Pharmaceuticals and personal care products (PPCPs) are widely used, resulting in trace amounts being detected in the aquatic environment. This presence is of human health and ecological concern and it is necessary to determine the best methods to eliminate them from our waters. The oxidation of PPCPs by permanganate was evaluated using a spectrophotometer to monitor permanganate reduction. Thirty-nine compounds were chosen to represent numerous classifications, including beta blockers, cephalosporins, fluoroquinolones, macrolides, non-steroidal anti-inflammatory drugs, phenol structures, polypeptides, sulfonamides, tetracyclines, and triazines. The reactivity of each compound was determined by measuring the absorbance of permanganate over time as it reacted with an excess of the compound. The absorbance data was fit to a pseudo-first-order reaction model that accounted for the growth of manganese dioxide colloids. The most reactive groups that reduced permanganate within minutes at pH 7.0 were the cephalosporins, phenol structures, and tetracyclines. The majority of the remaining pharmaceuticals and personal care products were moderately or weakly reactive (reducing permanganate within hours). Caffeine, carbadox, monensin, simetone, and tri(2-carboxyethyl)phosphine were poorly reactive (reducing permanganate over days). Metoprolol was the only selected compound that was determined to be potentially non-reactive (no reaction after 1 day). Polarizability and refractive index of the organic compounds showed significant positive correlations (R-squared > 0.50) with the first-order reaction rates for non-steroidal anti-inflammatory drugs and the phenol structures group. The half-life of each PPCP was determined based on a typical dosage of permanganate used for pre-oxidation. Eleven of the thirty-nine PPCPs had a half-life of less than thirty minutes (a typical contact time), indicating that oxidation by permanganate may be a viable option. There are many opportunities for further research in this area, including investigating more PPCPs, physicochemical property correlations, and the impact of water quality conditions

M. Tech. Metallurgical Engineering. / Investigate the dissolution behaviour of sphalerite minerals in sulphuric acid using ferric ions as oxidants. The specific objectives are to study the following: 1. the mineralogical characteristics of sphalerite ores ; 2. mineralogical effects on dissolution kinetics in sulphuric acid and 3. Effect of ferric ion concentration on the dissolution kinetics of sphalerite ores in sulphuric acid. Mineralogy is a critical area in mineral processing and has to be considered during process design stage, and during each processing stage. The type and concentration of oxidizing agent depend on the mineralogical composition of the ore. Many researchers investigations and test-works have been reported on leaching of sphalerite using both ferric sulphate and ferric chloride (Al-Harahsheh and Kingman, 2007; Rath et al., 1981). However, little or no studies have been reported on the combined oxidants.

Thesis (PhD) -- Macquarie University, Division of Environmental and Life Sciences, Dept. of Chemistry and Biomolecular Sciences, 2007. / Bibliography: leaves 295-322.

The oxidation of three alkyl thioethers, phenol and 2-propanol by trans-dioxo ruthenium porphyrin species, and the synthesis, characterization and reactivity of several new ruthenium porphyrin complexes are described in this thesis. The trans-dioxo species Ru(Porp)(O)₂ [Porp= the dianions of 5,10,15,20-tetramesitylporphyrin (TMP) and 5,10,15,20-(2,6-dichlorophenyl)porphyrin (OCP)] selectively oxidize diethyl-, di-n-butyl- and decylmethyl- sulfides to the corresponding sulfoxides at room temperature. The reaction is first order in [Ru] and in [thioether]. The second order rate constants for the first O-atom transfer from the Ru(TMP) system are: 7.54xl0⁻³, 1.23xl0⁻² and 1.14x10-¹ M⁻¹ s⁻¹ respectively for the three thioethers at 20.0 °C. The activation parameters for the O-atom transfer process are also determined: for Et₂S, ∆H‡= 58.3 kJ mol⁻¹ and ∆S‡= -86 J K⁻¹ mol⁻¹; for nBu₂S, AH‡= 47.4 kJ mol⁻¹and ∆S‡= -120 J K⁻¹ mol⁻¹; for DecMeS, ∆H‡= 56.5 kJ mo⁻¹ and ∆S‡= -70 J K⁻¹ mol⁻¹. A second order rate constant of 7.23xl0⁻²M⁻¹s⁻¹ is measured at 20.0 °C for the oxidation of Et₂S by Ru(OCP)(O)₂. The intermediates Ru(TMP)(OSEt₂)₂, Ru(TMP)(OSEt₂)(OSEt₂) and the final product Ru(TMP)(0SEt₂)₂,where O and S refer to O- and S- bonded sulfoxide, are observed by ¹H nmr, and the last mentioned is isolated and characterized. A mechanism is proposed, based on electrophilic attack of the O=Ru=O moiety on :SR₂ to form bis-O-bonded species which subsequently isomerizes