Large-Scale Testing to Study the Effects of Critical Parameters on the Aerodynamic Behavior of Long Span Bridges

Long-span bridges are flexible and therefore are sensitive to wind induced effects. One way to improve the stability of long span bridges against flutter is to use cross-sections that involve twin side-by-side decks. However, this can amplify responses due to vortex induced oscillations. Wind tunnel testing is a well-established practice to evaluate the stability of bridges against wind loads. In order to study the response of the prototype in laboratory, dynamic similarity requirements should be satisfied. One of the parameters that is normally violated in wind tunnel testing is Reynolds number. In this dissertation, the effects of Reynolds number on the aerodynamics of a double deck bridge were evaluated by measuring fluctuating forces on a motionless sectional model of a bridge at different wind speeds representing different Reynolds regimes. Also, the efficacy of vortex mitigation devices was evaluated at different Reynolds number regimes. One other parameter that is frequently ignored in wind tunnel studies is the correct simulation of turbulence characteristics. Due to the difficulties in simulating flow with large turbulence length scale on a sectional model, wind tunnel tests are often performed in smooth flow as a conservative approach. The validity of simplifying assumptions in calculation of buffeting loads, as the direct impact of turbulence, needs to be verified for twin deck bridges. The effects of turbulence characteristics were investigated by testing sectional models of a twin deck bridge under two different turbulent flow conditions. Not only the flow properties play an important role on the aerodynamic response of the bridge, but also the geometry of the cross section shape is expected to have significant effects. In this dissertation, the effects of deck details, such as width of the gap between the twin decks, and traffic barriers on the aerodynamic characteristics of a twin deck bridge were investigated, particularly on the vortex shedding forces with the aim of clarifying how these shape details can alter the wind induced responses. Finally, a summary of the issues that are involved in designing a dynamic test rig for high Reynolds number tests is given, using the studied cross section as an example.

Variable Speed Limit Strategies to Reduce the Impacts of Traffic Flow Breakdown at Recurrent Freeway Bottlenecks

Variable Speed Limit (VSL) strategies identify and disseminate dynamic speed limits that are determined to be appropriate based on prevailing traffic conditions, road surface conditions, and weather conditions. This dissertation develops and evaluates a shockwave-based VSL system that uses a heuristic switching logic-based controller with specified thresholds of prevailing traffic flow conditions. The system aims to improve operations and mobility at critical bottlenecks. Before traffic breakdown occurrence, the proposed VSL’s goal is to prevent or postpone breakdown by decreasing the inflow and achieving uniform distribution in speed and flow. After breakdown occurrence, the VSL system aims to dampen traffic congestion by reducing the inflow traffic to the congested area and increasing the bottleneck capacity by deactivating the VSL at the head of the congested area. The shockwave-based VSL system pushes the VSL location upstream as the congested area propagates upstream. In addition to testing the system using infrastructure detector-based data, this dissertation investigates the use of Connected Vehicle trajectory data as input to the shockwave-based VSL system performance. Since the field Connected Vehicle data are not available, as part of this research, Vehicle-to-Infrastructure communication is modeled in the microscopic simulation to obtain individual vehicle trajectories. In this system, wavelet transform is used to analyze aggregated individual vehicles’ speed data to determine the locations of congestion. The currently recommended calibration procedures of simulation models are generally based on the capacity, volume and system-performance values and do not specifically examine traffic breakdown characteristics. However, since the proposed VSL strategies are countermeasures to the impacts of breakdown conditions, considering breakdown characteristics in the calibration procedure is important to have a reliable assessment. Several enhancements were proposed in this study to account for the breakdown characteristics at bottleneck locations in the calibration process. In this dissertation, performance of shockwave-based VSL is compared to VSL systems with different fixed VSL message sign locations utilizing the calibrated microscopic model. The results show that shockwave-based VSL outperforms fixed-location VSL systems, and it can considerably decrease the maximum back of queue and duration of breakdown while increasing the average speed during breakdown.

