explores the use and development of novel fluorescence spectroscopictechniques for monitoring transient dark states.This work demonstrates that kinetic information regarding photoinduced transient dark states of fluorescent molecules can be obtained from the time-averaged fluorescence intensity of fluorescent molecules subject totemporally modulated illumination. Methods based on this approach havethe advantage that the light detectors can have a low time resolution, which allows for parallelization and screening of biomolecular interactions withhigh throughput. Transient state images are presented displaying local environmental differences such as those in oxygen concentration and quencher accessibility.Analysis of the fluorescence intensity fluctuations resulting from thetransitions to and from transient dark states can be used to obtain information regarding the transition rates and occupancy of the transient darkstates. Fluorescence fluctuation analysis was used to reveal rates of protonbinding and debinding to single fluorescent molecules located close to biological membranes and protein surfaces. The results from these studies show that the proton exchange rate increases dramatically when the fluorescent molecule is close to the membrane. / QC 20100809

Clostridium thermocellum is a thermophilic anaerobe that is capable of producing ethanol directly from lignocellulosic compounds, however this organism suffers from low ethanol tolerance and low ethanol yields. In vivo mathematical modeling studies based on steady state traditional metabolic flux analysis, metabolic control analysis, transient and steady states’ flux spectrum analysis (FSA) were conducted on C. thermocellum’s central metabolism. The models were developed in Matrix Laboratory software ( MATLAB® (The Language of Technical Computing), R2008b, Version 7.7.0.471)) based on known stoichiometry from C. thermocellum pathway and known physical constraints. Growth on cellobiose from Metabolic flux analysis (MFA) and Metabolic control analysis (MCA) of wild type (WT) and ethanol adapted (EA) cells showed that, at lower than optimum exogenous ethanol levels, ethanol to acetate (E/A) ratios increased by approximately 29% in WT cells and 7% in EA cells. Sensitivity analyses of the MFA and MCA models indicated that the effects of variability in experimental data on model predictions were minimal (within ±5% differences in predictions if the experimental data varied up to ±20%). Steady state FSA model predictions showed that, an optimum hydrogen flux of ~5mM/hr in the presence of pressure equal to or above 7MPa inhibits ferrodoxin hydrogenase which causes NAD re-oxidation in the system to increase ethanol yields to about 3.5 mol ethanol/mol cellobiose.

