Voltage-gated ion channels play fundamental roles in neural excitability and thus dysfunctional channels can cause disease. Understanding how the voltage-sensor of these channels activate and inactivate could potentially be useful in future drug design of compounds targeting neuronal excitability. The opening and closing of the pore in voltage-gated ion channels is caused by the arginine-rich S4 helix of the voltage sensor domain (VSD) moving in response to an external potential. Exactly how this movement is accomplished is not yet fully known and an area of hot debate. In this thesis I study how the opening and closing in voltage-gated potassium (Kv) channels occurs. Recently, both experimental and computational results have pointed to the possibility of a secondary structure transition from α- to 3(10)-helix in S4 being an important part of the gating. First, I show that the 3(10)-helix structure in the S4 helix of a Kv1.2-2.1 chimera protein is significantly more favorable compared to the α-helix in terms of a lower free energy barrier during the gating motion. Additional I suggest a new gating model for S4, moving as sliding 310-helix. Interestingly, the single most conserved residue in voltage- gated ion channels is a phenylalanine located in the hydrophobic core and directly facing S4 causing a barrier for the gating charges. In a second study, I address the problem of the energy barrier and show that mutations of the phenylalanine directly alter the free energy barrier of the open to closed transition for S4. Mutations can either facilitate the relaxation of the voltage-sensor or increase the free energy barrier, depending on the size of the mutant. These results are confirmed by new experimental data that supports that a rigid, cyclic ring at the phenylalanine position is the determining rate-limiting factor for the voltage sensor gating process. / QC 20110616

Car exhaust catalysts were introduced in the early 1980’s, to limit the release of pollutants such as hydrocarbons, carbon monoxides and nitrogen oxides. These catalysts contain noble metals such as palladium (Pd), platinum (Pt) and rhodium (Rh) and are able to simultaneously abate all three of the above-mentioned pollutants, hence the name three-way catalyst (TWC). The exposure to high temperatures (800-1000 °C) during operation and the presence of additives in petrol such as lead, calcium, silicon, magnesium, manganese, chromium, sulphur and phosphorus will after a certain time start to lower the overall effectiveness of the catalyst. These effects are either of a mechanical or a chemical nature. High temperatures reduce the active area by causing the noble metals to agglomerate and sinter whereas the additives alter the activity by either fouling the pores of the support material (phosphorus) or by interacting with the metals (sulphur and lead). The main objective of this work was to develop a method to redisperse the catalytically active sites, comprising Pd, Pt and Rh on the washcoat surface, in an effort to regain lost catalyst activity. For this purpose, a wide spectrum of different commercial car exhaust catalysts containing varying noble metal loadings, aged under various driving conditions and with mileages ranging from 30 to 100 000 km were evaluated. The influence of a thermal treatment in a controlled gas atmosphere, such as oxygen or hydrogen and a redispersing agent, e.g. chlorine, on the activity of TWC was investigated by means of laboratory-scale activity measurements. Several complementary characterisation methods such as SEM/TEM, XRD, BET and TPR were used to verify the effects of the regeneration treatments on the catalyst morphology (Paper I). Partial regeneration of catalyst activity and noble metal dispersion was achieved after thermal treatment in an oxygen-chlorine rich atmosphere at temperatures below 500 °C. Finally, an investigation of the effects of an oxy-chlorine thermal treatment for regeneration of a ‘full-scale’ commercial automotive three-way catalyst was performed. Catalyst activity and performance prior to and after the oxy-chlorine thermal treatment was measured on a test vehicle in accordance with the European driving cycle (EC2000). The catalyst surface was further characterised using XRD and EDX (Paper II). Improved catalyst activity for a high mileage catalyst could be observed, with emissions lowered by approximately 30 to 40 vol% over the EC2000 driving cycle

