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Li, Jianping. "High-resolution UV-Vis-NIR fourier transform imaging spectroscopy and its applications in biology and chemistry." HKBU Institutional Repository, 2010. http://repository.hkbu.edu.hk/etd_ra/1151.
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Mavadat, Maryam. "Characterization of biomedical used plasmas by IR and UV-VIS emission spectroscopy." Thesis, Université Laval, 2014. http://www.theses.ulaval.ca/2014/30780/30780.pdf.
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La modification de surface par plasma est une technique largement utilisée pour améliorer les propriétés de surface de polymères par le greffage de différents groupes fonctionnels. Dans ce projet de recherche, différentes méthodes pour améliorer les techniques de caractérisation de décharge micro-ondes de N2 et N2-H2 ont été étudiées dans le but d’optimiser le procédé de traitement de surface par plasma. Tout d'abord, un certain nombre de paramètres du plasma ont été mesurés à différentes conditions de traitement. Pour déterminer les paramètres du plasma, la spectroscopie d'émission optique a été utilisée dans la région l’ultraviolet, du visible et l’infrarouge (rarement utilisée dans la littérature scientifique). L’utilisation de la spectroscopie d'émission dans cette dernière région spectrale est avantageuse car elle permet d'éliminer les forts chevauchements entre les transitions atomiques et moléculaires et de pallier la faible intensité du signal observée dans la région de l’ultraviolet et du visible. Par la suite, la composition chimique de surface du PTFE a été analysée par XPS pour déterminer les concentrations en carbone, fluor, azote et des groupements amine suite à un traitement par plasma. Les résultats mentionnés ci-dessus ont été utilisés pour corréler les conditions de traitement et les paramètres de décharge micro-ondes à la composition chimique du PTFE modifié, dans l’objectif de mettre en évidence les paramètres expérimentaux du plasma et les espèces présentes dans le plasma qui jouent un rôle clé pour maximiser la fonctionnalisation de surface du polymère avec des groupements amine. En outre, un modèle mathématique a été développé en utilisant la technique de régression PLS. Pour construire ce modèle, un ensemble de données de variables d'entrée contenant les conditions de traitement et les paramètres spectroscopiques du plasma et une matrice de réponse contenant les propriétés de surface du polymère ont été générées. La base de données obtenue a été utilisée pour établir la relation entre les paramètres du plasma, les conditions de traitement et la chimie de surface du film. Cela a finalement permis de prédire la composition chimique de la surface à partir d’informations relatives au plasma, sans avoir à effectuer des analyses de surface après le traitement.Plasma surface modification is a widely used technique for improving the surface properties of polymers through the introduction of different functional groups. In the current research project, different methods to improve the characterization techniques of N2 and N2-H2 microwave discharge were investigated with the aim of optimizing the plasma surface process. First of all, a number of plasma parameters were measured at different process conditions. To determine the plasma parameters, optical emission spectroscopy was used not only within the well-documented UV-Visible region but also within the rarely studied infrared zone. Using infrared optical emission spectroscopy is advantageous as it eliminates the strong overlap between atomic and molecular transitions as well as the low intensity UV-Visible emission spectroscopy limitations. In the next step, the PTFE surface chemical composition was analyzed via XPS to quantify the concentrations of carbon, fluorine, and nitrogen after a plasma treatment in a N2-H2 gaseous environment. The XPS analyses were also performed after chemical derivatization to quantify the surface concentration of amino groups (%NH2) at different process conditions. The above-mentioned results were used to correlate process conditions and microwave N2-H2 discharge parameters to the chemical composition of the modified PTFE. The purpose was to determine the external plasma parameters and species present within the plasma which play a key role in the introduction of amino groups to the polymer surface. Furthermore, a mathematical model was developed using the Partial Least Squares Regression, (PLSR) using custom scripts written in MATLAB. A data set of input variables including the process conditions and plasma parameters for each experiment were generated along with the corresponding response matrix which in turn contained the surface properties of the film. The resulting database was used to build the relationship between the plasma parameters, process condition and the resulting film surface chemistry. This ultimately enabled to predict the PTFE surface chemistry from data originating from the plasma, without having to proceed to post-plasma surface characterization.
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Rüger, Robert, Thomas Niehaus, Lenthe Erik van, Thomas Heine, and Lucas Visscher. "Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding." AIP Publishing, 2016. https://ul.qucosa.de/id/qucosa%3A21502.
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We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner’s group, very good agreement with TD-DFT calculations using local functionals was achieved.
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Lai, Sin Pin. "Furan measurement in transformer oil by UV-Vis spectroscopy using fuzzy logic approach." Thesis, Curtin University, 2009. http://hdl.handle.net/20.500.11937/2342.
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An Ultraviolet to Visible (UV-Vis) spectroscopic analysis based on fuzzy logic approach has been developed for furan content measurement in transformer oil. Following the successful identification and quantification of furan derivatives in transformer oil by ASTM D5837 standard, the new approach is able to approximate the furan content more conveniently and economically. As furan concentration level would determine the absorption intensity in UV-Vis spectral range, the fuzzy logic software model developed would exploit this characteristic to aggregate the furans content level in transformer oil. The UV-Vis spectral response at other ambient temperature is also studied. The proposed technique provides a convenient alternative to conventional method of furan measurement by High Performance Liquid Chromatography (HPLC) or Gas Chromatography Mass Spectrometry (GC/MS) in ASTM D5837 Standard.