Discharge measurements and storm event chemistry at the San Francisco River station (Planta) in 2007-2008

To improve our knowledge of the influence of land-use on solute behaviour and export rates in neotropical montane catchments we investigated total organic carbon (TOC), Ca, Mg, Na, K, NO3 and SO4 concentrations during April 2007-May 2008 at different flow conditions and over time in six forested and pasture-dominated headwaters (0.7-76 km2) in Ecuador. NO3 and SO4 concentrations decreased during the study period, with a continual decrease in NO3 and an abrupt decrease in February 2008 for SO4. We attribute this to changing weather regimes connected to a weakening La Niña event. Stream Na concentration decreased in all catchments, and Mg and Ca concentration decreased in all but the forested catchments during storm flow. Under all land-uses TOC increased at high flows. The differences in solute behaviour during storm flow might be attributed to largely shallow subsurface and surface flow paths in pasture streams on the one hand, and a predominant origin of storm flow from the organic layer in the forested streams on the other hand. Nutrient export rates in the forested streams were comparable to the values found in literature for tropical streams. They amounted to 6-8 kg/ha/y for Ca, 7-8 kg/ha/y for K, 4-5 kg/ha/y for Mg, 11-14 kg/ha/y for Na, 19-22 kg/ha/y for NO3 (i.e. 4.3-5.0 kg/ha/y NO3-N) and 17 kg/ha/y for SO4. Our data contradict the assumption that nutrient export increases with the loss of forest cover. For NO3 we observed a positive correlation of export value and percentage forest cover.

Avaliação das condições de precipitação do azul da Prússia sobre pó de grafite visando o desenvolvimento de eletrodos de pasta de carbono para a quantificação de nitrito

An amperometric FIA method for nitrite quantification based on nitrite electroreduction and employing a carbon paste electrode (CPE) chemically modified with iron hexacyanoferrate (HCF) as an amperometric detector was developed. The influence of experimental conditions on the preparation of the electrode materials was evaluated and the materials obtained in each study were used for the development of modified electrodes. The electrochemical sensors were prepared by a fast, simple, and inexpensive procedure, and the long-term performance of the electrodes were quite satisfactory as the stability was maintained over one year. HCF was an effective redox mediator for nitrite electroreduction in acidic media, allowing nitrite detection at +0.2 V vs. Ag/AgClsat, which is a potential free of possible interfering species that are normally present in food and water samples. The electrochemical cell used in the FIA system was similar to a batch injection analysis cell, enabling recirculation of the carrier solution. This is an attractive feature because it allows the use of a high flow rate (6 mL min-1) leading to high sensitivity and analysis speed, while keeping reagent consumption low. The proposed method had a detection limit of 9 μmol L-1 and was successfully employed for nitrite quantification in spiked water and sausage samples. The obtained results were in good agreement with those provided by the spectrophotometric official method. At a 95 % confidence level it was not observed statistical differences neither in nitrite content nor in the precision provided by both methods. The experimental conditions for the synthesis of HCF were optimized and the best electrode material was prepared by mixing FeCl3, K4[Fe(CN)6] and carbon powder subjected to an acid and thermal treatment (400 ºC), followed by ultrasonic agitation at 4 °C. This material was used to construct an electrode with improved analytical performance to reduce nitrite, which presented greater stability compared to HCF film electrodeposited on the EPC, showing that the preparation procedure of the electrode material is an effective strategy for the development of HCF modified electrodes.

Carbon and Nitrogen Stable Isotopic Patterns in South Florida Coastal Ecosystems: Modern and Paleoceanographic Perspectives