<div>The commercial vehicle sector is an important enabler of the economy and is heavily dependent on fossil fuels. In the fight against climate change, reduction of emissions by improving fuel economy is a key step for the commercial vehicle sector. Improving fuel economy deals with reducing energy losses from fuel to the wheels. This study aims to analyze efficiency improvements for two systems that are important in reducing CO2 emissions - hybrid powertrains and natural gas engines. At first, a prototype series hybrid powertrain was analyzed based on on-highway data collected from its powertrain components. Work done per mile by the electrical components of the powertrain showed inefficient battery operation. The net energy delivery of the battery was close to zero at the end of the runs. This indicated battery was majorly used as an energy storage device. Roughly 15% of losses were observed in the power electronics to supply power from battery and generator to the motor. Ability of the hybrid system to capture regenerative energy and utilize it to propel the vehicle is a primary cause for fuel savings. The ability of this system to capture the regenerative energy was studied by modeling the system. The vehicle model demonstrated that the system was capturing most of the theoretically available regenerative energy. The thesis also demonstrates the possibility of reduction of vehicular level losses for the prototype truck. Drag and rolling resistance coefficients were estimated based on two coast down tests conducted. The ratio of captured regenerative to the drive energy energy for estimated drag and rolling resistant coefficients showed that the current system utilizes 4%-9% of its drive energy from the captured regenerative energy. Whereas a low mileage Peterbilt 579 truck could increase the energy capture ratio to 8%-18% for the same drive profile and route. Decrease in the truck’s aerodynamic drag and rolling resistance can potentially improve the fuel benefits.</div><div>The second study aimed to reduce the engine level pumping losses for a natural gas spark ignition engine by cylinder deactivation (CDA). Spark ignited stoichiometric engines with an intake throttle valve encounter pumping/throttling losses at low speed, low loads due to the restriction of intake air by the throttle body. A simulation study for CDA on a six cylinder natural gas engine model was performed in GT- Power. The simulations were ran for steady state operating points with a torque range 25-560 ftlbs and 1600 rpm. Two , three and four cylinders were deactivated in the simulation study. CDA showed significant fuel benefits with increase in brake thermal efficiency and reduction in brake specific fuel consumption depending on the number of deactivated cylinders. The fuel benefits tend to decrease with increase in torque. Engine cycle efficiencies were analyzed to investigate the efficiency improvements. The open cycle efficiency is the main contributor to the overall increase in the brake thermal efficiency. The work done by the engine to overcome the gas exchange during the intake and exhaust stroke is referred to the pumping losses. The reduction in pumping losses cause an improvement in the open cycle efficiency. By deactivating cylinders, the engine meets its low torque requirements by increase in the intake manifold pressure. Increased intake manifold pressure also resulted in reduction of the pumping loop indicating reduced pumping losses. A major limitation of the CDA strategy was ability to meet EGR fraction requirements. The increase in intake manifold pressure also caused a reduction in the delta pressure across the EGR valve. At higher torques with high EGR requirements CDA strategy was unable to meet the required EGR fraction targets. This limited the benefits of CDA to a specific torque range based on the number of deactivated cylinders. Some variable valve actuation strategies were suggested to overcome this challenge and extend the benefits of CDA for a greater torque range.</div><div><br></div>

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In this study, the hydrolytic kinetics of mixtures of cotton gin waste (CGW) and recycled paper sludge (RPS) at various initial enzyme concentrations of Spezyme AO3117 and Novozymes NS50052 was investigated. The experiments showed that the concentrations of reducing sugars and the conversions of the mixtures increased with increasing initial enzyme concentration. The reducing sugar concentration and conversion of the mixture of 75% CGW and 25% RPS were higher than those of the mixture of 80% CGW and 20% RPS. The conversion of the former could reach 73.8% after a 72-hour hydrolysis at the initial enzyme loading of 17.4 Filter Paper Unit (FPU)/g substrate. A three-parameter kinetic model with convergent property