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Lai, Sin Pin. "Furan measurement in transformer oil by UV-Vis spectroscopy using fuzzy logic approach." Curtin University of Technology, Department of Electrical and Computer Engineering, 2009. http://espace.library.curtin.edu.au:80/R/?func=dbin-jump-full&object_id=128452.
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An Ultraviolet to Visible (UV-Vis) spectroscopic analysis based on fuzzy logic approach has been developed for furan content measurement in transformer oil. Following the successful identification and quantification of furan derivatives in transformer oil by ASTM D5837 standard, the new approach is able to approximate the furan content more conveniently and economically. As furan concentration level would determine the absorption intensity in UV-Vis spectral range, the fuzzy logic software model developed would exploit this characteristic to aggregate the furans content level in transformer oil. The UV-Vis spectral response at other ambient temperature is also studied. The proposed technique provides a convenient alternative to conventional method of furan measurement by High Performance Liquid Chromatography (HPLC) or Gas Chromatography Mass Spectrometry (GC/MS) in ASTM D5837 Standard.
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Vidoto, Ednalva Aparecida. "Caracterização de Ferroporfirinas através das técnicas de ressonância paramagnética eletrônica (EPR) e absorção eletrônica na região do ultravioleta-visível (UV-Vis)." Universidade de São Paulo, 1999. http://www.teses.usp.br/teses/disponiveis/76/76132/tde-21022014-172954/.
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As ferroporfirinas sintéticas são sistemas complexos que vêm sendo amplamente estudadas. A dificuldade em obter informações estruturais, reações químicas e ligantes do íon central vêm estimulando o estudo pormenorizado desses sistemas. Nestes trabalho é apresentada a caracterização da série de FeP fluorosubstituídas, que compreende as mono-, di-, tri e tetra- fluorofenilporfirina, denominadas FeTF5PP, FeTF10PP, FeTF15PP e FeTF20PP, respectivamente. Essas FeP são estudadas em função dos solventes diclorometano (DCM), metanol (MeOH) e das várias misturas em volume desses dois. As técnicas espectroscópicas de Absorção Eletrônica na região do Ultravioleta ao Visível (UV-Vis) e Ressonância Paramagnética Eletrônica (EPR) são as duas ferramentas de estudos escolhidas para caracterizar esses sistemas. Partindo-se de uma solução de FeP dissolvida em DCM, foram adicionadas alíquotas de Me0H até completar-se 50% em volume desses dois solventes. Através dessa titulação, observamos a formação de diferentes espécies como conseqüência da coordenação do Me0H à FeP. Notamos também, as modificações estruturais reveladas principalmente pelo EPR, ocasionadas pelos diferentes números de substituintes fluorofenis. Essa técnica espectroscópica revelou ainda a existência de interações que não foram anteriormente observadas. Para a FeTFloPP foi verificada a interação super hiperfina entre o Fe e o ligante CF além da interação super hiperfina entre o Fe e os nitrogênios do anel porfirínico. Para a FeTF20PP foi verificada apenas a interação super hipeOna entre o Fe e o ligante Cl-. As demais FeP não apresentaram essas interaçõesSynthetic iron porphyrins are complex systems that have been largely studied. Difficulties to obtain structural information, chemical reactions and ligands of the central ions have been a subject to investigate details of these systems. In this work, a systematic characterization of one series of fluorophenyl iron porphyrins is presented. Mono-, di-, tri- and tetrafluorophenyl substituents called FeTF5PP, FeTF10PP, FeTF15PP, and FeTF20PP, respectively, are included in this series. Iron porphyrins were studied as a function of dichloromethane, methanol solvents and several of their mixture in volume. These systems were characterized by Ultraviolet- Visible and Electron Paramagnetic Resonance Spectroscopes. From iron porphyrin solutions, dissolved in dichloromethane, aliquots of methanol were added up to 50% in volume of these two solvents. With this titration, we found different species because of the methanol coordination to the iron porphyrins. We also observed the structures modification revealed by the EPR spectroscopy, as a function of different numbers of fluorophenyl substituents. The EPR spectroscopy also revealed the existence of the super hyperfine interactions not observed before. It was found for FeTFloPP between the central ion and the axial ligand chlorine Cl - ion, besides the hyperfine interaction between iron and the nitrogen of the pyrrole ring. For FeTF20PP only the super hyperfine interaction, Fe-C1 was found. These interactions were not observed for the other iron porphyrins
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Takara, Marcelo. "Propriedades ópticas de absorção e emissão fluorescente do ácido orto-aminobenzóico e seus derivados em meio solvente." Universidade de São Paulo, 2006. http://www.teses.usp.br/teses/disponiveis/59/59135/tde-20042010-171410/.
