"October 2002" / Includes bibliographical references (leaves 180-191) / v, 191 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemistry, 2003

ADR is an important public health problem which reduces quality of care patients receive and increases cost to healthcare system. Little is known about the incidence and economic burden of ADR-related ED visits and subsequent hospitalizations in Canada. This study estimated the incidence and cost of ADR-related ED visits and subsequent hospitalizations for patients (>65 years) in Ontario, and explored patient, drug and system factors associated with severe ADRs. In a population-based retrospective cohort of Ontario older adults, 7222 (0.75%) of all ED visits were ADR-related, and among these patients 21.56% were hospitalized in 2007; In 2007, the total measured cost of ADR-related visits and subsequent hospitalizations amounted to $13.6 million with the cost being $333.47 and $7528.64 per person for ED visits and subsequent hospitalizations, respectively. Severe ADRs were associated with sex, age, comorbidity, multiple drugs, multiple pharmacies, newly prescribed drugs, recent ED visit, recent hospitalization and LTC residents.

My research is focused on two main objectives, the study of catalytic efficiency and mechanism of palladium nanoparticles stabilized by poly(vinylpyrrolidone) (PVP) for carbon-carbon coupling reactions, and to rationally synthesize metal nanoparticles stabilized by metal-carbon bonds and apply them to catalyze carbon-carbon coupling reactions.<p> In the first project, Pd nanoparticles stabilized by PVP were used to catalyze carbon-coupling reactions, specifically the Stille and Suzuki reactions. The mechanism of carbon-carbon coupling reactions was studied. The uncertainty of whether nanoparticles or Pd salts are the catalyst was also examined using the same experimental procedure with Pd salts to examine their catalytic activity in carbon-carbon coupling reactions. Results show that the presence of O2 is crucial to the Stille reaction with the Pd nanoparticles, which are nearly completely inert under N2, while the K2PdCl4 precursor is itself quite active for the Stille reaction. However, the Pd nanoparticles were found to be active for the Suzuki reaction with high yields in the absence of O2. The yields for 4-chlorobenzoic acid are higher than 4-bromobenzoic acid and occur for un-catalyzed reactions, for reasons that are still unknown. Finally Au nanoparticles have been tested by the same experimental procedure and have no catalytic activity for these two reactions.<p> In the second project, the synthesis of Au and Pd monolayer protected clusters (MPCs) with metal carbon covalent linkages was examined, and the stability of the resulting MPCs was tested. UV-Vis spectra and TEM images show the formation of Au and Pd nanoparticles and 1H NMR was used to characterize the ligands attached to the surface of the nanoparticles. The decylphenyl-stabilized Pd MPCs were synthesized successfully and quite stable in air, while decylphenyl-stabilized Au MPCs prepared with the same protocol have less stability and are easily decomposed. XPS spectra indicate the composition of decylphenyl-stabilized Pd MPCs is a combination of Pd0 and Pd2+ species with the Pd2+ species in excess. In addition, alkylphenyl-stabilized Pd nanoparticles were shown to be effective catalysts for carbon-carbon coupling reactions such as Suzuki and Stille reactions as well as hydrogenation reactions. Finally, it was noted that Pd-C bonds could be easily reduced by H2 when performing hydrogenation reactions resulting in nanoparticle aggregation and precipitation under hydrogenation conditions.

ADR is an important public health problem which reduces quality of care patients receive and increases cost to healthcare system. Little is known about the incidence and economic burden of ADR-related ED visits and subsequent hospitalizations in Canada. This study estimated the incidence and cost of ADR-related ED visits and subsequent hospitalizations for patients (>65 years) in Ontario, and explored patient, drug and system factors associated with severe ADRs. In a population-based retrospective cohort of Ontario older adults, 7222 (0.75%) of all ED visits were ADR-related, and among these patients 21.56% were hospitalized in 2007; In 2007, the total measured cost of ADR-related visits and subsequent hospitalizations amounted to $13.6 million with the cost being $333.47 and $7528.64 per person for ED visits and subsequent hospitalizations, respectively. Severe ADRs were associated with sex, age, comorbidity, multiple drugs, multiple pharmacies, newly prescribed drugs, recent ED visit, recent hospitalization and LTC residents.