Long term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on coastal biogeochemistry. The present study sought to increase understanding of the coastal marine system of South Florida under modern conditions and through the anthropogenic changes in the last century, on scales ranging from individual nutrient cycle processes to seasonal patterns in organic material (OM) under varying hydrodynamic regime, to century scale analysis of sedimentary records. In all applications, carbon and nitrogen stable isotopic compositions of OM were examined as natural recorders of change and nutrient cycling in the coastal system. High spatial and temporal variability in stable isotopic compositions were observed on all time scales. During a transient phytoplankton bloom, ä15N values suggested nitrogen fixation as a nutrient source supporting enhanced productivity. Seasonally, particulate organic material (POM) from ten sites along the Florida Reef Tract and in Florida Bay demonstrated variable fluctuations dependent on hydrodynamic setting. Three separate intra-annual patterns were observed, yet statistical differences were observed between groupings of Florida Bay and Atlantic Ocean sites. The POM ä15N values ranged on a quarterly basis by 7‰, while ä13C varied by 22‰. From a sediment history perspective, four cores collected from Florida Bay further demonstrated the spatial and temporal variability of the system in isotopic composition of bulk OM over time. Source inputs of OM varied with location, with terrestrial inputs dominating proximal to Everglades freshwater discharge, seagrasses dominating in open estuary cores, and a marine mixture of phytoplankton and seagrass in a core from the boundary zone between Florida Bay and the Gulf of Mexico. Significant shifts in OM geochemistry were observed coincident with anthropogenic events of the 20th century, including railroad and road construction in the Florida Keys and Everglades, and also the extensive drainage changes in Everglades hydrology. The sediment record also preserved evidence of the major hurricanes of the last century, with excursions in geochemical composition coincident with Category 4-5 storms.

Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis

Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. delta 13C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significantly lighter with increasing seawater pCO2. Together with a decrease in the difference between delta 13C values of both fractions at the higher pCO2 sites, these results indicate there is a greater net autotrophic input to the A. viridis carbon budget under high pCO2 conditions. delta 15N values and C/N ratios did not change in Symbiodinium and host tissue along the pCO2 gradient. Additional physiological parameters revealed anemone protein and Symbiodinium chlorophyll a remained unaltered among sites. Symbiodinium density was similar among sites yet their mitotic index increased in anemones under elevated pCO2. Overall, our findings show that A. viridis is characterized by a higher autotrophic/heterotrophic ratio as pCO2 increases. The unique trophic flexibility of this species may give it a competitive advantage and enable its potential acclimation and ecological success in the future under increased ocean acidification.

Dissolution of a spatially variable DNAPL (dense non aqueous phase liquid) source

Dissolution of non-aqueous phase liquids (NAPLs) or gases into groundwater is a key process, both for contamination problems originating from organic liquid sources, and for dissolution trapping in geological storage of CO2. Dissolution in natural systems typically will involve both high and low NAPL saturations and a wide range of pore water flow velocities within the same source zone for dissolution to groundwater. To correctly predict dissolution in such complex systems and as the NAPL saturations change over time, models must be capable of predicting dissolution under a range of saturations and flow conditions. To provide data to test and validate such models, an experiment was conducted in a two-dimensional sand tank, where the dissolution of a spatially variable, 5x5 cm**2 DNAPL tetrachloroethene source was carefully measured using x-ray attenuation techniques at a resolution of 0.2x0.2 cm**2. By continuously measuring the NAPL saturations, the temporal evolution of DNAPL mass loss by dissolution to groundwater could be measured at each pixel. Next, a general dissolution and solute transport code was written and several published rate-limited (RL) dissolution models and a local equilibrium (LE) approach were tested against the experimental data. It was found that none of the models could adequately predict the observed dissolution pattern, particularly in the zones of higher NAPL saturation. Combining these models with a model for NAPL pool dissolution produced qualitatively better agreement with experimental data, but the total matching error was not significantly improved. A sensitivity study of commonly used fitting parameters further showed that several combinations of these parameters could produce equally good fits to the experimental observations. The results indicate that common empirical model formulations for RL dissolution may be inadequate in complex, variable saturation NAPL source zones, and that further model developments and testing is desirable.