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Nesta tese, apresentamos estudos experimentais e teóricos realizados com o Ácido orto-Aminobenzóico (o-Abz) e seus derivados 2-amino-benzamida (o-Abz-NH2), 2-amino-metil-benzamida (o-Abz-NH(CH3)) e 2-amino -dimetilbenzamida (o-Abz-N(CH3)2). Foram feitas medidas de absorção óptica, fluorescência estática e resolvida no tempo e anisotropia de fluorescência em solventes com diferentes graus de polaridade e diferentes capacidades de doar e aceitar prótons. Os resultados experimentais foram comparados aos resultados de simulações computacionais que simularam o sistema solventesoluto. Restrições impostas pelas limitações computacionais impedem cálculos totalmente quânticos via métodos ab-initio, porém uma metodologia que tem apresentado resultados satisfatórios é o método híbrido que envolve a mecânica quântica associada à mecânica molecular (QM/MM). No presente trabalho, foram combinados cálculos quânticos ab-initio e semi-empíricos na otimização de geometrias de moléculas isoladas e no cálculo de energias de transições respectivamente. Foram simulados os sistemas soluto+solvente via Método de Monte Carlo. Os espectros de absorção ótica obtidos via simulação demonstraram boa concordância com os resultados experimentais, identificando-se as bandas como oriundas das transições p-p*. Verificamos que a forma ácida aniônica do o-Abz é responsável pelo deslocamento para o azul, observado em solvente aquoso. A forma aniônica incrementa a eletronegatividade dos átomos de Oxigênio, aumentando a energia das ligações de hidrogênio. Essas ligações mais intensas estabilizam o estado excitado do o- Abz, e isso se reflete no deslocamento para azul. Da simulação, verificou-se também que na forma aniônica há uma inibição das ligações de hidrogênio do tipo doadoras por parte do grupo amina. Os derivados do o-Abz apresentam aumento na capacidade do grupo amina atuar como doador em ligações de hidrogênio e diminuição na soma de todas as ligações de hidrogênio entre soluto-solvente. Os derivados amida e monometilamida mantiveram elevado rendimento quântico e sensibilidade à polaridade ambiente. Por outro lado, o derivado o-Abz-N(CH3)2 mostra sensibilidade à presença de metilas que incrementam as vias de desexcitação não radiativa.In the present, we report experimental and theoretical studies on orthoaminobenzoic acid (o-Abz) and its derivatives 2 amino-benzamide (o-Abz-NH2), 2 amino-monomethyl-benzamide (o-Abz-NH(CH3)) and 2 amino-dimethyl-benzamide (o-Abz-N(CH3)2. We measured optical absorption, steady state and time-resolved fluorescence and fluorescence anisotropy of the compounds in solvents with different donor/acceptor character. The experimental results were compared with results of computational calculations which simulated solvent-solute systems. Due to the restrictions imposed by the computer limitations, it was not possible to do entire quantum calculations by ab-initio methods. We used then QM/MM methods, which involves quantum calculation with molecular mechanics simulations. In this work, ab-initio and semi-empiric quantum calculations were combined in the single molecule geometry optimization and energy transitions calculus, respectively. The solute-solvent system was simulated by Monte Carlo method. The optical absorption spectra obtained from simulations showed good agreement with experimental results, identifying the bands relative to p-p* transitions. It was observed that the anionic acid form of the o-Abz is responsible for the blue shift when it is in aqueous solution. Anionic form increases the electronegativity of Oxygen atoms, rising the energy of the hidrogen bonds. These strong bonds stabilize the fundamental state of o-Abz, resulting in a blue shift in absorption spetrum. From simulation, it was verified that in the anionic form of o-Abz there is also an inhibition of hidrogen bonds of the donor type by the amine group. Compared to o-Abz alone, the derivatives present an increase in the amine group capacity to act as a hidrogen bond donor. The o-Abz-NH2 and o-Abz- NH(CH3) derivatives preserved the high quantum yield and the sensitivity for the environment polarity, while in the dimethyl amide derivative, the presence of methyl groups increases the deexcitation by non-radiactive pathways.
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Gulses, Alkan Ali. "Ellipsometric And Uv-vis Transmittance Analysis Of Amorphous Silicon Carbide Thin Films." Master's thesis, METU, 2004. http://etd.lib.metu.edu.tr/upload/12605589/index.pdf.
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The fundamentals of the ellipsometry are reviewed in order to point out the strengths and weaknesses of the ellipsometric measurements. The effects of the surface conditions (such as degree of cleanliness, contaminated thin layer, roughness etc&hellip) on the ellipsometric variables are experimentally studied
the optimum procedures have been determined. Hydrogenated amorphous silicon carbide (a-Si1-xCx:H) thin films are produced by plasma enhanced chemical vapor deposition (PECVD) technique with a circular reactor, in a way that RF power and carbon contents are taken as variables. These samples are analyzed using multiple angle of incidence ellipsometer and uv-vis spectrometer. These measurements have inhomogeneities in optical constants, such as thicknesses, refractive indices and optical energy gaps along the radial direction of the reactor electrode for different power and carbon contents.
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Sátorová, Kateřina. "Optimalizace stanovení rozdělení tenzidu při fázové separaci v systému polymer-tenzid." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2015. http://www.nusl.cz/ntk/nusl-217116.
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This diploma thesis is focused on the determination of distribution a surfactant at phase separation in polymer-surfactant system. Sodium hyaluronate of three molecular weights was chosen as a polymer, CTAB was used as a surfactant. The experiments were performed in an environment of 0,15 M NaCl. The measurement of the CTAB concentration in samples was based on the formation of coloured complexes of CTAB and picric acid in chloroform. UV-VIS spectroscopy was used for the detection of these complexes. The content of CTAB was determined in four gels of different composition (2% Hya + 200 mM CTAB, 2 % Hya + 50 mM CTAB, 0,5 % Hya + 200 mM CTAB, 0,5 % Hya + 50 mM CTAB). All gels were gradually washed five times with 0,15 M NaCl. The content of CTAB was determined for newly prepared gels and for gels after 2 and 4 months since the preparation. Initial concentrations of CTAB and hyaluronan have greater influence on the distribution of CTAB after phase separation, than the molecular weight of hyaluronan. The content of CTAB in newly prepared gels and after 4 months since preparation is very similar and demonstrates the stability of the system.
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Templeton, John Andrew. "Magnetite Oxidation in Aqueous Systems." Thesis, Virginia Tech, 2008. http://hdl.handle.net/10919/43468.