based on enzyme deactivation and its analytical expression were derived. Using nonlinear regression, the parameters of the model were determined from the experimental data of hydrolytic kinetics of the mixtures. Based on this kinetic model of hydrolysis, two profit rate models, representing two kinds of operating modes with and without substrate recycling, were developed. Using the profit rate models, the optimal enzyme loading and hydrolytic time could be predicted for the maximum profit rate in ethanol production according to the costs of enzyme and operation, enzyme loading, and ethanol market price. Simulated results from the models based on the experimental data of hydrolysis of the mixture of 75% CGW and 25% RPS showed that use of a high substrate concentration and an operating mode with feedstock recycle could greatly increase the profit rate of ethanol production. The results also demonstrated that the hydrolysis at a low enzyme loading was economically required for systematic optimization of ethanol production. The development of profit rate model points out a way to optimize a monotonic function with variables, such as enzyme loading and hydrolytic time for the maximum profit rate. The study also investigated the ethanol production from the steam-exploded mixture of 75 wt% cotton gin waste and 25 wt% recycled paper sludge at various influencing factors, such as enzyme concentration, substrate concentration, and severity factor, by a novel operating mode: semi-simultaneous saccharification and fermentation (SSSF) consisting of a pre-hydrolysis and a simultaneous saccharification and fermentation (SSF). Four cases were studied: 24-hour pre-hydrolysis + 48-hour SSF (SSSF 24), 12-hour pre-hydrolysis + 60-hour SSF (SSSF 12), 72-hour SSF, and 48-hour hydrolysis + 12-hour fermentation (SHF). SSSF 24 produced higher ethanol concentration, yield, and productivity than the other operating modes. The higher temperature of steam explosion favored of ethanol production, but the higher initial enzyme concentration could not increase the final ethanol concentration though the hydrolytic rate of the substrate was increased. A mathematical model of SSSF, which consisted of an enzymatic hydrolysis model and a SSF model including four ordinary differential equations that describe the changes of cellobiose, glucose, microorganism, and ethanol concentrations with respect to residence time, was developed, and was used to simulate the data for the four components in the SSSF processes of ethanol production from the mixture. The model parameters were determined by a MATLAB program based on the batch experimental data of the SSSF. The analysis to the reaction rates of cellobiose, glucose, cell, and ethanol using the model and the parameters from the experiments showed that the conversion of cellulose to cellobiose was a rate-controlling step in the SSSF process of ethanol production from cellulose. / Ph. D.

The environmentally unsafe by-products (CO2, H2S, NOx and SO2 for example) of using carbon-based fuels for energy generation have paved the way for research on cleaner, renewable and possibly cheaper alternative energy production methods. Hydrogen gas, which is considered as an energy carrier, can be applied in a fuel cell setup for the production of electrical energy. Although various methods of hydrogen production are available, sulphur-based thermochemical processes (such as the Hybrid Sulfur Process (HyS)) are favoured as alternative options for large scale application. The SO2 electrolyser is applied in producing H2 gas and H2SO4 by electrochemically converting SO2 gas and water. This study focused firstly on the evaluation of the performance of the SO2 electrolyser for the production of hydrogen and sulphuric acid, using commercially available PFSA (perfluorosulfonic acid) (Nafion®) as benchmark by evaluating i) various operating parameters (such as cell temperature and membrane thickness), ii) the influence of MEA (membrane electrode assembly) manufacturing parameters (hot pressing time and pressure) and iii) the effect of H2S as a contaminant. Subsequently, the suitability of novel PBI polyaromatic blend membranes was evaluated for application in an SO2 electrolyser. The parametric study revealed that, depending on the desired operating voltage and acid concentration, the optimisation of the operating conditions was critical. An increased cell temperature promoted both cell voltage and acid concentration while the use of thin membranes resulted in a reduced voltage and acid concentration. While an increased catalyst loading resulted in increased cell efficiency, such