My research is focused on two main objectives, the study of catalytic efficiency and mechanism of palladium nanoparticles stabilized by poly(vinylpyrrolidone) (PVP) for carbon-carbon coupling reactions, and to rationally synthesize metal nanoparticles stabilized by metal-carbon bonds and apply them to catalyze carbon-carbon coupling reactions.<p> In the first project, Pd nanoparticles stabilized by PVP were used to catalyze carbon-coupling reactions, specifically the Stille and Suzuki reactions. The mechanism of carbon-carbon coupling reactions was studied. The uncertainty of whether nanoparticles or Pd salts are the catalyst was also examined using the same experimental procedure with Pd salts to examine their catalytic activity in carbon-carbon coupling reactions. Results show that the presence of O2 is crucial to the Stille reaction with the Pd nanoparticles, which are nearly completely inert under N2, while the K2PdCl4 precursor is itself quite active for the Stille reaction. However, the Pd nanoparticles were found to be active for the Suzuki reaction with high yields in the absence of O2. The yields for 4-chlorobenzoic acid are higher than 4-bromobenzoic acid and occur for un-catalyzed reactions, for reasons that are still unknown. Finally Au nanoparticles have been tested by the same experimental procedure and have no catalytic activity for these two reactions.<p> In the second project, the synthesis of Au and Pd monolayer protected clusters (MPCs) with metal carbon covalent linkages was examined, and the stability of the resulting MPCs was tested. UV-Vis spectra and TEM images show the formation of Au and Pd nanoparticles and 1H NMR was used to characterize the ligands attached to the surface of the nanoparticles. The decylphenyl-stabilized Pd MPCs were synthesized successfully and quite stable in air, while decylphenyl-stabilized Au MPCs prepared with the same protocol have less stability and are easily decomposed. XPS spectra indicate the composition of decylphenyl-stabilized Pd MPCs is a combination of Pd0 and Pd2+ species with the Pd2+ species in excess. In addition, alkylphenyl-stabilized Pd nanoparticles were shown to be effective catalysts for carbon-carbon coupling reactions such as Suzuki and Stille reactions as well as hydrogenation reactions. Finally, it was noted that Pd-C bonds could be easily reduced by H2 when performing hydrogenation reactions resulting in nanoparticle aggregation and precipitation under hydrogenation conditions.

No description available.

The objective of this study was to establish a rapid and efficient assay that would assess acrosomal status and function of the stallion acrosome. Ejaculates from fertile and subfertile stallions were extended to 25x106/mL and divided into aliquots (1mL) treated with no ionophore (control) or 10µM A23187 and incubated at 37ºC for 0, 1, 2, and 3h. Following incubation, samples were fixed with 2% paraformaldehyde for 10 minutes at room temperature; then stored at 4°C in Dulbecco’s Phosphate-buffered saline (DPBS) for 0, 24, and 72 hours (i.e. post-fixation storage). After post-fixation storage samples were then permeabilized with 95% ethanol at -20ºC for 10 minutes. Samples were resuspended in 20% fetal bovine serum in DPBS, labeled with fluorescein isothiocyanate for 10 minutes, and analyzed by flow cytometry. Post-fixation storage produced fewer (P<0.05) acrosome intact (AI) spermatozoa and a higher (P<0.05) fluorescence intensity than respective fresh samples. Regardless of incubation time or treatment, cool-stored samples averaged ~6% lower (P<0.001) AI spermatozoa than the corresponding fresh semen; however, cooled storage did not alter (P>0.2) the overall fluorescence properties as compared to fresh semen (730±8.08 vs. 734±8.01 fluorescence intensity units, respectively). For fertile stallions, the percentage of AI spermatozoa was higher (p<0.01) in control samples than A23187 samples at incubation times 1, 2, and 3h (Control-59, 56, and 51% vs. A23187- 46, 29, and 23%, respectively), but not at Time 0. For subfertile stallions, the percentage of AI spermatozoa was not affected by ionophore treatment (P>0.05) or incubation period (P>0.05). The results suggest that post-fixation storage in DPBS for up to three days is still representative of the acrosomal competence of the original sample. In addition, spermatozoa stored for 24 hours in an Equitainer™ exhibited a small (~6%) but significant decrease in the percentage AI spermatozoa. Storage conditions may therefore, affect acrosomal integrity and contribute to reduced fertility when cooled-semen is used. Subfertile stallions exhibited little response [<11% acrosome reacted (AR)] after 3h of A23187 exposure, while the fertile stallions demonstrated a substantial response (≥ 36% AR) as soon as 1h after ionophore exposure. This assay diagnosed acrosomal dysfunction in stallions with unexplained subfertility.