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Magnetite, an iron oxide, is a possible candidate for in situ remediation of contaminated groundwater systems due to its oxidation/reduction potential for reduction of contaminants such as carbon tetrachloride. Little characterization and analysis has been done to describe the kinetics of magnetite transformation during oxidation. This work focuses on monitoring the concentrations of magnetite and one of its oxidation transformation products, maghemite, by the use of UV-Vis-NIR spectroscopy. As oxidation proceeded at a constant specific temperature, the concentration of magnetite decreases, which was indicated by a decrease in absorption in the NIR-region of the spectrum. As magnetite concentrations decreased, the concentration of maghemite increased, which was indicated by an increase in absorption in the UV-region. The temperature at which the suspensions of magnetite and maghemite were measured was of great importance for complete understanding of the magnetite transformation as seen by UV-Vis-NIR spectroscopy analysis. Higher measurement temperatures produced higher absorptivities of FeII-FeIII electron hopping transitions, while decreasing the absorptivity of FeIII-FeIII in the NIR and UV-regions respectively. Lower temperatures produced the opposite effects on the iron oxidesâ transitions. Higher temperature increased the rate of oxidation.Master of Science
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Williams, Elizabeth Mary. "Oxidation of human nitrosylhemoglobin monitored by UV-Vis and EPR Spectroscopies: detection of products and intermediates." Thesis, Montana State University, 2005. http://etd.lib.montana.edu/etd/2005/williams/WilliamsE0805.pdf.
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Šejnohová, Michaela. "Studium interakcí hyaluronan-tenzidy dialyzační technikou." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2014. http://www.nusl.cz/ntk/nusl-217017.
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This diploma thesis is concentrated on the interactions between polyelectrolyte (hyaluronan) and cationic surfactant (CTAB). The experiments were performed in an aqueous solution and in an environment of physiological ionic strength (0,15mmoldm-3 NaCl). The determination of the surfactant concentration in solutions was based on the formation of colored complexes of CTAB and picric acid in chloroform. The concentrations of surfactant were measured by UV-VIS spectroscopy. The stability of CTAB+HyA was examined by a dialysis method. The results showed that, regardless of the environment, the presence of HyA in solution reduces the number of free molecules of CTAB which can be determined in the sample. It has been proved that there is an interaction between HyA and surfactant and that CTAB has greater affinity for HyA then for the picric acid. The stability of CTAB+HyA was determined by dialysis of 120 hours. After that time, the concentrations of the retentate and permeate were settled. The results showed that in the membrane remains a certain amount of CTAB bounded to hyaluronan. The system can be suitable for the preparation of targeted carriers of biologically active substances.
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Tumová, Šárka. "Vliv fotochromního aditiva na optické a elektrické vlastnosti polymerních matric." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2017. http://www.nusl.cz/ntk/nusl-316197.
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This thesis is focused on the photochromic molecule of spiropyran, which changes its structure as well as physical and chemical properties after UV irradiation. These changes are reversible, the molecule thermally restore its initial structure. For the study, the molecule SP1 with the systematic name 1',3'-dihydro-1',3',3'-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2'-(2H)-indole] was used. This molecule was incorporated within polymers PVK, Tg PPV, PCBTDPP and PCDTBT and the method of UV-VIS spectroscopy was used to observe the photochromic activity within these matrices. The influence of matrices to the ability to undergo UV induced photochromic conversion as well as to the reverse conversion to the initial structure induced by heat was monitored. Furthermore, the influence of spiropyran to the electrical properties of individual matrices was studied. The effect of photochromic conversion to both, the mobility of charge carriers and to the photogeneration was observed. For this purpose, the method of current-voltage measurement was used.
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Lambert, Alexander S. "Application of UV-Vis Spectroscopy to the Monitoring, Characterization and Analysis of Chemical Equilibria of Copper Etching Baths." Thesis, University of North Texas, 2017. https://digital.library.unt.edu/ark:/67531/metadc1011880/.
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The continuously increasing demand for innovation in the miniaturization of microelectronics has driven the need for ever more precise fabrication strategies for device packaging, especially for printed circuit boards (PCBs). Subtractive copper etching is a fundamental step in the fabrication process, requiring very precise control of etch rate and etch factor. Changes in the etching chemical equilibrium have significant effects on etching behavior, and CuCl2 / HCl etching baths are typically monitored with several parameters including oxidation-reduction potential, conductivity, and specific gravity. However, the etch rate and etch factor can be difficult to control even under strict engineering controls of those monitoring parameters. The mechanism of acidic cupric chloride etching, regeneration and recovery is complex, and the current monitoring strategies can have difficulty controlling the interlocking chemical equilibria. A complimentary tool, thin-film UV-Vis spectroscopy, can be utilized to improve the current monitoring strategies, as UV-Vis is capable of identifying and predicting etching behavior that the current standard methodologies have difficulty predicting. Furthermore, as a chemically-sensitive probe, UV-Vis can investigate the complex changes to the chemical equilibrium and speciation of the etch bath, and can contribute overall to significant improvements in the control of the copper etching system in order to meet the demands of next-level design strategies.
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Anisur, Rahman. "PREDICTION OF FISH FRESHNESS USING UV-VISIBLE SPECTROSCOPY OF EYE FLUID." Kyoto University, 2015. http://hdl.handle.net/2433/202812.
