<p>Since their discovery by Burg and Schlesinger in 1937, amine-boranes have enjoyed a rich preparative history and have experienced reinvigorated interest as valuable reagents for organic syntheses. Previously, the Herbert C. Brown Center for Borane Research has reported their synthesis from NaBH₄ and amines via the intermediacy of (NH₄)₂SO4 or NaHCO₃. Described herein is a CO₂-mediated amine-borane synthesis that accommodates all classes of amines, particularly long-chain trialkyl- and pyridine-like heteroarylamines.</p>

<p></p><p> My thesis work revolves around the ability to modify the 1,4,8,11-tetraazacyclotetradecane (cyclam) framework in order tune the electronic properties of resulting metal complexes towards real life applications. A huge direction for science and engineering is the pursuit of Moore’s Law, to constantly miniaturize electronic processes while improving their performance. With the physical limits of copper wiring being reached on nanoscale levels, alternative resources must be utilized. Naturally, the absolute limit of wiring would be on the single molecular scale. It is this idea that Chapters 1-3 are founded upon. Moving forward, I deemed three key concepts are important for success of this project: (1) the ability for modification of the molecule to be incorporated into existing technologies, (2) redox stability of the molecular complexes to allow multiple charges to pass through without losing integrity, and (3) the ability to function as a wire and allow current to pass through. Requirement (1) has been proven possible in previous work on cyclam, however (2) and (3) were yet to be shown for any cobalt tetraazamacrocyclic complex until this work.</p><p> Chapter 1 covers my first successful exploration into modification of the cylcam ligand in order to obtain favorable electronic properties. Cobalt complexes utilizing the MPC ligand (5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane) show stability upon reduction, whereas the cyclam analogues did not. In fact, [Co(MPC)(C₂Ph)₂]⁺ was the first cobalt based tetraazamacrocyclic alkynyl complex to show such redox stability without the use of heavily electron withdrawing axial ligands. It was found that this improvement of redox stability is a result of the weakened equatorial ligand field caused by the steric bulk of the phenyl substituents of the cyclam framework. This in turn led to improved axial ligand bonding and hence greater stability. This work shows the Co^III(MPC) framework can satisfy requirement (2).</p><p> Based on the results of Chapter 1, Chapter 2 realizes the idea that with improved axial ligand bond strengths in Co^III(MPC) complexes, the possibility for electronic delocalization between cobalt and the axial ligand performing as the wire is opened. A series of dinuclear Co^III(MPC) complexes, with cobalt centers linked through a butadiyndiyl bridge, were prepared. With each cobalt being identical, theoretically each should behave electrochemically similar and reduction of the complex should be a single two electron event. It is however shown that this two electron event was, in fact, split into two single electron events. The source of this result is the delocalization of the first added electron between both cobalt centers, effectively making two half-reduced metals. Therefore, the ability for Co^III(MPC) complexes to satisfy requirement (3) has been proven.</p><p> Chapter 3 expands on the results shown in Chapters 1 and 2. Where Chapter 2 showed delocalization of an electron between cobalt centers, Chapter 3 shows delocalization of a hole through cobalt between ethynylferrocene ligands. With this, all three requirements are met and the ability as Co(MPC) to function as a wire has been proven for both oxidation and reduction, both between cobalt and through cobalt.</p><p> </p><p> Chapter 4 takes a new direction, however applies the same basic principle as the previous three in modifying the cyclam ligand to achieve desired properties. Where application in electronic devices are made stable by use of the bulky MPC ligand, application towards catalysis requires an open catalytic site and weak enough axial coordination to allow the substrate to leave once reduced. Through the alkyl substitution of the cyclam ligand in Ni^II(CTMC) (5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradecane) in place of the MPC ligand, electronically donating properties of the macrocycle were maintained while opening the axial catalytic site. In this work, it was shown that reduction in steric bulk of the ligand from phenyl to ethyl to methyl, while maintaining electron donating properties, improved catalytic efficiency and all complexes were superior to Ni^II(cyclam).</p><p></p>

