No description available.

Thesis (PhD)--University of South Australia, 2001.

Class of 2005 Abstract / Objective: The goal of this study was to determine the presence of erythro-methylphenidate (erythro-MPH) isomers contained within methylphenidate HCl (Metadate CD®) capsules. Methods: This experiment was conducted at a pharmaceutical manufacturing facility located in Tucson, Arizona. Methylphenidate HCl (MPH) capsules by Celltech Pharmaceuticals, Inc. were analyzed and compared to a reference standard. Thin-layer chromatography (TLC) was the technique used to qualitate the samples. The main outcome measure was the Rf values which were used to determine whether or not the MPH capsules contained erythro-MPH. Results: The study included ten, 20 mg MPH capsules and a reference standard (50 mg strength USP MPH related compound). The Rf value of the reference standard was 0.073 while the Rf value of the MPH samples ranged from 0.42 - 0.85. Conclusion: In this qualitative analysis of MPH capsules, there was no erythro-MPH isomers present in the MPH capsules.

No description available.

This investigation applied the techniques of polarography and controlled potential electrolytic reduction to the study of a series of unsymmetrical benzils. Eleven unsymmetrical benzils were synthesized and studied in 50% ethanol-water (by volume) solvent systems buffered at pH 1, 5, and 13. The results showed that, with unsymmetrical benzils substituted with electron-withdrawing or electrondonating groups, the carbonyl closest to the ring with the least electron-donating power was the preferred reaction site. However, the dicarbonyl system was nevertheless reduced as a unit, and Hammett sigma values of disubstituted symmetrical benzils were approximately additive. This was ascertained by comparing the ease of reduction of eight unsymmetrical benzils to the ease of reduction of the corresponding disubstituted symmetrical benzils. It was proposed that the electrons were added to the oxygen of one carbonyl, and that the second carbonyl was involved in the reduction chiefly through complete polarization of the dicarbonyl system at the electrode. In general, the reduction of unsymmetrical benzils appeared to follow the same path previously reported for symmetrical benzils.

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No description available.

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Nanotechnology holds great potential for improving our lives by creating many new materials and devices in medical sciences, electronics and also in energy production. Molecularly imprinted polymers (MIPs) are highly stable synthetic polymers that possess molecular recognition properties due to cavities created in the polymer matrix that are complementary to an analyte both in shape and in positioning of functional groups. These MIPs have been widely employed for diverse applications (e.g., in chromatographic separation, drug screening, chemosensors, catalysis, immunoassays etc) due to their specificity towards the target molecules and high stability against physicochemical perturbations. Conductive polymers, (CPs) such as polypyrrole, can be likened to semiconductors because of small band gaps and low electronic mobility. CPs are exploited as an excellent tool for the preparation of nanocomposites with nano scaled biomolecules. Polypyrrole (Ppy) was the first of this key family of compounds to show high conductivity. So, electrically conducting polypyrrole (Ppy) has numerous applications. In this study, caffeine imprinted electrodes (CIE) were prepared and characterized. This research project mainly focused on three important aspects: &#;To determine the thickness of the polymeric film. &#;To determine the Limit of detection (LOD) of the polymeric film at different conditions. &#;To determine the Analytical Sensitivity (γ) of the polymeric film at varied conditions. In summary these are conclusions stated: •The thickness of the electrode increased with an increase in the number of pulses. The film thickness increased linearly up to an application of 30 pulses and after 30 pulses, an increase in slope occurred with again a linear correlation up to the maximum applied number of pulses, 42. This change in slope may indicate a different mechanism taking place. •LOD is improved as the caffeine load is reduced from 10.0 to 3.0 mM and as the number of pulses is reduced from 36 to 24. •γ increases the number of pulses increase from 24 to 36 and also increases as the caffeine load increases.