Seawater carbonate chemistry and biological processed during experiments with corals Porites sp. & Stylophora pistillata, 2010

Uptake of anthropogenic CO2 by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (omega arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistilata, exposed to high pCO2(or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistilata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO2 conditions, corresponding to pHTvalues of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater omega arag <1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C) and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO2 (low pH) conditions. Both species showed similar trends of delta11B depletion and delta18O enrichment under reduced pH, whereas the delta13C results imply species-specific metabolic response to high pCO2 conditions. The skeletal delta11B values plot above seawater delta11B vs. pH borate fractionation curves calculated using either the theoretically derived deltaB value of 1.0194 (Kakihana et al., Bull. Chem. Soc. Jpn. 50(1977), 158) or the empirical deltaB value of 1.0272 (Klochko et al., EPSL 248 (2006), 261). However, the effective deltaB must be greater than 1.0200 in order to yield calculated coral skeletal delta11B values for pH conditions where omega arag >1. The delta11B vs. pH offset from the literature seawater delta11B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal delta13C and delta18O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeleton

Do Changes in Current Flow as a Result of Arrays of Tidal Turbines Have an Effect on Benthic Communities?

Arrays of tidal energy converters have the potential to provide clean renewable energy for future generations. Benthic communities may, however, be affected by changes in current speeds resulting from arrays of tidal converters located in areas characterised by strong currents. Current speed, together with bottom type and depth, strongly influence benthic community distributions; however the interaction of these factors in controlling benthic dynamics in high energy environments is poorly understood. The Strangford Lough Narrows, the location of SeaGen, the world’s first single full-scale, grid-compliant tidal energy extractor, is characterised by spatially heterogenous high current flows. A hydrodynamic model was used to select a range of benthic community study sites that had median flow velocities between 1.5–2.4 m/s in a depth range of 25–30 m. 25 sites were sampled for macrobenthic community structure using drop down video survey to test the sensitivity of the distribution of benthic communities to changes in the flow field. A diverse range of species were recorded which were consistent with those for high current flow environments and corresponding to very tide-swept faunal communities in the EUNIS classification. However, over the velocity range investigated, no changes in benthic communities were observed. This suggested that the high physical disturbance associated with the high current flows in the Strangford Narrows reflected the opportunistic nature of the benthic species present with individuals being continuously and randomly affected by turbulent forces and physical damage. It is concluded that during operation, the removal of energy by marine tidal energy arrays in the far-field is unlikely to have a significant effect on benthic communities in high flow environments. The results are of major significance to developers and regulators in the tidal energy industry when considering the environmental impacts for site licences.

Continuous flow gas phase photoreforming of methanol at elevated reaction temperatures sensitised by Pt/TiO2

Gas phase photoreforming of methanol using a Pt/TiO2 photocatalyst has been performed under flow conditions at elevated temperatures. Comparing the activity of the reforming process as a function of temperature under dark and irradiated conditions shows a significant enhancement in the rate of H2 production using the photo-assisted conditions at temperatures between 100-140 °C. At higher temperatures, the effect of irradiation is small with the process dominated by the thermal process. Deactivation of the catalyst was observed under irradiation but the catalyst was easily regenerated using an oxygen treatment at 120 °C. Diffuse Reflectance Infra-red Fourier Transform Spectroscopy (DRIFTS) showed that the activity of the catalyst could be correlated with the presence of the photogenerated trapped electrons. In addition, lower amounts of CO adsorbed on Pt, compared to those observed in the dark reaction, were found for the UV-irradiated systems. It is proposed that CO and adsorbed intermediates, such as formate, can act as inhibitors in the photoreforming process and this is further supported by the observation that, before and after the regeneration process in O2, the CO and surface adsorbed organic intermediate products are removed and the activity is recovered.

Catalytic reactions with palladium supported on mesocellular foam : Applications in hydrogenation, isomerization, and C-C bond forming reactions