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Kyoto University (京都大学)0048
新制・課程博士
博士(農学)
甲第19378号
農博第2148号
新制||農||1037(附属図書館)
学位論文||H28||N4958(農学部図書室)
32392
新制||農||1037
京都大学大学院農学研究科地域環境科学専攻
(主査)教授 近藤 直, 教授 飯田 訓久, 准教授 小川 雄一
学位規則第4条第1項該当
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Schutte, Carol Lynn. "Sol-gel coatings containing inorganic and organic compounds--studies using Rutherford backscattering spectrometry and UV-VIS spectroscopy." Thesis, Massachusetts Institute of Technology, 1990. http://hdl.handle.net/1721.1/13639.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1990.Vita.
Includes bibliographical references (leaves 135-139).
by Carol Lynn Schutte.
Ph.D.
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Gonçalves, Tássia de Souza. "Caracterização estrutural e espectroscópica de vidros fluorofosfatos dopados e co-dopados com Er3+ e Yb3+." Universidade de São Paulo, 2014. http://www.teses.usp.br/teses/disponiveis/18/18158/tde-18082014-150349/.
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Atualmente, vidros e vitrocerâmicas dopados com íons terras raras trivalentes TR3+ constituem a mais importante classe de materiais para aplicações laser e em outros dispositivos ópticos, na região do infravermelho próximo e visível. Neste contexto, um dos desafios está em encontrar uma matriz hospedeira adequada que assegure qualidade óptica e um ótimo desempenho dos íons dopantes (altas seções de choque de absorção e emissão, baixa probabilidade de decaimentos não radiativos, tempos de vida de estado excitado suficientemente longos), mantendo estabilidade térmica e mecânica. Entre os possíveis candidatos, estão os vidros fosfatos com alta capacidade de dispersão dos dopantes, baixo índice de refração e propriedades termo-ópticas superiores aos silicatos, calcogenetos e fluoretos. Contudo, estes vidros apresentam alta energia de fônons, menor estabilidade química e mecânica e são higroscópicos, o que pode constituir um significativo mecanismo de supressão da luminescência devido ao acoplamento de transições dos TR3+ com vibrações de grupos hidroxila. Se por um lado vidros fluoretos podem ser obtidos com baixas energias de fônon e alta estabilidade química, os mesmos são mecanicamente frágeis e apresentam más características termo-ópticas. Para superar estas limitações, vidros oxifluoretos como fluorofosfatos têm sido explorados com a promessa de combinar os méritos dos fluoretos (baixas energias de fônon, baixos índices de refração, extensa janela de transmissão óptica) e dos óxidos (alta estabilidade química e resistência mecânica, maior solubilidade dos TR3+). Do ponto de vista das aplicações, considerando a transmissão e amplificação de sinais em telecomunicação em torno de 1,5 µm, e geração de ação laser de alta potência em torno de 1,0 µm, materiais dopados com Er3+ e Yb3+ estão entre os mais importantes. Neste trabalho apresenta-se a síntese e caracterização estrutural e espectroscópica de novos vidros fluorofosfatos dopados com Er3+ ou Yb3+ e co-dopados com ambos, no sistema composicional 25BaF225SrF2(30-x)Al(PO3)3xAlF3 (20-z)YF3:zTRF3 com x = 20 ou 15, TR = Er3+ e/ou Yb3+ e z = 0,25, 0,5, 1,0, 2,0, 3,0, 4,0 e 5,0 mol%. As amostras foram obtidas pelo método convencional de fusão e resfriamento e caracterizadas por Raman, Ressonância Magnética Nuclear de estado sólido e espectroscopia UV-VIS. Dos estudos por RMN de 19F verificou-se que há uma perda máxima de fluoreto de ~20% nas amostras. Ainda assim, a quantidade remanescente foi suficiente para garantir um ambiente químico favorável às emissões e poucas diferenças foram notadas entre as amostras com 20 e 15 mol% AlF3 contendo a mesma concentração de dopantes. Para o Er3+, tempos de vida do estado emissor 4I13/2 da ordem de 10 ms implicam em altos valores de eficiência quântica (η= 85%) e para o Yb3+ tempos de vida do estado emissor 2F5/2 similarmente longos (τ = 1,7 ms) foram medidos. Em amostras co-dopadas com 4,0 mol% YbF3 e 0,25, 1,0 e 2,0 mol% ErF3 o decréscimo do tempo de vida do Yb3+ e acréscimo do tempo de vida do Er3+ indicam que a transferência Yb→Er foi eficiente neste sistema. De maneira geral, os resultados indicam que os vidros estudados são potenciais candidatos a aplicações ópticas como as mencionadas acima.Currently, glasses and glass ceramics doped with trivalent rare earth ions RE3+ represent the most important class of materials for laser and other optical applications in the visible and near-infrared spectral regions. In this context, one of the challenges is to find host matrices that assure good optical quality and optimum performance of the dopant ions (high absorption and emission cross sections, low probability of non-radiative decays, sufficiently long excited state lifetimes), while still maintaining thermal and mechanical stabilities. Among the candidates, phosphate glasses with high capacity for RE3+ dispersion, low refractive index and superior thermo-optical properties than silicate, chalcogenide and fluoride glasses are largely studied. However, phosphates present high phonon energies, lower chemical and mechanical stabilities and they are hygroscopic, which can imply in significant luminescence quenching effects. If on one hand fluoride glasses may be designed with low phonon energies and higher chemical stability, they are frail and present less than ideal thermo-optical properties. In order to overcome these drawbacks, oxyfluoride glasses such as fluorophosphates have been explored with the promise to combine the merits of fluorides (low