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The effectiveness of advanced oxidation techniques in degrading steroids in wastewaterArwood, Bryan Stuart. January 2010 (has links) (PDF)
Thesis (M.S.)--University of Alabama at Birmingham, 2010. / Title from PDF t.p. (viewed June 30, 2010). Includes bibliographical references (p. 19-22).
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Síntese e fotoatividade de macroiniciadores baseados em tioxantona - estudo mecanístico e aplicações / Synthesis and photoinitiation activity of macroinitiators based on thioxanthone - mechanistic studies and applicationsRicardo Augusto Escriptorio 13 October 2011 (has links)
Três macroiniciadores foram sintetizados baseados em tioxantona; MMa-co-TXA, BMa-co-TXA e HMa-co-TXA. Estes macroiniciadores possuem vantagens em relação aos compostos de baixa massa molar apesar do seu alto custo. A fotoatividade destes macroiniciadores e da tioxantona para a polimerização de monômeros monofuncional (MMA) e multifuncionais, 2,2-bis[4-(2-hidroxi-3-metacriloxipropoxi)fenil]propano (Bis-GMA) e dimetacrilato de trietilenoglicol (TEGDMA) foi examinada com as técnicas de Fotocalorimetria Exploratória Diferencial e Espectroscopia de Infravermelho por Transformada de Fourier com acessório de ATR. Os co-iniciadores usados foram as aminas EDB, TEA e DMAEMA. Todos os sistemas foram estudados na ausência de solvente. Os resultados mostraram que os macroiniciadores são mais eficientes do que o composto de baixa massa molar. Medidas de fotólise por pulso de laser permitiram obter o espectro de absorção de transientes dos compostos estudados, bem como a constante de supressão do estado triplete pelas aminas e pelo monômero. A polimerização fotoiniciada pelos macroiniciadores na presença de aminas e dos monômeros foi estudada com o objetivo de se determinar o mecanismo que leva à formação dos radicais iniciadores. Expressões para o rendimento quântico de radicais ativos foram deduzidas a partir do mecanismo proposto. Resultados mostraram que a produção de radicais ativos para os macroiniciadores é maior do que a tioxantona. / In this work three macroinitiators based on thioxanthone were synthesized and characterized; MMA-co-TXA, BMA-co-TXA and HMA-co-TXA. Macroinitiators offer some advantages when compared with their corresponding low molecular weight analog. The photopolymerization initiated by macroinitiators and thioxanthone of methyl methacrylate (MMA) and mixtures of 2,2-bis[4-(2-hydroxy- 3-metacryloxipropoxi)phenyl]propane (Bis-GMA) and triethyleneglycol dimethacrylate (TEGDMA) was studied through Photocalorimetry (Photo-DSC) and Fourier Transform Infrared Spectroscopy with ATR accessory. All systems were studied in the absence of solvent (bulk) using EDB, TEA and DMAEMA, as co-initiators. Measures of Laser Flash Photolysis determined the transient absorption spectra of the compounds and also the bimolecular rate constants for the triplet quenching of the compounds. The polymerization reaction of the macroinitiator in presence of amine and monomer was studied in order to determine the mechanism leading to the formation of radical initiators. Expressions for the quantum yield of radicals assets were deducted from the proposed mechanism. Results showed that the radical production assets to macroinitiator is greater than the thioxanthone, making macroinitiators more efficient than the low molecular weight compound.
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Fotofísica e fotoquímica de tioxantonas aneladas e avaliação de sua eficiência como fotoiniciador na polimerização de diacrilatos / Photophysic and photochemistry of annelated thioxanthones and evaluation of efficiency as photoinitiator in polymerization of diacrylateDouglas Rosa Bernardo 14 April 2011 (has links)
Foram sintetizados a 5-tia-pentaceno-14-ona (TX-A) e a 5-tia-naftaceno-12-ona (TX-Np), dois compostos derivados da tioxantona, para serem usados como fotiniciadores em reações de polimerização de diacrilatos. Após purificação usando cromatografia em coluna e líquida de alta eficiência, esses compostos foram caracterizados por análise elementar (AE), espectroscopia na região do infravermelho (IV) e de ressonância magnética nuclear de próton (1H RMN). A caracterização do comportamento espectroscópico dos compostos foi feita utilizando-se espectroscopia na região do ultravioleta e visível (UV-vis) e de fluorescência. A UV-vis revelou que a TX-A apresenta maior absorção na região do visível em relação à TX-Np. Os resultados de fluorescência evidenciaram a dependência do solvente na emissão, juntamente com o comportamento das transições presentes. Os tempos de vida das espécies singlete foram determinados como sendo da ordem de nanosegundos, sendo maior em meio de solventes hidroxílicos polares. A fotólise por pulso de laser foi utilizada para estudar a absorção dos transientes, demonstrando que a TX-Np apresenta três máximos de absorção em 340, 450 e 590 nm, que foram atribuídos aos transientes do estado triplete/radical, radical cetila e ao estado triplete respectivamente, cujos tempos de vida se situam na ordem de microssegundos. Já a TX-A apresentou dois máximos de absorção em 415 e 515 nm, que correspondem à absorção do estado triplete do antraceno resultante da transferência de intramolecular de energia entre grupos da molécula. A avaliação do desempenho de ambos os compostos