Trichloroethylene, a simple and very inexpensive material, has been identified as a tri- and tetrafunctionalizable building block. A combination of selective palladium-catalyzed cross-coupling reactions with standard lithiation and electrophilic quenching yields a wide variety of unsaturated linear or cyclic compounds in excellent yields in few synthetic steps. Dichlorovinyl ethers, obtained from a nucleophilic displacement reaction with trichloroethylene, are the basic starting materials. Two sets of conditions have been developed to achieve the reaction of either electron-rich or –deficient phenols with trichloroethylene to give the resultant dichlorovinyl ethers in high yields. Site selective palladium-catalyzed cross-coupling for the specific functionalization of a single C-Cl bond was developed, and could install alkyl, alkenyl, alkynyl and (hetero)aryl moieties. The resulting electrophiles could be reacted with a second organometallic nucleophile forming trisubstituted, electron-rich alkenes, dienes, trienes or enynes in only two or three steps. Alternatively, the product from the first cross-coupling reaction could be isolated, deprotonated and quenched with an electrophile, then cross-coupled with a second organometallic nucleophile to give tetrasubstituted, electron-rich alkenes and dienes. In the course of studying the site selective cross-coupling, it was found that prolonged exposure of the C1-functionalized materials to palladium promoted an intramolecular C-H activation, forming 2-substituted benzofurans. This reaction proved to be very general, and a wide variety of benzofurans were synthesized, containing both electron-withdrawing and electron-donating group groups in the donor arenes, as well as alkyl, alkenyl, alkynyl and aryl functionalities at the 2-position. This method was also extended to the synthesis of 2-substituted indoles from anilines, trichloroethylene and boronic acids.

No description available.

No description available.

Delineating the extent of brine contamination in shallow groundwater systems using piezometers is costly and does not provide adequate data resolution. Direct-push (D-P) electrical conductivity (EC) profiling enables rapid in situ measurements of bulk soil EC (ECa) at the cm scale. Previous studies using D-P EC profiling to detect contaminant plumes have solely relied on ECa measurements, and where attempts were made to isolate pore-water salinity variations from changes in ECa they were accomplished using simple linear methods. In this study D-P EC profiling was used to define groundwater salinity distributions using an established soil conductance model and estimate the timing of groundwater contamination at a long-term potash mine in south-central Saskatchewan, Canada. The site was dominated by fine-grained postglacial and glacial sediments with known Na-K-Cl brine impacts resulting from mining activities. Coreholes (n=22) were drilled to 7.6-12.2 m below ground (mbg) to obtain continuous cores for detailed geologic descriptions and measurements of index parameters (n=522) below the water table. Pore-water EC (ECw) and Cl- results from squeezed core samples (n=142) at 12 locations were compared to ECa measurements collected using a D-P probe adjacent to each corehole. Measured ECw and pore-water Cl- results ranged from 1.94-55.1 mS/cm and 87-20,700 mg/L, respectively. In situ D-P EC values from logs collected adjacent to all 22 coreholes ranged from 2-8 mS/cm within the oxidized zone (5-6 mbg) and decreased to background values of 0.3-2 mS/cm within the underlying unoxidized zone. Significant linear ECa–ECw regressions established for four lithological groups (r2=0.78-0.95) were used with porosity and dry density measurements to generate high-resolution depth profiles of ECw from D-P EC measurements. A significant linear ECw–Cl regression (r2=0.92) further enabled the generation of pore-water Cldepth profiles from ECw predictions. Observed 1D vertical profiles of Cl-, ECw, and ECa at three locations were modeled. Results suggested solute transport can be described as diffusion-dominated below depths of 3-5 mbg and that groundwater contamination began shortly after the onset of mining. Based on the results attained, this method can generate high-resolution depth profiles of pore-water salinity that can be used to define the lateral and vertical extent of brine contamination, dominant solute transport mechanisms, and timing of groundwater contamination.

No description available.

No description available.

The study of single-plume sprays into cross-flowing air is found extensively in literature, however, with the continued development of the Spark Ignition Direct Injection (SIDI) engine, the behaviour of multi-plume sprays in cross-flowing conditions is of interest. In the present work, the injection of a multi-plume spray into a high-velocity cross-flow is investigated; an experimental apparatus capable of providing a cross-flow with core velocities higher than 200 m/s is developed; analysis techniques are developed to characterize the cross-flow and multi-plume spray independently; the multi-plume spray is characterized as it issues into the cross-flowing air. The round air jet used for the cross-flow was designed using the concepts put forth for the design of wind tunnel contractions. The axial and radial velocities were measured using a Particle Image Velocimetry system from LaVision Inc. and the potential core length determined for the core velocities corresponding to Mach numbers of 0.35 and 0.58. It was determined that the potential core length increases with increasing Mach number and that increased compressibility, leads to reduced mixing within the core. Furthermore, velocity profiles of the air jet show that self-similarity is preserved within the shear layer of the initial region. The multi-plume spray was also characterized in quiescent conditions for 10 and 15 MPa injection pressures. It was found that the penetration depth and spray width increased with increasing injection pressure, but that the spray angle decreased with increasing pressure. The increase in penetration depth is consistent with the findings presented in literature, while the decrease in spray angle with increasing pressure is contrary to literature. Next, the multi-plume spray, injected at 10 and 15 MPa, is characterized as it issues into the cross-flowing air stream at Mach numbers equal to 0.35 and 0.58. The tail length and penetration are measured and it is found that for the first, the cross-flow velocity is the primary factor with higher cross-flow velocity resulting in a longer tail length, while for the latter, the injection pressure is the major factor, with higher injection pressures resulting in higher penetrations. That being said, the injection pressure does play a small role in the tail length, with the 15 MPa injection having a slightly longer tail length than the 10 MPa injection in the Mach number 0.58 cross-flow. This is attributed to the finer atomization, which is expected from the 15 MPa injection and which leads to quicker entrainment of fuel droplets into the cross-flow. The spray axis was predicted for each set of conditions from 0.1 ms to 1.0 ms after Start of Fuel (SOF). It was found that before 0.3 ms, the spray retains its multi-plume nature, while after 0.3 ms it behaves like a single-plume spray. Once the spray has crossed this transition point, the spray axis is temporally independent and can be predicted by the logarithmic models, similar to those used for single-plume sprays in cross-flow. The accuracy of this fit is improved upon, with the presentation of a modified correlation, which includes the momentum flux ratio inside of the logarithmic term. Finally, the multi-plume spray issuing into the cross-flow is characterized using PIV to measure droplet velocities. It is observed that the cross-flow momentum is imparted to the smaller droplets within the 15 MPa spray more easily than to those of the 10 MPa injection, but that the 15 MPa sprays also retain their momentum in the radial direction longer than the 10 MPa sprays. As such, the 10 MPa sprays align with the cross-flow axis faster.