phonon energies and refractive index, extensive optical window) and of oxides (high chemical stability and chemical resistance, higher solubility of RE3+). From the viewpoint of applications, when it comes to the transmission and amplification of signal in telecommunications around 1.5 µm, and the generation of high power lasers around 1.0 µm, materials doped with Er3+ and Yb3+ are among the favorite. Furthermore, because Yb3+ presents higher absorption cross-section than Er3+ at the preferred excitation wavelength for both these ions (980 nm), the former can act as an efficient sensitizer of excitation energy with subsequent transfer to the latter. We present the synthesis, and structural and spectroscopic characterization of new flurophosphate glasses doped with Er3+ or Yb3+ and co-doped with both, in the compositional system 25BaF225SrF2(30x)Al(PO3)3 xAlF3 (20- z)YF3:zREF3 with x = 20 or 15, RE = Er3+ and/or Yb3+ and z = 0.25, 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0 mol%. The samples were obtained by conventional melt quenching technique and characterized by Raman, solid state NMR and UV-VIS spectroscopy. From the NMR studies of 19F, it was shown that there is a maximum fluoride loss of 20% in the samples. Even so, the remaining quantity was enough to assure a favorable chemical environment to the RE3+ emissions. Little differences were detected between the samples with 20 and 15 mol% AlF3 for the same dopant concentration. For Er3+, lifetimes of the emitting level 4I13/2 of the order of 10 ms result in fluorescence quantum efficiency values (η = 85%), and similarly, for Yb3+, long lifetimes of the excited state 2F5/2 (τ = 1,7 ms) were measured. In co-doped samples with 4.0 mol% YbF3 and 0.25, 1.0 and 2.0 mol% ErF3 the decrease in lifetime of Yb3+ and increase in lifetime of Er3+ indicate that the Yb→Er energy transfer is efficient in this system. In general, the results indicate that the studied glasses are potential candidates for optical applications.
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Gonçalves, Tássia de Souza. "Rare earth doped fluorophosphate glass and glass-ceramics: structure-property relations." Universidade de São Paulo, 2018. http://www.teses.usp.br/teses/disponiveis/18/18158/tde-30102018-100600/.
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Rare earth RE3+ doped fluorophosphates glasses and glass ceramics are among the most promising candidates for high efficiency laser generation in the near-infrared spectral region. Glass ceramics are polycrystalline materials of fine microstructure that are produced by the controlled crystallization (devitrification) of a glass. By developing fluorophosphate base glasses with appropriate compositions and by controlling crystal nucleation and growth in them, glass ceramics with special properties can be fabricated combining the advantages of fluorides (low phonon energy, low refractive indexes, extensive optical window, lower hygroscopicity) and oxides (high chemical and mechanical stability and high dopant solubility), resulting in enhancement of the RE3+ emissive properties. In this study, we present the synthesis by melting/quenting and structural/spectroscopic investigation of new glasses and glass ceramics with composition 25BaF225SrF2(30-x)Al(PO3)3xAlF3(20-z)YF3: zREF3, where x = 15, 20 or 25, RE = Er3+ an/or Yb3+ and Nd3+. A detailed structural investigation of a series of this glasses has been conducted, using Raman, solid-state nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies.Vidros e vitrocerâmicas fluorofosfatos dopados com íons terras raras (TR3+) estão entre os candidatos mais promissores para a geração de laser de alta eficiência na região espectral do infravermelho próximo. As vitrocerâmicas são materiais policristalinos com microestrutura bem definida obtida a partir da cristalização controlada do vidro base. Desenvolvendo vidros base de fluorofosfato com composições apropriadas e controlando a nucleação e crescimento de cristais, vitrocerâmicas com propriedades especiais podem ser fabricadas combinando as vantagens dos fluoretos (baixa energia de fônons, baixos índices de refração, janela ótica extensa, baixa higroscopicidade) e óxidos (alta estabilidade química e mecânica e alta solubilidade dopante), resultando no aumento das propriedades emissoras dos íons TR3+. Neste estudo, apresentamos a síntese por fusão/resfriamento e investigação estrutural/espectroscópica de novos vidros e vitrocerâmicas com composição 25BaF225SrF2(30-x)Al(PO3)3xAlF3(20-z)YF3: zREF3, onde x = 15, 20 ou 25, RE = Er3+ an / ou Yb3+ e Nd3+. Uma investigação estrutural detalhada de uma série destes vidros foi conduzida utilizando espectroscopias Raman, de ressonância magnética nuclear de estado sólido (RMN) e de ressonância paramagnética eletrônica (EPR).
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Bradshaw, John Thomas. "BROADBAND COUPLING INTO SINGLE MODE, PLANAR INTEGRATED OPTICAL WAVEGUIDE STRUCTURES FOR SPECTRAL ANALYSIS OF THIN FILM ANALYTES AND INTERFACIAL CHEMICAL ENVIRONMENTS." Diss., Tucson, Arizona : University of Arizona, 2005. http://etd.library.arizona.edu/etd/GetFileServlet?file=file:///data1/pdf/etd/azu%5Fetd%5F1144%5F1%5Fm.pdf&type=application/pdf.
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May, John. "Investigating the binding mode of azide labelled derivatives of Hoechst 33258 by NMR, UV-Vis and IR spectroscopy." Thesis, University of Strathclyde, 2016. http://digitool.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=27859.