It is demonstrated that by using a miniature chemical reaction vessel under adaptive mechatronic control, it is possible to design and construct a low-cost carbon dioxide measurement system. With further development such a system would be potentially suitable for low-cost commercial application, in particular as sacrificial, single-mission instrumentation packages in horticultural cargo monitoring. Current instrumentation systems for carbon dioxide (CO2) gas measurement are reviewed and their limitations with respect to low cost commercial applications determined. These utilise technology intended for laboratory measurements. In particular the optical energy absorbance of CO2 in the infra-red electromagnetic spectrum. These systems require large optical paths (typically 10cm) in order to measure small CO2 concentrations. This in turn has a large impact on the physical size of the sensing system. Of the many applications requiring online CO2 sensing packages (such as medical, petroleum, environmental and water treatment)the horticultural industry is the primary focus for this research. CO2 sensing systems are primarily used in horticulture to monitor the produce environment and help extend storage time. For these applications CO2 concentrations are typically low (in the range 0 to 1%) and the paramount need is for low-cost (and possibly disposable) sensing packages. The basis of the measurement technique is the use of bulk (but small volume) aqueous chemical reaction under mechatronic control. Unlike thin film technologies where very thin membranes are passively exposed to the gaseous sample, here a small volume (approximately 2mL) of simple and very cheap liquid chemical indicator (calcium hydroxide solution) is used to produce an opaque precipitate. CO2 concentration is then assessed by low-cost optical attenuation measurements of the developing opacity of the solution. The instrumentation package comprises pumps, flowmeter, reaction cell and infra-red optics for the turbidity measurement, plus reagent and waste vessels, pipelines and electronics. During each measurement cycle, the reaction cell is flushed, with fresh chemical indicator and a sample of gas admitted. The indicator and the sample gas are then vigorously mixed and the change in the indicators optical properties measured at regular intervals. An embedded 8-bit microcontroller performs the necessary analysis to deduce the CO2 concentration (as percentage by volume) for the sample gas by reference to one or more of five ``Time-To-Threshold'' calibration models. These models evaluate the trend in turbidity development as precipitate is formed. First and second prototypes of the measurement system have been constructed and their (low-cost) components and overall performance evaluated, the first a `proof-of-concept' and the second to investigate methodology shortcomings. As a result the design of a third prototype is outlined. The measurement systems have been shown to work adequately well within expected limitations, resulting in a usable low-cost measurement technique. The current prototypes have a useful range of at least 5% to 100% CO2 with a discrimination of typically +-6%. Deficiencies, particularly performance at low concentrations, are identified and potential enhancements for future prototypes proposed.

Carbon dioxide (CO2) sequestration is one of the most attractive methods to reduce the amount of CO2 in the atmosphere by injecting it into the geological formations. Furthermore, it is also an effective mechanism for enhanced oil recovery. Simulation of CO2 injection based on a suitable modeling is very important for explaining the fluid flow behavior of CO2 in a reservoir. Increasing of CO2 injection may cause a structural deformation of the medium. The structural deformation modeling in carbon sequestration is useful to evaluate the medium stability to avoid CO2 leakage to the atmosphere. Therefore, it is important to include such effect into the model. The purpose of this study is to simulate the CO2 injection in a reservoir. The numerical simulations of two-phase flow in homogeneous and heterogeneous porous media are presented. Also, the effects of gravity and capillary pressure are considered. IMplicit Pressure Explicit Saturation (IMPES) and IMplicit Pressure-Displacements and an Explicit Saturation (IMPDES) schemes are used to solve the problems under consideration. Various numerical examples were simulated and divided into two parts of the study. The numerical results demonstrate the effects of buoyancy and capillary pressure as well as the permeability value and its distribution in the domain. Some conclusions that could be derived from the numerical results are the buoyancy of CO2 is driven by the density difference, the CO2 saturation profile (rate and distribution) are affected by the permeability distribution and its value, and the displacements of the porous medium go to constant values at least six to eight months (on average) after injection. Furthermore, the simulation of CO2 injection provides intuitive knowledge and a better understanding of the fluid flow behavior of CO2 in the subsurface with the deformation effect of the porous medium.