As the demands of computational science and engineering simulations increase, the size and capabilities of High Performance Computing (HPC) clusters are also expected to grow. Consequently, the software providing the application programming abstractions for the clusters must adapt to meet these demands. Specifically, the increased cost of interprocessor synchronization and communication in larger systems must be accommodated. Non-blocking operations that allow communication latency to be hidden by overlapping it with computation have been proposed to mitigate this problem. In this work, we investigate offloading a portion of the communication processing to dedicated hardware in order to support communication/computation overlap efficiently. We work with the Message Passing Interface (MPI), the de facto standard for parallel programming in HPC environments. We investigate both point-to-point non-blocking communication and collective operations; our work with collectives focuses on the allgather operation. We develop designs for both flat and hierarchical cluster topologies and examine both eager and rendezvous communication protocols. We also develop a generalized primitive operation with the aim of simplifying further research into non-blocking collectives. We propose a new algorithm for the non-blocking allgather collective and implement it using this primitive. The algorithm has constant resource usage even when executing multiple operations simultaneously. We implemented these designs using CORE-Direct offloading support in Mellanox InfiniBand adapters. We present an evaluation of the designs using microbenchmarks and an application kernel that shows that offloaded non-blocking communication operations can provide latency that is comparable to that of their blocking counterparts while allowing most of the duration of the communication to be overlapped with computation and remaining resilient to process arrival and scheduling variations. / Thesis (Master, Electrical & Computer Engineering) -- Queen's University, 2014-05-29 11:55:53.87

Multinational enterprises (MNEs) are central drivers behind neo-liberal globalisation. These enterprises are usually centred in developed countries, with competitive operations in developing countries. The literature on MNEs and foreign direct investment usually focus on the motivation for investment, decisions on expansion, the structure of ownership of investment, the mode of entry, and the perception of risk. Fluctuation in the exchange rate is a source of uncertainty that affects MNEs' and other enterprises' market values. Enterprises' exposure to changes in the exchange rate has increased with the adoption of floating exchange rates and more intensive involvement in international trade. The conventional belief is that competition in the export market is positively related to a depreciation of the exchange rate, which will in turn be advantageous to the stock market, while the opposite is true for an appreciation of the exchange rate. If the contribution of import or intermediate imported inputs to the final production were quite large, an appreciation of the exchange rate will have a positive effect on input costs and the stock market. This study investigates the exchange rate exposure of multinational enterprises in South Africa to the bilateral exchange rate of the rand against the US dollar and the nominal effective exchange rate of the rand. It presents evidence on the direction and magnitude of currency exposure. From the empirical results presented in this study it can be concluded that the majority of MNEs are not significantly exposed to either one of the exchange rate changes. It has also been found that the majority of enterprises lose market value when their local currency depreciate against the US dollar, while the majority of South African enterprises are positively related to changes in the nominal effective exchange rate of the rand. MNEs that are not significantly exposed to changes in exchange rates could be subject to three possibilities. (1) The most obvious reason is that enterprises are not exposed to changes in the exchange rate. Enterprises in liberated (or •open") countries are more exposed to exchange rate movements as opposed to those in closed countries, such as the USA. (2) Enterprises could be engaged in on and off balance sheet hedging activities, which would reduce exchange rate exposures. (3) The methodology used in a study does not present the correct exposure results. / Thesis (M.Com. (Economics))--North-West University, Potchefstroom Campus, 2005.

In this dissertation 9 social workers working in Pretoria, Gauteng Province were interviewed. The focus of these interviews was regarding the use of direct observation as a measuring instrument for the purpose of assessing attachment of the caregiver-and-child's relationship. This information jointly with a two-fold literature study served as the foundation for a proposed preliminary practise framework. The completed research is described in the article format in two articles. Article 1 contains the literature study on attachment theory and its application to direct observation of attachment of the caregiver and child's relationship. Article 2 contains the literature study on direct observation measuring instruments for the purpose of assessing attachment of the caregiver-and-child's relationship. Direct observation measuring instruments used by experienced social workers were also examined by means of an empirical investigation. The practise framework acts as preliminary guidelines giving direction into the usage of direct observation as a structured measuring instrument in assessing the caregiver-and-child's attachment relationship. / Thesis (M.A. (MW))--North-West University, Potchefstroom Campus, 2009.