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This thesis describes attempts to develop a method for studying the dynamics of dsDNA: small molecule ligand association and dissociation through 2D-IR spectroscopy. The strategy employed was to synthesise azide-bearing derivatives of the archetypal minor groove binding ligand, Hoechst 33258, with the azide acting as a reporter functional group. Chapter 1 describes both the state of the art, and also what is unknown regarding the processes of association and dissociation of small molecules from dsDNA, and how this project aims to gain a fuller understanding of the dynamics of association between dsDNA and a smallmolecule MGB. The clinical significance of minor groove binders is also discussed. Chapter 2 describes the synthesis of two azide-bearing derivatives of H33258 through an amide coupling strategy, and the significant problems encountered with the purification of these compounds. Future alternative pathways to these compounds are proposed. An investigation into the spectroscopic properties of the azide functional groups in the free compounds is also presented. Chapter 3 describes the investigation of the utility of the azide functional group through a comparative study of the thermal dissociation of these compounds from dsDNA. It was found that the utility of the azide was dependent on the position of the azide within the molecule, and is sensitive to the changes in solvation of the minor groove of dsDNA. One compound in particular exhibited a marked change in both the shape and the intensity of the azide absorptionband and was commensurate with the melting temperature, Tm of the complex. Chapter 4 describes the investigation into the structural origins of the marked difference in the azide absorption band of one MGB when in complex with a dsDNA oligomer through structural characterization of this complex by NMR spectroscopy. It was found that the azidefunctional group is in close proximity to the exocyclic amine of guanosine, and this specificinteraction is proposed to give rise to the observed changes in the azide absorption band. The orientation of the molecule was found to be opposite to that reported for H33258, a reason why this is the case is also proposed.
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Aritani, Hirofumi. "Characterization of Active Species in Molybdenum-and Copper-Based Catalysts by Means of XAFS and UV-VIS Spectroscopy." Kyoto University, 1996. http://hdl.handle.net/2433/77836.
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Rodrigues, Matthew. "An investigation into the catalytic mechanism of vitamin B6 biosynthesis using X-ray crystallography and UV-Vis spectroscopy." Thesis, University of Southampton, 2017. https://eprints.soton.ac.uk/405821/.
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The catalytic mechanism of the Pdx1 subunit of the pyridoxal 5’-phosphate (PLP) syn-thase enzyme complex has been the subject of intense study since its discovery in 1999. Pdx1 uses two active sites (P1 and P2) to perform a complex reaction combining ribose 5-phosphate, ammonia and glyceraldehyde 3-phosphate to form PLP. While some aspects of the Pdx1 mechanism are now understood, several questions re-main, in particular how the enzyme transfers the reaction from one active site to the next and how the reactions in the two sites are coordinated. In this investigation, X-ray crystallography and UV-Vis spectrophotometry have been used to determine the struc-ture of the protein in various intermediate states and elucidate the catalytic mechanism. The role of specific active site residues in catalysis of PLP biosynthesis by the Arabidop-sis thaliana Pdx1 protein is investigated using site-directed mutagenesis. The crystal structures presented in this thesis demonstrate that the Pdx1 enzyme uses a novel relay mechanism to covalently transfer intermediates between active sites and to coordinate substrate binding, intermediate shuttling and catalysis. Chapter 1 provides an introduction to the biological role of pyridoxal 5’-phosphate and its biosynthesis by the PLP synthase enzyme complex. Chapter 1 also describes the use of X-ray crystallography to understand how proteins function and how complementary methods such as UV-Vis spectrophotometry can be used to track the effects of site-specific radiation damage during collection of X-ray diffraction data. The methods used to produce, purify and investigate the Pdx1 enzyme are described in Chapter 2. Chapter 3 provides an analysis of the activity of wild type AtPdx1.3 using UV-Vis spectropho-tometry and X-ray crystallography to monitor the accumulation of chromophoric inter-mediates and the product, PLP. Chapter 4 describes the use of site-directed mutagenesis to trap the Pdx1 protein in additional intermediate states and the characterisation of these intermediate states using UV-Vis spectroscopy and crystallography. UV-Vis spectra of Pdx1 crystals were collected to ensure that the Pdx1 enzyme was in the desired intermediate state before collection of X-ray diffraction data. It became clear that the UV-Vis spectra of the Pdx1 crystals in some intermediate states were changing during X-ray data collection. Chapter 5 describes the experiments that were performed to check that the Pdx1 structures obtained were not affected by site-specific radiation damage. The use of multi-crystal data collection strategies and UV-Vis spectroscopy showed that changes in the spectra were instead caused by radiolysis of the solvent surrounding the crystals.
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Holland, Torrey. "VIBRATIONAL SPECTROSCOPY ANALYSES OF THE DEGRADATION AND CONTAMINATION OF ENGINE OIL LUBRICANTS COUPLED WITH MULTIPLE SPECTROSCOPIC TECHNIQUES." OpenSIUC, 2018. https://opensiuc.lib.siu.edu/theses/2399.
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The spectral analysis techniques afforded us from the field of physics has enabled us to explore the spectral signatures of trace contaminants and degradation products in used or in service engine oil through atomic and molecular spectroscopy. Here we have examined the need to address proper preparation of calibrating samples for infrared spectroscopy analysis by inducing emulsification and have evaluated multiple procedures for proper emulsification of samples with the intent to help establish the protocols that are not explicitly set forth in the ASTM International standard. We have also explored the use of Fourier-transform infrared spectroscopy techniques to examine the suppression of the O–H stretching mode of water due to the influence of ethylene glycol, which may help in the quantification of water when both are present in oil. This was done in conjunction with exploring alternative methods for direct and indirect measurement of the glycol contamination by use of UV/Vis spectroscopy, Raman, and laser-induced breakdown spectroscopy. An exploration of FT-IR and UV/Vis data on the oxidation of oil by means of ANOVA calculations has led to the reporting of highly significant differences in the data of differing oxidation times and in regions of the spectrum not known to have been previously reported.