The objective of this research is to evaluate the potential of thermal energy storage in supermarkets with CO2 refrigeration systems. Suitable energy storage techniques are investigated and the seasonal storage technology of boreholes is chosen to be the focus of the study. The calculations are done for five supermarket refrigeration systems with different combinations of heating systems and borehole thermal energy storage control strategies. The two heating systems analyzed are the ground source heat pump and the heat recovery from the supermarket’s refrigeration system. The simulation results show that the introduction of thermal energy storage in the scenarios with heat pump can reduce the annual total energy by 6.3%. It is also shown that increasing the number of boreholes can decrease the life cycle cost of the system. Moreover, it is established that a supermarket system with heat recovery consumes 8.1% less energy than the one using heat pump and adding thermal energy storage on the heat recovery system further improves the energy consumption by 3.7% but may become costly.

yes / Heavy petroleum industries, including the Fluid Catalytic Cracking (FCC) unit, are among some of the biggest contributors to global greenhouse gas (GHG) emissions. The FCC unit’s regenerator is where these emissions originate mostly, meaning the operation of FCC regenerators has come under scrutiny in recent years due to the global mitigation efforts against climate change, affecting both current operations and the future of the FCC unit. As a result, it is more important than ever to develop models that are accurate and reliable at predicting emissions of various greenhouse gases to keep up with new reporting guidelines that will help optimise the unit for increased coke conversion and lower operating costs. Part 1 of this paper was dedicated to reviewing the riser section of the FCC unit. Part 2 reviews traditional modelling methodologies used in modelling and simulating the FCC regenerator. Hydrodynamics and kinetics of the regenerator are discussed in terms of experimental data and modelling. Modelling of constitutive parts that are important to the FCC unit, such as gas–solid cyclones and catalyst transport lines, are also considered. This review then identifies areas where the current generation of models of the regenerator can be improved for the future. Parts 1 and 2 are such that a comprehensive review of the literature on modelling the FCC unit is presented, showing the guidance and framework followed in building models for the unit.

No description available.

Balancing indoor comfort and energy consumption is crucial to building energy efficiency. Occupancy information is a vital aspect in this process, as it determines the energy demand. Although there are various sensors used to gather occupancy information, environmental sensors stand out due to their low cost and privacy benefits. Machine learning algorithms play a critical role in estimating the relationship between occupancy levels and environmental data. To improve performance, more complex models such as deep learning algorithms are necessary. Long Short-Term Memory (LSTM) is a powerful deep learning algorithm that has been utilized in occupancy estimation. However, recently, an algorithm named Attention has emerged with improved performance. The study proposes a more effective model for occupancy level estimation by incorporating Attention into the existing Long Short-Term Memory algorithm. The results show that the proposed model is more accurate than using a single algorithm and has the potential to be integrated into building energy control systems to conserve even more energy. / Master of Science / The motivation for energy conservation and sustainable development is rapidly increasing, and building energy consumption is a significant part of overall energy use. In order to make buildings more energy efficient, it is necessary to obtain information on the occupancy level of rooms in the building. Environmental sensors are used to measure factors such as humidity and sound to determine occupancy information. However, the relationship between sensor readings and occupancy levels is complex, making it necessary to use machine learning algorithms to establish a connection. As a subfield of machine learning, deep learning is capable of processing complex data. This research aims to utilize advanced deep learning algorithms to estimate building occupancy levels based on environmental sensor data.