The major part of this thesis concerns the development of catalytic methodologies based on palladium nanoparticles immobilized on aminopropyl-functionalized siliceous mesocellular foam (Pd0-AmP-MCF). The catalytic activity of the precursor to the nanocatalyst, PdII-AmP-MCF is also covered by this work. In the first part the application of Pd0-AmP-MCF in Suzuki-Miyaura cross-coupling reactions and transfer hydrogenation of alkenes under microwave irradiation is described. Excellent reactivity was observed and a broad range of substrates were tolerated for both transformations. The Pd0-AmP-MCF exhibited high recyclability as well as low metal leaching in both cases. The aim of the second part was to evaluate the catalytic efficiency of the closely related PdII-AmP-MCF for cycloisomerization of various acetylenic acids. The catalyst was able to promote formation of lactones under mild conditions using catalyst loadings of 0.3 - 0.5 mol% at temperatures of up to 50 oC in the presence of Et3N. By adding 1,4-benzoquinone to the reaction, the catalyst could be recycled four times without any observable decrease in the activity. The selective arylation of indoles at the C-2 position using Pd-AmP-MCF and symmetric diaryliodonium salts is presented in the third part. These studies revealed that Pd0-AmP-MCF was more effective than PdII-AmP-MCF for this transformation. Variously substituted indoles as well as diaryliodonium salts were tolerated, giving arylated indoles in high yields within 15 h at 20 - 50 oC in H2O. Only very small amounts of Pd leaching were observed and in this case the catalyst exhibited moderate recyclability. The final part of the thesis describes the selective hydrogenation of the C=C in different α,β-unsaturated systems. The double bond was efficiently hydrogenated in high yields both under batch and continuous-flow conditions. High recyclability and low metal leaching were observed in both cases.

Oil Flow Rate Measurements Using 198au And Total Count Technique

In industrial plants, oil and oil compounds are usually transported by closed pipelines with circular cross-section. The use of radiotracers in oil transport and processing industrial facilities allows calibrating flowmeters, measuring mean residence time in cracking columns, locate points of obstruction or leak in underground ducts, as well as investigating flow behavior or industrial processes such as in distillation towers. Inspection techniques using radiotracers are non-destructive, simple, economic and highly accurate. Among them, Total Count, which uses a small amount of radiotracer with known activity, is acknowledged as an absolute technique for flow rate measurement. A viscous fluid transport system, composed by four PVC pipelines with 13m length (12m horizontal and 1m vertical) and ½, ¾, 1 and 2-inch gauges, respectively, interconnected by maneuvering valves was designed and assembled in order to conduct the research. This system was used to simulate different flow conditions of petroleum compounds and for experimental studies of flow profile in the horizontal and upward directions. As 198Au presents a single photopeak (411,8 keV), it was the radioisotope chosen for oil labeling, in small amounts (6 ml) or around 200 kBq activity, and it was injected in the oil transport lines. A NaI scintillation detector 2”x 2”, with well-defined geometry, was used to measure total activity, determine the calibration factor F and, positioned after a homogenization distance and interconnected to a standardized electronic set of nuclear instrumentation modules (NIM), to detect the radioactive cloud.

Sediment Budget for Cane Land on the Lower Herbert River Floodplain, North Queensland, Australia