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Roughly focus on two major kinds of ligand (H[PNP] and [PO3]H3) my work since more than one year. One of them R[PNP]H (R=iPr, Ph), We take these two ligands reacting with a series of Cu¡BAg,by good luck ,we get seven metal complexes. Among them that quite make us pleasantly surprised is Ph [PNP ] Cu dimer have quite good luminescence characteristics under the general visible light condition of the room temperature, we are sure that this characteristic can be used in many aspects such as electrochemical divices, as sensors and biological imaging agents, and in solar conversion schemes. Nitrogen fixation catalyzed by nitrogenases is an important process in biology. Recently, we are interested in this topic, and devoted in creating new metal complexes could play as an nitrogenases. For this reson, we use a bulky ligand [PO3]H3 reacting with lots of different meals including Li¡BCo¡BSn and group IV. We report herein the synthesis, characterization of them.

Although Pd-Au high-surface area catalysts are used in industry to improve activity and selectivity, a thorough understanding of the nature of these enhancements is lacking. A molecular-level understanding of catalytic reactions under actual reaction conditions is the ultimate goal. This thesis is mainly focused on the application of Pd-Au supported catalysts for vinyl acetate synthesis and CO oxidation reactions using highsurface area catalysts. We have attempted to improve the conventional Pd-Au based catalyst by synthesizing novel acetate-based and polymer-based catalysts. The corresponding catalytic reactivity and selectivity were measured and compared to conventional Pd-Au based catalyst systems. Subsequent characterization was performed using characterization techniques, such as, X-ray diffraction (XRD) and transmission electron microscopy (TEM). From our bimetallic catalytic studies, it was evident that the addition of Au to Pd leads to increased reactivity and selectivity. This surface modification is an important factor in the altered reaction kinetics for vinyl acetate (VA) synthesis and CO oxidation reactions. Promoted and unpromoted Pd-Au/SiO2/K+ catalyst were used for VA synthesis and the effect of pre-adsorbed O2, acetic acid and the role of oxygen were explored. The VA reaction rate of novel acetate-based Pd-Au/SiO2 catalyst was 3.5 times higher than conventional Pd-Au catalysts. Also, 100% selectivity was obtained for acetate-based Pd-Au/SiO2 at 130 oC and the VA formation rate was comparable to that of conventional Pd-Au catalysts. Therefore, the acetate-based Pd-Au/SiO2 catalyst seems very promising and can be explored further. Also, Pd(1):Au(4)/SiO2 catalysts demonstrate 100% CO conversion at much lower temperatures (90 oC) compared with other Pd-Au based catalysts. Furthermore, we were successful in obtaining sufficient CO oxidation activity with increased metal loading (5 wt%) and these catalysts did not deactivate under above-ambient reaction temperature conditions, which make 1:4 Pd- Au/SiO2 catalyst a good candidate for further exploration in CO oxidation reactions.