to bis-S-bonded species via mixed species. The Ru(TMP)(O)₂/Et₂S/O₂ system at room temperature is catalytic in complex, but produces only about 5 turnovers due to poisoning of the catalyst by the reaction product. The same system at >65 °C gives higher turnovers, but now porphyrin ligand degradation is observed, perhaps via oxidation by the O=Ru=O moiety. The Ru(OCP)(0)₂/Et₂S/O₂ system at 100 °C catalytically oxidizes Et₂S to Et₂SO and Et₂SO₂ (in ~ 4:1 ratio) and the porphyrin ligand does not undergo oxidative destruction. The Ru(TMP)(O)₂ species reacts with phenol via an observed intermediate Ru(TMP)(p-O(H)C₆H₄OH)₂ to form Ru(IV)(TMP)(OC₆H₄OH)₂, a paramagnetic (S=l) complex which is isolated and characterized. The oxidation reaction is first order in both [Ru] and [phenol] with a second order rate constant 6.90x10⁻² M⁻¹ s⁻¹at 20.0 °C. A mechanism based on electrophilic attack by the O=Ru=O moiety on the aryl ring followed by proton migration is proposed. This mechanism also explains the formation of some free para-benzoquinone and 1 equivalent of water per Ru. No ortho-benzoquinone is formed in the reaction. Preliminary ⁻H nmr studies reveal that 2-propanol is oxidized to acetone by Ru(TMP)(O)₂. A paramagnetic species (S= 1) was isolated as the only porphyrin product but not characterized. A range of novel ruthenium porphyrin complexes is also prepared. The reaction of acetylene with the four-coordinate Ru(TMP) species forms [Ru(TMP)]₂(u-C₂H₂), the first reported organometallic ruthenium porphyrin dimer. The complexes, Ru(TMP)(PhCCPh) and Ru(TMP)(PhCCH), the first π-bonded alkyne species in ruthenium porphyrin chemistry, are characterized in solution. The π-bonded alkene complexes Ru(TMP)(CH₂CH₂) OPrOH).(iPrOH) and Ru(TMP)(CH₂CH₂) are isolated and characterized, while the Ru(TMP)(cyclohexene) complex is characterized in situ. The Ru(TMP)(OSEt₂)₂ complex is isolated also by the reaction of Ru(TMP)(CH₃CN)₂with Et₂SO. The Ru(TMP)(L)₂ complexes, L= OSMe₂, OSnPr₂ and OSnBu₂ are also prepared via the above method and characterized. Some new Ru(OCP) complexes, (the monocarbonyl, the bis-acetonitrile and the dioxo- species) are also isolated and characterized. / Science, Faculty of / Chemistry, Department of / Graduate

Menhaden is the major source of fish oil in the United States. Due to a high amount of polyunsaturated fatty acids which are highly susceptible to autoxidation, menhaden oil deteriorates rapidly, leading to objectionable off-odors and off-flavors. The purpose of this study was to investigate if the enzyme lipoxygenase is present in menhaden gill tissue and if it is a contributing factor in menhaden oil oxidation. Peroxide, TBA and anisidine values of undeodorized and deodorized menhaden oils exhibited two maxima during 20 weeks of storage at 30°C. Peroxide values of the undeodorized oil peaked at week 1 with 6.71 meq/kg and at week 12 with 21.50 meq/kg, while in the deodorized oil it peaked at week 8 (9.28 meq/kg) and week 20 (18.71 meq/kg). TBA maxima were observed at week 2 (1416 μMol/kg) and week 12 (4951 μMol/kg) and at week 8 (1397 μMol/kg) and week 20 (4284 μMo/kg) for undeodorized and deodorized menhaden oil respectively. Anisidine values showed maxima at the same weeks. These results indicate that lipid peroxidation of the deodorized oil lagged a few weeks behind the undeodorized oiL In this study, the conjugated diene and fluorescence analyses were found to be poor indicators for monitoring lipid oxidation in menhaden oil. Enzyme assays indicated that lipoxygenase activity is present in menhaden gill tissue with maximum activity at pH 9-10, resembling that of soybean lipoxygenase-l. A sensory panel judged omega-3 fatty acid ester concentrates treated with the enzyme extract as having a significantly (p < 0.03) stronger smell than the control ester for the first four weeks of an eight week study. However, no significant difference was found between the TBA values of the esters. Of the 60 volatile compounds identified by GC-MS in the undeodorized menhaden oil, 19 were aldehydes, 9 were alcohols and 8 were ketones. Volatiles that are potentially Ii poxygenase derived, namely 2-octenal, 1-octen-3-01, 2-nonenal, 2,6-nonadienal (E,Z), and 2,5-octadien-l-ol were among those identified in the undeodorized menhaden oil. The deooorized oil contained fewer total volatiles, and fewer aldehydes (6), ketones (1) and alcohols (8), but more long chain aliphatic compounds such as hydrocarbons, many of which were not possible to positively identify. No lipoxygenase derived volatiles were identified in the deooorized oil. Most of the volatiles in the omega-3 fatty acid ester concentrates were identified as esterified short chain fatty acids. No