Les travaux de reconnaissance menés par la société Lyon-Turin-Ferroviaire (LTF) pour le projet de tunnel international ont conduit à l'acquisition de diagraphies différées sur un grand nombre de forages profonds. La synthèse des données a permis de mettre en évidence des anomalies thermiques profondes au sein du massif à proximité du front du Houiller et dans la série siliceuse de Vanoise. Ces anomalies sont confrontées à un modèle conceptuel intégrant des circulations d'eaux souterraines homogènes dans les zones décomprimées de versant et localisées dans les zones profondes ainsi que les effets thermiques associés. Le modèle conceptuel considère un état thermique transitoire des massifs dépendant du contexte paléo-climatique.A proximité du front du Houiller, une modélisation numérique du secteur a permis de montrer que les anomalies thermiques rencontrées sont cohérentes avec l'hypothèse d'une perturbation froide associée à l'activation, au début de l'Holocène, d'une circulation profonde localisée qui se propage par conduction dans le massif. La prise en compte, dans la modélisation, du changement de température au début de l'Holocène conduit à l'adoption d'un flux géothermique de 100mWm-2, donc plus élevé que les flux généralement considérés dans les Alpes.Dans la série siliceuse de Vanoise, les anomalies observées de gradients profonds peuvent être expliquées par une augmentation de la température des circulations dans la zone décomprimée de l'ordre de 2.4°C vers la fin du Petit Âge Glaciaire. Le réchauffement des circulations plus important par rapport au réchauffement de l'air à cette période est expliqué par une diminution des apports d'eau de fusion nivale dans la zone décomprimée. Ce résultat repose sur le développement d'une méthode 1D permettant d'estimer l'âge et l'amplitude d'une variation brutale de température à la limite d'un milieu semi-infini en conduction. Avant d'être appliquée aux données de diagraphies de forage, la méthode a été testée sur des données issues de simulations numériques reproduisant les températures obtenues dans un contexte de versant intégrant les effets du relief et la présence d'un flux géothermique. / The reconnaissance works for the Lyon-Turin railway tunnel project have led to well logs acquisition for a large number of deep boreholes. Data synthesis enabled to identify deep thermal disturbances inside the mountain massif in the siliceous series of Vanoise and in the vicinity of the Houiller Front. On the base of the well logs analysis and the mountain hydrogeology previous knowledge, a conceptual model of groundwater flows and their thermal effects in the massif is proposed to explain the observed thermal disturbances. It integrates both a uniform water flow in decompressed zone of the valley sides and local deep flows in the massif. The model assumes a transient thermal state related to the paleo-climate environment.First, 2D numerical modelling is used to simulate the thermal disturbances encountered under the valley side in the vicinity of the Houiller Front. In one hand, a thermal transfer by conduction in the massif and a cold temperature imposed near the Houiller Front at the beginning of the Holocene period leads to the current transient thermal state of the massif. The cold temperature near the Houiller Front is assumed to be the consequence of the activation of local deep cold groundwater flows. In a second hand, to simulate the thermal disturbances related to the air temperature change at the beginning of the Holocene, a geothermal heat flux of 100mWm-2 is necessary.Secondly, we develop a method 1D for estimating the age and amplitude of a sudden temperature change at the boundary of a semi-infinite medium in conduction. The method is tested previously on data resulting from numerical simulations in order to assess its use under a valley side and with a geothermal heat flow. Applied to the temperature disturbances observed the siliceous series of Vanoise, the method leads to a 2,4°C increase of groundwater temperature in decompressed zone around the end of Little Ice Age. The value of 2,4°C is higher than the air temperature increase and explained by a decrease in snow meltwater contribution to the decompressed zone.

(i) The thesis sets out to address the problematic phenomenon of Systems of Congestion via Basic Queueing Theory. The theory, and its application in practice, appears to be a field of study which is the common domain of “theorists” and “practitioners”. (ii) This professional dichotomy has come about due to diverging interests in that one group is mainly interested in the purity of mathematical modelling, and the other group is motivated to use modelling, which conveniently employs applications oriented solutions. (iii) The schism between the groups has been accentuated by the “practitioners” who in addition to having an interest in steady state system behaviour make use of methods of modelling of the transient operation of complex Systems of Congestion. (iv) At the outset the thesis demonstrates how closed form solutions are obtained for steady state and transient state operation of a selection of Systems of Congestion. The attendant mathematical derivations are elegant and intricate. (v) Having revealed the limited utility of closed-form solutions the thesis proceeds to investigate the feasibility of using dynamical systems theory to study the transient behaviour of complex Systems of Congestion. (vi) The creation of Chaos Theory in recent decades suggests that it may be employed as a useful tool in analysing Systems of Congestion. Iterative Chaos Theory methods of orbit generation for complete Systems of Congestion are therefore examined. The use of such orbit generation methods is found to be satisfactory for simple Systems of Congestion. More than a perfunctory knowledge of chaos mapping is however required. The simplicity of modelling is emphasized. (vii) Based on the results of benchmarking the creation of dynamic system orbits against an existing simulation method, the research advances to modelling of the transient operation of complex systems. Once again the iterative method of orbit generation displays the ease of modelling while simultaneously unfolding system dynamics graphically. (viii) One may hopefully contend that a tool of eminent utility has been developed to aid practitioners in studying and optimizing Systems of Congestion. / Thesis (PhD (Industrial Engineering))--University of Pretoria, 2006. / Industrial and Systems Engineering / Unrestricted