Perfluorooctane sulfonate (PFOS) and related perfluoroalkyl surfactants (PFAS) are ubiquitous contaminants of increasing public concern due to their environmental persistence, toxicity, and bioaccumulation. These perfluorinated compounds have been used for more than half a century in a wide variety of industrial and consumer products ranging from stain repellents such as Teflon® to aqueous fire-fighting foams and to grease-proof food packing. The public health and environmental risks posed by PFAS have driven environmental agencies and the industry to restrict their use to specific applications where they cannot be replaced by other chemicals. The sources and pathways of PFOS and its derivatives in the environment are not well understood. Analysis of environmental samples is critical to understand the fate, transport and persistence of these emerging contaminants. Techniques based on fluorine nuclear magnetic resonance (¹⁹F NMR) spectroscopy and high performance liquid chromatography (HPLC) with suppressed conductivity detection were successfully developed to monitor the presence of PFAS in water samples. Chromatographic separation of C₄ to C₈ PFAS surfactants was achieved using a C₁₈ reversed-phase column and a mobile phase consisting of a mixture of boric acid and acetonitrile at mixing ratios ranging from 75:25 to 45:55 (v/v). The combination of these two techniques was very effective for characterization and routine quantification of PFOS and related chemicals. Analytical methods based on ¹⁹F NMR, HPLC-suppressed conductivity detection, and liquid chromatography with tandem mass spectrometry (LC-MS/MS) were employed to characterize commercial PFOS samples. Linear and branched PFOS isomers in a percentage ratio of 75:25 were identified. Municipal wastewater treatment systems are one of the major sources of PFAS emissions into the environment. The presence of PFAS in sewage sludge from two wastewater treatment plants in Tucson, Arizona, was investigated. Sludge samples were washed with acetic acid and extracted with a mixture of acetic acid and methanol. The extract was cleaned and concentrated by means of solid phase extraction. LC-MS/MS operating in the selective ion monitoring (SIM) mode was employed to assess the presence of perfluorosulfonates, perfluorosulfonamides, and perfluorocarboxylates in sewage sludge samples. PFOS was the only perfluoroalkyl chemical detected in municipal sludge samples at a concentration of 77 ± 5 g kg⁻¹ sludge dry weight. Cost-effective treatment techniques for removing PFAS from industrial effluents are needed to minimize discharges of these pollutants. Reductive dehalogenation is widely applied to the degradation of highly chlorinated compounds. Hence, the susceptibility of PFOS and related compounds to biological and chemical reductive dehalogenation was evaluated in batch assays. PFAS were not reductively dehalogenated by different microbial consortia even after periods of incubation exceeding 2 y, confirming the high resistance of these compounds to microbial degradation. The anaerobic biodegradability of PFOS and perfluorobutane sulfonate (PFBS) samples exposed to electrochemical pretreatment with boron-doped diamond film electrodes was also investigated. The oxidation decreased the concentration of PFAS and dissolved organic carbon in solution, confirming the destruction of these compounds. However, the oxidative treatment did not enhance the susceptibility of PFAS to microbial degradation even after extended periods of incubation (> 1 y). In contrast, PFOS was reductively dehalogenated with a biomimetic system based on vitamin B12 as the catalyst and Ti(III) citrate as the reducing agent. The optimal treatments conditions of the reaction were 260 μM vitamin B₁₂, 36 mM Ti(III) citrate, 70°C and solution pH 9.0. Interestingly, branched PFOS isomers were more prone to degradation by vitamin B₁₂ catalysis compared to the linear isomer. Removal of 3 mol Fper mol of technical PFOS and 12 mol F- per mol of branched PFOS isomers was achieved. Defluorination of PFOS was also observed at environmental relevant conditions of 30°C and pH 7.0, albeit at lower degradation rates. Fluoride and carbon dioxide were identified as the major products of the chemical defluorination. Traces of partially fluorinated volatile compounds were also detected in the headspace. The feasibility of removing PFAS compounds from aqueous streams by sorption onto granular activated carbon (GAC), zeolite, and wastewater treatment sludge was examined in batch isotherm experiments. The fluorocarbon chain and the functional group influenced sorption of the anionic surfactants, PFOS adsorbed more strongly to GAC than perfluorooctanoic acid (PFOA) and PFBS. Activated carbon showed the highest affinity for PFOS (Freundlich K(F) values of 36.7 to 60.9) followed by the hydrophobic, high-silica zeolite NaY (Si/Al 80, K(F) of 31.8) and lastly anaerobic sludge (K(F) of 0.95 to 1.85). GAC sorption is a suitable treatment for the removal of anionic perfluoroalkyl surfactants when present at low concentrations. Fluoride has been identified as the major product of the reductive dehalogenation of PFOS and derivatives. Thus, the toxicity of inorganic fluoride towards the main microbial populations responsible for the removal of organic constituents and nutrients in wastewater treatment processes was also studied. Fluoride concentrations ranging from 18 to 43 mg L⁻¹ caused 50% inhibition (IC₅₀) of the activity of propionate- and butyratedegrading microorganisms and of acetate-utilization by methanogens evaluated under mesophilic and thermophilic conditions. All other microbial populations evaluated in this study, i.e., glucose fermenters, aerobic glucose-degrading heterotrophs, denitrifying bacteria, and H₂-utilizing methanogens tolerated fluoride at very high concentrations (> 500 mg L⁻¹). In the same manner, H₂-utilizing methanogens also tolerated PFOS and PFBS at concentrations as high as 200 and 500 mg L⁻¹, respectively.