difference in the amount of total volatiles was found between four esters that were treated with and without the enzyme extract, a boiled enzyme extract and an enzyme extract that was inocculated with esculetin. However, in a repetition of just the control and the enzyme treated ester, a significantly (p < 0.02) higher amount of total volatiles was found in the enzyme treated ester, supporting the results of the sensory analysis. It was not possible to identify specific volatiles in the enzyme treated ester that were present in larger concentrations than in the other ester treatments. Volatiles identified in EPA and DHA ethyl esters were similar to those volatiles found in the undeodorized and deodorized menhaden oil as well as the omega-3 fatty acid ester concentrates, but no lipoxygenase derived volatiles were found. While lipoxygenase activity was found in the gill extract of menhaden, and sensory analysis was able to distinguish between a control and an enzyme incubated oil, the enzymatic activity was low (apparent Km = 16.7 μMol) and volatile analysis of various oils did not support the hypothesis that lipoxygenase is a major contributor to menhaden oil oxidation. Future research should include isolation and purification of menhaden gill lipoxygenase and the study of model systems to develop a better understanding of the contribution of lipoxygenase activity to oxidation of menhaden oil. / Ph. D.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-08-18T17:45:44Z No. of bitstreams: 1 2010 - Isabel Matos de Fraga.pdf: 5201934 bytes, checksum: 6bbaeba09901aea4cbaa9f69dbb0402e (MD5) / Made available in DSpace on 2017-08-18T17:45:44Z (GMT). No. of bitstreams: 1 2010 - Isabel Matos de Fraga.pdf: 5201934 bytes, checksum: 6bbaeba09901aea4cbaa9f69dbb0402e (MD5) Previous issue date: 2010-12-08 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior, CAPES, Brasil. / The researches on recycling of industrial wastes has been stepped up around the world to enhance the quality of the recycled product and provide greater efficiency of the productive system. The recycling of plastic materials has also grown in recent years, with Brazil improving its market position. In this way, this work aimed the development of composite materials using as a matrix, the low density polyethylene recycled (PEBDrec), chemical treated with oxidizing agents and, as fillers, E-cat and waste of scale. The PEBDrec was treated with oxidizing agent in order to cause modifications over its chemical structure and to improve compatibility with the residues of scale and E-cat. Were produced composites of PEBDrec treated with hydrogen peroxide (H2O2) and scale; PEBDrec treated with hydrogen peroxide and E-cat; PEBDrec treated with potassium permanganate (KmnO4) and scale and PEBDrec treated with potassium permanganate and E-cat. Were also obtained composites of PEBDrec untreated and mixed with scale or E-cat, to evaluate the action of the oxidizing agent in the compatibility between fillers that were used and the polymer matrix. The results obtained by the analysis of FTIR, XDR, TGA, SEM and mechanicals tests presented that the composites of PEBDrec treated with oxidizing agents showed a good interaction between the dispersed phase and the polymer matrix in comparison to composites PEBDrec without chemical treatment, and this compatibility was better for the lowest proportions. But this good interaction resulted in a decrease of thermal stability of composites in relation to the polymer matrix. It was also observed that the oxidizing agent KMnO4 was more effective in increasing the compatibility between the polymer and the E-cat, while the oxidizing agent H2O2 acted more strongly on increasing the compatibility between the polymer and scale. The composites of PEBDrec untreated, compared to the composites of PEBDrec treated with H2O2 and treated with KMnO4 , had a lower water absorption, indicating that chemical treatment was effective to modify the structure of the polymer, inducing the surface to a greater polarity, giving the chemical treated composites of PEBDrec a higher affinity to water. However a material more mechanical resistant was obtained just with the untreated polymer. The incorporation of the charges in the polymer matrix did not change the density of the material composites, indicating that despite of these materials be crystalline, they present low density, being possible to be used in civil construction. / As pesquisas sobre a reciclagem de res?duos industriais v?m sendo intensificadas em todo o mundo a fim de aumentar a qualidade do produto reciclado e propiciar maior efici?ncia do sistema produtivo. O reaproveitamento de materiais pl?sticos tamb?m tem crescido nos ?ltimos anos, com o Brasil melhorando seu posicionamento no mercado. Nesse sentido, essa disserta??o objetivou o desenvolvimento de materiais comp?sitos utilizando como matriz, o polietileno de baixa densidade reciclado (PEBDrec), tratado quimicamente com agentes oxidantes e como cargas, res?duos de Carepa e E-cat. O PEBDrec foi submetido a tratamento com agentes oxidantes com o objetivo de causar modifica??es na sua estrutura qu?mica e, propiciar uma melhoria na compatibilidade com os res?duos de carepa e E-cat. Foram produzidos comp?sitos de PEBDrec tratado com per?xido de hidrog?nio (H2O2) e carepa; PEBDrec tratado com per?xido de hidrog?nio e E-cat; PEBDrec tratado com permanganato de pot?ssio (KMnO4) e carepa e PEBDrec tratado com permanganato de pot?ssio e E-cat. Tamb?m foram obtidos comp?sitos de PEBDrec n?o tratado misturado a carepa ou E-cat, para avaliar a a??o do agente oxidante na compatibilidade entre a matriz polim?rica e as cargas utilizadas. Os resultados obtidos pelas an?lises de FTIR, DRX, TGA, MEV e ensaios mec?nicos mostraram que os comp?sitos de PEBDrec tratado com os agentes oxidantes apresentaram uma boa intera??o entre a fase dispersa e a matriz polim?rica em compara??o aos comp?sitos de PEBDrec sem o tratamento qu?mico, e essa compatibilidade foi melhor para as menores propor??es. Por?m, essa boa intera??o acarretou em uma diminui??o da estabilidade t?rmica dos comp?sitos, em rela??o a matriz polim?rica. Tamb?m foi poss?vel observar que o agente oxidante KMnO4 foi mais eficaz no aumento da compatibilidade entre o pol?mero e o E-cat, enquanto que o agente oxidante H2O2 atuou mais fortemente no aumento da compatibilidade entre o pol?mero e a carepa. Os comp?sitos de PEBDrec n?o tratado, em compara??o aos comp?sitos de PEBDrec tratados com H2O2 e tratados com KMnO4, apresentaram uma menor absor??o de ?gua, indicando que o tratamento qu?mico foi eficaz para modificar a estrutura do pol?mero deixando sua superf?cie com maior polaridade e conferindo aos comp?sitos de PEBDrec tratado quimicamente uma maior afinidade pela ?gua. Por?m um material mais resistente mecanicamente s? foi obtido com o pol?mero n?o tratado. A incorpora??o das cargas na matriz polim?rica praticamente n?o alterou a densidade desses materiais comp?sitos, indicando que apesar de eles serem materiais cristalinos, eles apresentam baixa densidade, sendo poss?vel suas aplica??es no ramo da constru??o civil.

Nanoenergetic composite materials have been synthesized by a sol-gel chemical process where the addition of a weak base molecule induces the gelation of a hydrated metal salt solution. A proposed proton scavenging mechanism, where a weak base molecule extracts a proton from the coordination sphere of the hydrated iron (III) complex in the gelation process to form iron (III) oxide/hydroxide, FeIIIxOyHz, has been confirmed for the weak base propylene oxide (PO), a 1,2 epoxide, as well as for the weak bases tetrahydrofuran (THF), a 1,4 epoxide, and pyridine, a heterocyclic nitrogen-containing compound. THF follows a similar mechanism as PO; the epoxide extracts a proton from the coordination sphere of the hydrated iron complex forming a protonated epoxide which then undergoes irreversible ring-opening after reaction with a nucleophile in solution. Pyridine also extracts a proton from the hydrated metal complex, however, the stable six-membered molecule has low associated ring strain and does not endure ring-opening. Fe2O3/Al energetic systems were synthesized from the epoxides PO, trimethylene oxide (TMO) and 3,3 dimethyl oxetane (DMO). Surface area analysis of the synthesized matrices shows a direct correlation between the surface area of the iron (III) oxide matrix and the quantified exothermic heat of reaction of the nano-scaled aluminum-containing energetic material due to the magnitude of the interfacial surface area contact between the iron (III) oxide matrix and the aluminum particles. The Fe2O3(PO)/Al systems possess the highest heat of reaction values due to the oxide interfacial surface area available for contact with the aluminum particles. Also, reactions containing nano-scale aluminum react differently than those containing micron-scale aluminum. RuO2/Al energetic systems behave differently dependent on the atmosphere the sample is heated. Heating the RuO2/Al samples in an inert atmosphere results in the complete reduction of the ruthenium oxide matrix to Ru(0) before reaction with the aluminum particles, resulting in the exothermic formation of RuxAly intermetallics, with the stoichiometry dependent on the initial Ru:Al concentration. However, heating the samples in an oxygen-rich atmosphere results in an exothermic reaction between RuO2 and Al.