Land use in the river catchments of tropical North Queensland appears to have increased the export of sediment and nutrients to the coast. Although evidence of harmful effect of sediment on coastal and riverine ecosystems is limited, there is a growing concern about its possible negative impacts. Sugarcane cultivation on the floodplains of the tropical North Queensland river catchments is thought to be an important source of excess sediment in the river drainage systems. Minimum-tillage, trash blanket harvesting has been shown to reduce erosion from sloping sugarcane fields, but in the strongly modified floodplain landscape other elements (e.g. drains, water furrows and headlands) could still be important sediment sources. The main objectives of this thesis are to quantify the amount of sediment coming from low-lying cane land and identify the important sediment sources in the landscape. The results of this thesis enable sugarcane farmers to take targeted measures for further reduction of the export of sediment and nutrients. Sediment budgets provide a useful approach to identify and quantify potential sediment sources. For this study a sediment budget is calculated for a part of the Ripple Creek catchment, which is a sub-catchment of the Lower Herbert River. The input of sediment from all potential sources in cane land and the storage of sediment within the catchment have been quantified and compared with the output of sediment from the catchment. Input from, and storage on headlands, main drains, minor drains and water furrows, was estimated from erosion pin and surface profile measurements. Input from forested upland, input from fields and the output at the outlet of the catchment was estimated with discharge data from gauged streams and flumes. Data for the sediment budget were collected during two ‘wet’-seasons: 1999-2000 and 2000-2001. The results of the sediment budget indicate that this tropical floodplain area is a net source of sediment. Plant cane fields, which do not have a protective trash cover, were the largest net source of sediment during the 1999-2000 season. Sediment input from water furrows was higher, but there was also considerable storage of sediment in this landscape element. Headlands tend to act as sinks. The source or sink function of drains is less clear, but seems to depend on their shape and vegetation cover. An important problem in this study is the high uncertainty in the estimates of the sediment budget components and is, for example, likely to be the cause of the imbalance in the sediment budget. High uncertainties have particularly affected the results from the 20002001 season. The main source of uncertainty is spatial variation in the erosion and deposition processes. Uncertainty has to be taken into consideration when interpreting the budget results. The observation of a floodplain as sediment source contradicts the general understanding that floodplains are areas of sediment storage within river catchments. A second objective of this thesis was therefore to provide an answer to the question: how can floodplains in the tropical North Queensland catchments can be a source of sediment? In geomorphic literature various factors have been pointed out, that could control floodplain erosion processes. However, their importance is not 'uniquely identified'. Among the most apparent factors are the stream power of the floodwater and the resistance of the floodplain surface both through its sedimentary composition and the vegetation cover. If the cultivated floodplains of the North Queensland catchments are considered in the light of these factors, there is a justified reason to expect them to be a sediment source. Cultivation has lowered the resistance of their surface; increased drainage has increased the drainage velocity and flood control structures have altered flooding patterns. For the Ripple Creek floodplain four qualitative scenarios have been developed that describe erosion and deposition under different flow conditions. Two of these scenarios were experienced during the budget study, involving runoff from local hillslopes and heavy rainfall, which caused floodplain erosion. In the longer term larger flood events, involving floodwater from the Herbert River, may lead to different erosion and deposition processes. The present study has shown that the tropical floodplain of the Herbert River catchment can be a source of sediment under particular flow conditions. It has also shown which elements in the sugarcane landscape are the most important sediment sources under these conditions. This understanding will enable sugarcane farmers to further reduce sediment export from cane land and prevent the negative impact this may have on the North Queensland coastal ecosystems.

Greener methodology for the synthesis of alpha-diazocarbonyl compounds and a novel approach to dioxinone derivatives

This thesis outlines a more environmentally benign approach to diazo transfer, and the investigation of the reactivity of -diazocarbonyl compounds when subjected to transition metal and lanthanide catalysis. Extensive studies were carried out to find the optimum conditions for a greener diazo transfer methodology, and this was also applied to a continuous process for the synthesis of -diazo--ketoesters. The first chapter includes a literature review of the synthesis and subsequent reactivity of -diazocarbonyl compounds. An overview of the applications of flow chemistry for the synthesis of hazardous intermediates is also included. The applications of lanthanide catalysts in organic synthesis is also discussed. The second chapter outlines the extensive studies undertaken to determine the optimum conditions for a greener diazo transfer methodology, including base and solvent studies. Use of water as a viable solvent for diazo transfer was successfully investigated. Diazo transfer to a range of -diazo--ketoesters was achieved using 5 mol% triethylamine or DMAP in water with high conversions. Polystyrene-supported benzenesulfonyl azide as an alternative diazo transfer reagent was also explored, as well as investigations into cheaper generation of this safer reagent. This polymer-supported benzenesulfonyl azide was used with 25 mol% of base in water to achieve successful diazo transfer to a range of -diazo--ketoesters. The third chapter describes the application of the new methodology developed in Chapter 2 to a continuous processing approach. Various excellent conditions were identified for both batch and flow reactions. A series of -diazo--ketoesters were synthesised with excellent conversions using 25 mol% triethylamine in 90:10 acetone water using flow chemistry. Successful diazo transfer was also achieved using a polymer-supported benzenesulfonyl azide in water under flow conditions. The fourth chapter discusses the reactivity of -diazo--ketoesters under transition metal and lanthanide catalysis. This chapter describes the synthesis of a range of -ketoesters via transesterification, which were used to synthesise a range of novel -diazo--ketoesters that were used in subsequent decomposition reactions. A novel route to dioxinones via rhodium(II) catalysis is reported. Attempted OH and SH insertion reactions in the presence of various lanthanide(II) catalysts are outlined, leading to some unexpected and interesting rearrangement products. The experimental details, including spectroscopic and analytical data for all compounds prepared, are reported at the end of each chapter.