como fotoiniciadores foi feita com o auxílio da Fotocalorimetria Exploratória Diferencial (Foto-DSC) usando-se como modelo uma mistura dos monômeros BisGMa (dimetacrilato de bisfenilglicidila) e TEGDMA (dimetacrilato de trienilo glicol) nas proporções: 70:30; 30:70 e 50:50 (m/m), respectivamente. Estes estudos demonstraram que utilizando-se a TX-Np como fotoiniciador, a polimerização ocorreu com maior velocidade no sistema contendo maior proporção de BisGMA, que torna o sistema mais viscoso. Entretanto, maiores graus de conversão foram obtidos utilizando maiores proporções de TEGDMA, ou seja, misturas menos viscosa. Utilizando a TX-A, o sistema contendo BisGMA e TEGDMA na proporção 70:30 (m/m), apresentou maior velocidade de polimerização, enquanto a mistura contendo quantidades de massa iguais dos dois monômeros foi a que apresentou o maior grau de conversão. Quanto à influência de O2, apenas a TX-A apresentou resultado significativo na polimerização, quando o experimento foi realizado em ar. / The 5-thia-pentacene-14-one (TX-A) and 5-thia-naphthacene-12-one (TX-Np), both derivatives of thioxanthone have been synthesized and evaluated in relation to their performance as photoinitiators in diacrylates polymerization reaction. After purifying by column and liquid chromatography the compounds were characterized by elemental analysis (EA), spectroscopy in the infrared region (IR) and proton nuclear magnetic resonance (1H NMR). The spectral behavior of the thioxanthone derivatives was performed by spectroscopy in the ultraviolet and visible range (Uv-vis) and fluorescence. The UV-vis results revealed that TX-A presents higher absorption in the visible range than the TX-Np. The fluorescence data evidenced a dependence of the solvent nature in the emission. The life time of singlet species was determined as in the nano-seconds level, being higher in polar hydroxilic solvents medium. The laser flash-photolysis was used to investigate the transients absorption, revealing that the TX-Np have three absorption maxima at 340, 450 and 590 nm, which were attributed to the triplet state/radical, cetyl radical and triplet state, respectively, whose lifetimes were in the microseconds scale. Meanwhile, the TX-A showed two absorption maxima at 415 and 515 nm corresponding to the anthracene triplet state absorption from an intramolecular energy transfer between groups of the molecule. The performance of both photoinitiators had been evaluated by Photocalorimetry, using a mixture of bisphenylglycidyl dimetacrilate (BisGMA) and triethileneglycol dimetracrylate (TEGDMA) containing 70:30; 30:70 and 50:50 (w/w) of each monomer respectively. Such studies demonstrated that using TX-Np as a photoinitiator the rate of polymerization was higher when larger amounts of BisGMA is used in the mixture, making the system more viscous. However higher conversion degrees were found when higher amounts of TEGDMA are used, that means in less viscous mixtures. When TX-A is used as a photoinitiator the system containing 70:30 (w/w) of BisGMA and TEGDMA, showed higher rate of polymerizations while the mixture containing equal amounts of both monomers presented a higher conversion degree. Concerning the O2 influence, only the TX-A presented a significant polymerization extent when the experiment was performed in the presence of air.
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Kinetic Investigation of Atomic Hydrogen with Sulfur-Containing SpeciesKerr, Katherine Elaine 12 1900 (has links)
The reactions of atomic hydrogen with methanethiol and that of atomic hydrogen with carbon disulfide were studied experimentally using flash-photolysis resonance-fluorescence techniques. Rate constants were determined over a range of temperatures and pressures, and through analysis and comparison to theoretical work details of the reactions were ascertained.
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Studies of Solvent Displacement from Solvated Metal Carbonyl Complexes of Chromium, Molybdenum, and TungstenZhang, Shulin 08 1900 (has links)
Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of Cr.
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Characterizing triplet azo biradical and corannulene- halogen complexes by laser flash photolysisLi, Qian January 2012 (has links)
No description available.
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Photochemistry of Photodynamic Organic Azides and Peroxide in Crystals and ComplexesMerugu, Rajkumar 02 June 2023 (has links)
No description available.
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Mechanistic Study on Photogeneration of Nitrogen Based Reactive Intermediates via Transient Spectroscopy & Infrared Matrix Isolation Study on Organometallic Reactions with Ozone Forming Metal OxidesSriyarathne, H. Dushanee M. 30 October 2017 (has links)
No description available.
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Applications Focused Synthetic Modification on Photoremovable Protecting Groups (PRPG) & Photochemical Analysis on Organic Azides and IsoxazolesThenna Hewa, Kosala R. S. January 2017 (has links)
No description available.
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From high spin systems to photorelease: Reactivity of twisted-triplet alkene 1,2 biradicalRajam, Sridhar 06 August 2010 (has links)
No description available.
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