The injection of carbon dioxide (CO2) into saline formations for the purpose of limiting greenhouse gas emissions has been proposed as an alternative to the atmospheric venting of carbon dioxide. In the evaluation process for selecting a potential target saline formation for the disposal of carbon dioxide, flow characterisation of the disposed plume should be undertaken by reservoir simulation of the target formation. The movement of injected carbon dioxide in the saline formation is influenced by many factors including the physics of carbon dioxide at deep formation depths and pressure, physical interactions with formation rock and pore water and variations in the rock flow pathways through changes in formation heterogeneity. This thesis investigates the roles of physical interactions on the disposal of carbon dioxide and the ability to contain the injected gas through evaluation of trapping mechanisms such as dissolution of CO2 in formation water and residual gas trapping through the process of gas-water relative permeability hysteresis. Variable formation heterogeneity is evaluated for its impact on the migration of injected CO2 plume movement and the role of formation heterogeneity in impeding or accelerating the immobilisation of injected carbon dioxide. Multiple reservoir simulation studies were conducted to evaluate, initially, the role of different trapping mechanisms in immobilising the movement of injected carbon dioxide and subsequently, the role of variations in formation rock in the migration and trapping of and injected plume of carbon dioxide. The major simulation study shows that the selection process for identifying appropriate saline formations should not only consider their size and permeability but should also consider their degree of heterogeneity endemic to the formation. / A set of reservoir performance metrics were developed for the CO2 disposal projects. The metrics were applied to compare plume migration of injected CO2 (both vertically and laterally) and containment (through dissolution and residual phase trapping) in these studies. The findings demonstrate how formation heterogeneity has a significant impact on the subsurface behaviour of the carbon dioxide. Formation dip influences the rate of migration, with low formation dipping reservoirs having slower rates of vertical migration. Increasing the tortuousity of the migration flow path by either increasing the shale (non-reservoir) content or lengthening the shale baffles in the formation (corresponding to a gradual decrease in reservoir quality), can progressively inhibit the vertical flow of the plume whilst promoting its lateral flow. The increase in the tortuosity of the CO2 migration pathway delays the migration of CO2 and increases the residence time for the CO2 in the formation. Thus, formation heterogeneity impedes the onset of residual gas trapping through hysteresis effects. Ultimately less carbon dioxide is likely to collect under the seal in heterogeneous formations due to increased reservoir contact and long residence times, thereby reducing the risk of seepage to overlying formations. / Given sufficient permeability for economic injection of CO2, then low to mid net-to-gross heterogeneous saline formations with low formation dip and lengthy intra-bedded shales are desirable for selection for the geological disposal of CO2. Detailed reservoir characterisation of any potential geological disposal saline formations is required in order to accurately predict the range of outcomes in the long term flow characterisation of injected CO2 into those formations.

The primary objective of the research was to study the physiological and biochemical changes in Hass avocado fruit stored in different combination of oxygen and carbon dioxide concentrations at both 0 degrees and 5 degrees Centigrade (C), and to determine whether storage in controlled atmosphere (CA) can decrease the incidence of chilling injury (CI). A secondary objective was to identify possible correlations between CA, the incidence of CI, the activity of some ripening related enzymes and changes in proteins during ripening at 20 degrees C following storage at low temperatures. Fruit suffered no CI and ripened normally following CA storage for 3 weeks at both 0 degrees and 5 degrees C, then transferred to air for 6 days at 20 degrees C. CI symptoms did develop after CA storage for 6 and 9 weeks at 0 degrees C. Changes in proteins during ripening were analysed by 2D-PAGE. Some polypeptides were detected in unripe fruit but decreased with ripening. Polypeptides of 16.5, 25, 36 and 56 kD (kilo Dalton) were present early in ripening and their levels further increased during ripening. The appearance of three ripening related polypeptides with estimated molecular weights 80 kD (pI 3.6), 36 kD (pI 5.8) and 16.5 kD (pI 5.7) was observed in fruit at the climacteric stage. Three polypeptides with estimated molecular weights of 41 kD (pI7.8), 36 kD (pI 5.8) and 33 kD (pI 5.1) were found in air stored fruit but were not detected in fruit stored in CA. This research showed that CA did not ameliorate CI at 0 degrees C, instead storage at 0 degrees C caused a premature increase in ethylene production when the fruit were returned to air at 20 degrees C. In contrast, CA storage at 5 degrees C retarded ethylene production and ripening in fruit after it was returned to air at 20 degrees C. / Doctor of Philosophy (PhD)