Shapes and Dynamics of Blood Cells in Poiseuille and Shear Flows

The dynamics, shape, deformation, and orientation of red blood cells in microcirculation affect the rheology, flow resistance and transport properties of whole blood. This leads to important correlations of cellular and continuum scales. Furthermore, the dynamics of RBCs subject to different flow conditions and vessel geometries is relevant for both fundamental research and biomedical applications (e.g drug delivery). In this thesis, the behaviour of RBCs is investigated for different flow conditions via computer simulations. We use a combination of two mesoscopic particle-based simulation techniques, dissipative particle dynamics and smoothed dissipative particle dynamics. We focus on the microcapillary scale of several μm. At this scale, blood cannot be considered at the continuum but has to be studied at the cellular level. The connection between cellular motion and overall blood rheology will be investigated. Red blood cells are modelled as viscoelastic objects interacting hydrodynamically with a viscous fluid environment. The properties of the membrane, such as resistance against bending or shearing, are set to correspond to experimental values. Furthermore, thermal fluctuations are considered via random forces. Analyses corresponding to light scattering measurements are performed in order to compare to experiments and suggest for which situations this method is suitable. Static light scattering by red blood cells characterises their shape and allows comparison to objects such as spheres or cylinders, whose scattering signals have analytical solutions, in contrast to those of red blood cells. Dynamic light scattering by red blood cells is studied concerning its suitability to detect and analyse motion, deformation and membrane fluctuations. Dynamic light scattering analysis is performed for both diffusing and flowing cells. We find that scattering signals depend on various cell properties, thus allowing to distinguish different cells. The scattering of diffusing cells allows to draw conclusions on their bending rigidity via the effective diffusion coefficient. The scattering of flowing cells allows to draw conclusions on the shear rate via the scattering amplitude correlation. In flow, a RBC shows different shapes and dynamic states, depending on conditions such as confinement, physiological/pathological state and cell age. Here, two essential flow conditions are studied: simple shear flow and tube flow. Simple shear flow as a basic flow condition is part of any more complex flow. The velocity profile is linear and shear stress is homogeneous. In simple shear flow, we find a sequence of different cell shapes by increasing the shear rate. With increasing shear rate, we find rolling cells with cup shapes, trilobe shapes and quadrulobe shapes. This agrees with recent experiments. Furthermore, the impact of the initial orientation on the dynamics is studied. To study crowding and collective effects, systems with higher haematocrit are set up. Tube flow is an idealised model for the flow through cylindric microvessels. Without cell, a parabolic flow profile prevails. A single red blood cell is placed into the tube and subject to a Poiseuille profile. In tube flow, we find different cell shapes and dynamics depending on confinement, shear rate and cell properties. For strong confinements and high shear rates, we find parachute-like shapes. Although not perfectly symmetric, they are adjusted to the flow profile and maintain a stationary shape and orientation. For weak confinements and low shear rates, we find tumbling slippers that rotate and moderately change their shape. For weak confinements and high shear rates, we find tank-treading slippers that oscillate in a limited range of inclination angles and strongly change their shape. For the lowest shear rates, we find cells performing a snaking motion. Due to cell properties and resultant deformations, all shapes differ from hitherto descriptions, such as steady tank-treading or symmetric parachutes. We introduce phase diagrams to identify flow regimes for the different shapes and dynamics. Changing cell properties, the regime borders in the phase diagrams change. In both flow types, both the viscosity contrast and the choice of stress-free shape are important. For in vitro experiments, the solvent viscosity has often been higher than the cytosol viscosity, leading to a different pattern of dynamics, such as steady tank-treading. The stress-free state of a RBC, which is the state at zero shear stress, is still controversial, and computer simulations enable direct comparisons of possible candidates in equivalent flow conditions.