increase would result in an increase in manufacturing costs. Using electrochemical impedance spectroscopy at the optimised operating conditions, the MEA manufacturing process was optimised with respect to hot press pressure and time, while the effect of selected operating conditions was used to evaluate the charge transfer resistance, ohmic resistance and mass transport limitations. Results showed that the optimal hot pressing conditions were 125 kg.cm-2 and 50 kg.cm-2 for 5 minutes when using 25 and 10 cm2 active areas, respectively. The charge transfer resistance and mass transport were mostly influenced by the hot pressing procedure, while the ohmic resistance varied most with temperature. Applying the SO2 electrolyser in an alternative environment to the HyS thermochemical cycle, the effect of H2S on the SO2 electrolyser anode was investigated for the possible use of SO2 electrolysis to remove SO2 from mining off-gas which could contain H2S. Polarisation curves, EIS and CO stripping were used to evaluate the transient voltage response of various H2S levels (ppm) on cell efficiency. EIS confirmed that the charge transfer resistance increased as the H2S competed with the SO2 for active catalyst sites. Mass transport limitations were observed at high H2S levels (80 ppm) while the ECSA (electrochemical surface area obtained by CO stripping) showed a significant reduction of active catalyst sites due to the presence of H2S. Pure SO2 reduced the effective active area by 89% (which is desired in this case) while the presence of 80 ppm H2S reduced the active catalyst area to 85%. The suitability of PBI-based blend membranes in the SO2 electrolyser was evaluated by using chemical stability tests and electrochemical MEA characterisation. F6PBI was used as the PBI-containing base excess polymer which was blended with either partially fluorinated aromatic polyether (sFS001), poly(2,6-dimethylbromide-1,4-phenylene oxide (PPOBr) or poly(tetrafluorostyrene-4-phosphonic acid) (PWN) in various ratios. Some of the blend membranes also contained a cross-linking agent which was specifically added in an attempt to reduce swelling and promote cross-linking within the polymer matrix. The chemical stability of the blended membranes was confirmed by using weight and swelling changes, TGA-FTIR and TGA-MS. All membranes tested showed low to no chemical degradation when exposed to 80 wt% H2SO4 at 80°C for 120 h. Once the MEA doping procedure had been optimised, electrochemical characterisation of the PBI MEAs, including polarisation curves, voltage stepping and long term operation (> 24 h) was used to evaluate the MEAs. Although performance degradation was observed for the PBI membranes during voltage stepping, it was shown that this characterisation technique could be applied with relative ease, producing valuable insights into MEA stability. Since it is expected that the SO2 electrolyser will be operated under static conditions (cell temperature, pressure and current density) in an industrial setting (HyS cycle or for SO2 removal), a long term study was included. Operating the SO2 electrolyser under constant current density of 0.1 A cm-2 confirmed that PBI-based polyaromatic membranes were suitable, if not preferred, for the SO2 environment, showing stable performance for 170 hours. This work evaluated the performance of commercial materials while further adding insights into both characterisation techniques for chemical stability of polymer materials and electrochemical methods for MEA evaluation to current published literature. In addition to the characterisation techniques this study also provides ample support for the use of PBI-based materials in the SO2 electrolyser. / PhD (Chemistry), North-West University, Potchefstroom Campus, 2015

The environmentally unsafe by-products (CO2, H2S, NOx and SO2 for example) of using carbon-based fuels for energy generation have paved the way for research on cleaner, renewable and possibly cheaper alternative energy production methods. Hydrogen gas, which is considered as an energy carrier, can be applied in a fuel cell setup for the production of electrical energy. Although various methods of hydrogen production are available, sulphur-based thermochemical processes (such as the Hybrid Sulfur Process (HyS)) are favoured as alternative options for large scale application. The SO2 electrolyser is applied in producing H2 gas and H2SO4 by electrochemically converting SO2 gas and water. This study focused firstly on the evaluation of the performance of the SO2 electrolyser for the production of hydrogen and sulphuric acid, using commercially