Creating new carbon-carbon bonds is one of the most important and challenging reactions in organic synthesis. Metal-catalyzed cross-coupling reactions have emerged as one of the preferred methods of producing new carbon-carbon bonds, and this work led to the 2010 Nobel Prize in Chemistry. This thesis was aimed at expanding the current research in the area of metal-catalyzed cross-coupling reactions to include new applications with dithiolane and dithiane protecting groups. 1,3-Dithiolane and 1,3-dithiane derivatives are particularly interesting molecules in that they can be deprotonated by a strong base to form anions, which can then be used for carbon-carbon bond synthesis. This thesis describes the investigation into the use of dithiolanes and dithianes in metal-catalyzed cross-coupling reactions, as well as some of the challenges faced in performing this sulfur-based chemistry.

The research presented herein describes the coupling of acoustic and heat release fluctuations in a perfectly-premixed swirl-stabilized combustor by analysis of simultaneous high-repetition-rate laser diagnostics data. Nine cases are studied, varying the thermal power and the equivalence ratio. Proper orthogonal decomposition (POD) of the velocity data shows that cases with higher amplitude thermoacoustic oscillations have flow fields containing helical vortex cores (HVC); these cases are further analysed to determine the driving mechanisms of the oscillations. Flow and flame statistics are compiled as a function of both the phase in the thermoacoustic cycle and a phase representing the azimuthal position of the HVC relative to the measurement plane. These data are used to spatially map the thermoacoustic energy transfer field, as described by the Rayleigh integral. It is found that periodic deformations of the HVC cause large-scale flame motions, resulting in regions of positive and negative energy transfer.

No description available.

No description available.

Creating new carbon-carbon bonds is one of the most important and challenging reactions in organic synthesis. Metal-catalyzed cross-coupling reactions have emerged as one of the preferred methods of producing new carbon-carbon bonds, and this work led to the 2010 Nobel Prize in Chemistry. This thesis was aimed at expanding the current research in the area of metal-catalyzed cross-coupling reactions to include new applications with dithiolane and dithiane protecting groups. 1,3-Dithiolane and 1,3-dithiane derivatives are particularly interesting molecules in that they can be deprotonated by a strong base to form anions, which can then be used for carbon-carbon bond synthesis. This thesis describes the investigation into the use of dithiolanes and dithianes in metal-catalyzed cross-coupling reactions, as well as some of the challenges faced in performing this sulfur-based chemistry.

The characterization of all components of pharmaceutical preparations, especially in the analysis of impurities present at levels higher than 0.05% of the main component, is a challenge in the pharmaceutical industry because no single detector can detect all impurities present. All commercial detection methods suffer from certain disadvantages. Universal sensitive detection with a wide dynamic range is strongly demanded. This results in an increasing interest in the development of universal sensitive detection methods for the pharmaceutical industry, which was the goal of this project. In this project, universal detection of analytes by HPLC-FID coupling was explored. Due to the large volume of the vapours of the mobile phase in HPLC, flame-based detection systems are prone to flame instability. To overcome this problem, a series of improvements were evaluated: 1) a fraction of the total volume of the effluent was delivered to the flame of the FID in a split mode; 2) a tubular oven was used before the FID to preheat the effluent and remove a large fraction of the mobile phase before the detector; 3) oxygen gas and a modified FID with an elongated burner were used to improve the performance of the FID. Finally, optimization of the FID design and parameters was performed by running a series of tests in flow injection mode using simplex optimization method.

No description available.

Standard local control theory, which describes Ca²⁺ release during excitation-contraction coupling (ECC), assumes that all Ryanodine Receptor (RyR) complexes are equivalent. Recent data from our laboratory has called this assumption into question. Specifically, we have shown that RyR complexes in ventricular myocytes differ depending on their location within the cell. This, and other data, has led us to hypothesize that similar differences occur within the rat atrial cell. To test this hypothesis, we have triple-labeled enzymatically-isolated, fixed myocytes to examine the distribution and colocalization of RyR, calsequestrin (CSQ), voltage-gated Ca²⁺ channels (Cav1.2), sodium-calcium exchangers (NCX), and caveolin-3 (cav-3). All images were acquired on a wide-field microscope, deconvolved, and subject to extensive analysis, including a novel method of measuring statistical significance of the recorded colocalization values. Overall, eight surface RyR populations were identified, depending on its binding partners. One of these groups, in which RyR, Cav1.2, and NCX colocalize, may provide the structural basis for ‘eager’ sites of Ca²⁺ release in atria, while other groups were defined based on their association with cav-3, and are therefore highly likely to be under the influence of other signaling molecules located within caveolae. Importantly, although a small portion of the surface RyR in atria do colocalize with NCX alone, the majority are tightly linked to Cav1.2 alone or Cav1.2 and NCX together. Therefore, it appears likely that Cav1.2-mediated calcium-induced calcium release (CICR) is the primary method of initiating Ca²⁺ release from the SR during EC coupling. / Medicine, Faculty of / Cellular and Physiological Sciences, Department of / Graduate

With a large number of carbon-carbon spin-spin coupling constants now determined and the dihedral angle dependence of vicinal coupling constants reported, application of this coupling constants data was attempted to a conformational study.

In the last centuries, transition metal chemistry beсome one оf the mоst іmportant tооls for synthesis of valuable organic compounds and different chemical transformations. In particular, transition metal catalysis are capable of forming novel cross coupling bonds. In this background, photocatalysis was developed later to create new chemical transformations by the irradiation with visible light. In this regard, the combination of transition metal catalysis and photochemistry is a breakthrough in catalysis that has provided impossible transformations in organochemistry. One of the widely available reactants in synthesis are alkyl chlorides. However, it is hard to activate chemically stable C(sp3 )-Cl bond at room temperature. In this study, we overcome this limitation by excited-state palladium catalysis under mild conditions. The reaction goes through the hybrid alkyl-Pd radical as a key intermediate. The procedure provides the synthesis of oxindole and isoquinolinedione derivatives mainly from alkyl chlorides via annulation overcoming its chemical limitations. This work will focus on the generation of alkyl radicals from unactivated C(sp3 )-Cl using simple palladium catalysis