Thesis (PhD) -- Macquarie University, Division of Environmental and Life Sciences, Dept. of Chemistry and Biomolecular Sciences, 2007. / Bibliography: leaves 295-322. / Generation of peroxide groups in proteins exposed to a wide variety of reactive oxygen species (ROS) requires an initial formation of protein carbon-centred or peroxyl free radicals, which can be reduced to hydroperoxides. Both protein radicals and protein hydroperoxides are capable of oxidizing important biomolecules and thus initiate biological damage. In this study, we investigated the inhibition of protein hydroperoxide formation by ascorbate and GSH in gamma-irradiated HL-60 cells.--We used HL-60 cells as a model for general protection of living organisms by ascorbate (Asc) and glutathione (GSH) from the deleterious effects of protein hydroperoxides generated by radicals produced by gamma radiation. Measurement by HPLC indicated that incubation of HL-60 cells with Asc in the presence of ascorbate oxidase resulted in the accumulation of intracellular Asc. The intracellular Asc levels were lowered by irradiation, demonstrating intracellular consumption of Asc by the radiation-generated radicals. Exposure of HL-60 cells to increasing gamma irradiation doses resulted in increasing accumulation of protein peroxides in the cells. This was measured by the FOX assay. A significant decrease in intracellular protein hydroperoxides was noted when the cells were treated with ascorbic acid before irradiation. A dose-dependent protective effect of Asc was observed. Asc loading also provided strong protection from radiation-generated protein hydroperoxides independently of the composition of the external medium, showing that only the radicals formed within the cells were effective in oxidizing the cell proteins. Similarly, protein peroxidation was inhibited in cells with enhanced levels of GSH and increased when the intracellular GSH concentration was reduced. These findings indicate that ascorbate and GSH are important antioxidants in protecting cells from oxidative stress associated with the generation of protein hydroperoxide. / Mode of access: World Wide Web. / xxix, 322 leaves ill

[Truncated abstract] This study investigates the thermal stability of Plasma Enhanced Chemical Vapor Deposited (PECVD) silicon nitride thin films. Effects of heat-treatment in air on the chemical composition, atomic bonding structure, crystallinity, mechanical properties, morphological and physical integrity are investigated. The chemical composition, bonding structures and crystallinity are studied by means of X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) Spectroscopy and Transmission Electron Microscopy (TEM). The mechanical properties, such as hardness and Young’s modulus, are determined by means of nanoindentation. The morphological and physical integrity are analyzed using Scanning Electron Microscopy (SEM) . . . The Young’s modulus (E) and hardness (H) of the film deposited at 448 K were measured to have E=121±1.8 GPa and H=11.7±0.25 GPa. The film deposited at 573 K has E=150±3.6 GPa and H=14.7±0.6 GPa. For the film deposited at 573 K, the Young’s modulus is not affected by heating up to 1148 K. Heating at 1373 K caused significant increase in Young’s modulus to 180∼199 GPa. This is attributed to the crystallization of the film. For the film deposited at 448 K, the Young’s modulus showed a moderate increase, by ∼10%, after heating to above 673 K. This is consistent with the much lower level of crystallization in this film as compared to the film deposited at 573 K. In summary, low temperature deposited PECVD SiNx films are chemically and structurally unstable when heated in air to above 673 K. The main changes include oxidation to SiO2, crystallization of Si3N4 and physical cracking. The film deposited at 573 K is more stable and damage and oxidation resistant than the film deposited at 448 K.