available PFSA (perfluorosulfonic acid) (Nafion®) as benchmark by evaluating i) various operating parameters (such as cell temperature and membrane thickness), ii) the influence of MEA (membrane electrode assembly) manufacturing parameters (hot pressing time and pressure) and iii) the effect of H2S as a contaminant. Subsequently, the suitability of novel PBI polyaromatic blend membranes was evaluated for application in an SO2 electrolyser. The parametric study revealed that, depending on the desired operating voltage and acid concentration, the optimisation of the operating conditions was critical. An increased cell temperature promoted both cell voltage and acid concentration while the use of thin membranes resulted in a reduced voltage and acid concentration. While an increased catalyst loading resulted in increased cell efficiency, such increase would result in an increase in manufacturing costs. Using electrochemical impedance spectroscopy at the optimised operating conditions, the MEA manufacturing process was optimised with respect to hot press pressure and time, while the effect of selected operating conditions was used to evaluate the charge transfer resistance, ohmic resistance and mass transport limitations. Results showed that the optimal hot pressing conditions were 125 kg.cm-2 and 50 kg.cm-2 for 5 minutes when using 25 and 10 cm2 active areas, respectively. The charge transfer resistance and mass transport were mostly influenced by the hot pressing procedure, while the ohmic resistance varied most with temperature. Applying the SO2 electrolyser in an alternative environment to the HyS thermochemical cycle, the effect of H2S on the SO2 electrolyser anode was investigated for the possible use of SO2 electrolysis to remove SO2 from mining off-gas which could contain H2S. Polarisation curves, EIS and CO stripping were used to evaluate the transient voltage response of various H2S levels (ppm) on cell efficiency. EIS confirmed that the charge transfer resistance increased as the H2S competed with the SO2 for active catalyst sites. Mass transport limitations were observed at high H2S levels (80 ppm) while the ECSA (electrochemical surface area obtained by CO stripping) showed a significant reduction of active catalyst sites due to the presence of H2S. Pure SO2 reduced the effective active area by 89% (which is desired in this case) while the presence of 80 ppm H2S reduced the active catalyst area to 85%. The suitability of PBI-based blend membranes in the SO2 electrolyser was evaluated by using chemical stability tests and electrochemical MEA characterisation. F6PBI was used as the PBI-containing base excess polymer which was blended with either partially fluorinated aromatic polyether (sFS001), poly(2,6-dimethylbromide-1,4-phenylene oxide (PPOBr) or poly(tetrafluorostyrene-4-phosphonic acid) (PWN) in various ratios. Some of the blend membranes also contained a cross-linking agent which was specifically added in an attempt to reduce swelling and promote cross-linking within the polymer matrix. The chemical stability of the blended membranes was confirmed by using weight and swelling changes, TGA-FTIR and TGA-MS. All membranes tested showed low to no chemical degradation when exposed to 80 wt% H2SO4 at 80°C for 120 h. Once the MEA doping procedure had been optimised, electrochemical characterisation of the PBI MEAs, including polarisation curves, voltage stepping and long term operation (> 24 h) was used to evaluate the MEAs. Although performance degradation was observed for the PBI membranes during voltage stepping, it was shown that this characterisation technique could be applied with relative ease, producing valuable insights into MEA stability. Since it is expected that the SO2 electrolyser will be operated under static conditions (cell temperature, pressure and current density) in an industrial setting (HyS cycle or for SO2 removal), a long term study was included. Operating the SO2 electrolyser under constant current density of 0.1 A cm-2 confirmed that PBI-based polyaromatic membranes were suitable, if not preferred, for the SO2 environment, showing stable performance for 170 hours. This work evaluated the performance of commercial materials while further adding insights into both characterisation techniques for chemical stability of polymer materials and electrochemical methods for MEA evaluation to current published literature. In addition to the characterisation techniques this study also provides ample support for the use of PBI-based materials in the SO2 electrolyser. / PhD (Chemistry), North-West University, Potchefstroom Campus, 2015