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Gueneau, Basile. "Etude et utilisation de complexes polypyridiniques du cuivre (II) dans le cadre de la catalyse de la délignification des pâtes papetières." Thesis, Grenoble, 2012. http://www.theses.fr/2012GRENV023.
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L’utilisation de dioxygène lors de la délignification des pâtes à papier permet une réduction considérable des coûts de production et de l’impact environnemental du procédé de blanchiment. Seulement, le taux de délignification est limité par le fait qu’une partie de la lignine résiduelle n’est pas réactive vis-à-vis du dioxygène et que la cellulose est partiellement dépolymérisée au cours du procédé. L’utilisation de catalyseur pourrait permettre d’améliorer l’efficacité et la sélectivité de la délignification au dioxygène comme le suggèrent certaines études. Le complexe cuivre(II)-phénanthroline présente des résultats prometteurs en termes d’efficacité, mais entraîne une dégradation importante de la cellulose. Différents ligands polypyridiniques ont été étudiés dans ces travaux, afin de trouver un complexe du cuivre(II) présentant une affinité forte vis-à-vis de la lignine et faible vis-à-vis de la cellulose. Les complexes formés ont été caractérisés par spectroscopie UV/Vis et voltammétrie cyclique et étudiés comme catalyseurs de l’oxydation de différents substrats : un composé modèle de lignine non phénolique et des substrats lignocellulosiques (un modèle de cellulose, un modèle de lignine native et une pâte kraft industrielle). Les résultats ont montré que la nature même du ligand a un effet important sur l’activité catalytique du complexe de Cuivre (II) lors de l’oxydation du composé modèle de lignine. En revanche, les complexes actifs présentent une activité faible lors de la délignification d’une pâte kraft et oxydent fortement les hydrates de carbone. Ce manque de sélectivité ne permet pas une application pour la production de pâte à papier mais oriente l’utilisation de ce type de catalyseur dans de nouvelles applications n’ayant pas les mêmes contraintes sur le degré de polymérisation de la celluloseDioxygen delignification considerably reduces the operating cost of the bleaching process and decreases the environmental impact of the bleaching effluent. Unfortunately the performance of dioxygen delignification is limited since part of the residual lignin is not reactive toward dioxygen while cellulose depolymerisation occurs. Studies suggested that dioxygen delignification could be improved thanks to the use of catalysts such as copper(II)–phenanthroline type complexes which have shown promising results on delignification efficiency. However cellulose was also more degraded. Different polypyridinyl ligands have been studied in this work, in an attempt to find copper(II) complexes that have more affinity toward lignin and less toward cellulose. Complexes have been characterised by UV/Vis spectroscopy, cyclic volammetry, and they were studied for the catalysed oxidation of various substrates: a non phenolic lignin model compound and lignocellulosic substrates (a model of cellulose, a model of native lignin and an industrial kraft pulp). It has been shown that the nature of the ligand had a significant effect on the catalytic activity of Cu(II) complexes in the oxygen oxidation of the lignin model compound. However, the active complexes only show a limited activity during the delignification of a kraft pulp and oxidize carbohydrates. This lack of selectivity prevents from an industrial application for paper pulp production but may be useful for the design of products with fewer constraints on cellulose polymerization degree
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Rouxinol, Maria Inês Silva Caçador Pereira. "Determinação das principais antocianinas em castas tintas no Alentejo." Master's thesis, Universidade de Évora, 2016. http://hdl.handle.net/10174/20869.
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Os compostos fenólicos (incluindo as antocianinas) estão presentes no vinho e possuem
atividade antioxidante relevante, protegendo as células contra processos oxidativos, podendo
ser importantes na prevenção de doenças cardiovasculares, neurodegenerativas e
cancerígenas, entre outras.
O objetivo deste trabalho é a avaliação da composição em antocianinas em castas de uvas
tintas desde ao pintor até ao final da maturação. As antocianinas foram quantificadas por
HPLC. Adicionalmente o conteúdo total em compostos fenólicos foi determinado por
espectrometria UV-Vis. Observou-se nos resultados de todas as análises efetuadas um
padrão repetido e consistente de evolução dos compostos em estudo.
Foi ainda testado neste trabalho a quantificação das antocianinas totais, de malvidina-3-
glucósido e dos compostos fenólicos totais através de um método espectroscópico baseado
no espectro de absorção da zona UV. Embora a calibração deste método não tenha
apresentado valores muito robustos, poderá no futuro ser utilizada como método alternativo
rápido para a quantificação de antocianinas e compostos fenólicos; Abstract:
«Quantification of Anthocyanins in Red Wine Grapes in Alentejo»
Phenolic Compounds (including anthocyanins) are present in wine and possess significant
antioxidant activity, protecting cells against oxidative processes, and preventing prevent
cardiovascular, neurodegenerative and cancer diseases, among others.
The aim of this study is the evaluation of the anthocyanins composition in red wine grapes
from the verásion until the end of ripening. Anthocyanins were quantified by HPLC.
Additionally the total content of phenolic compounds was determined by UV-Vis
spectrometry. It was possible to verify in all tests that the results have a consistent evolution
pattern considering different tested compounds.
Anthocyanins, malvidin-3-glucoside and phenolic compounds were also quantified by a
spectroscopic method based on the UV absorption spectrum. Although the calibration of this
method has not presented very sturdy values, it should be improved in the future and used as
an alternative method for rapid quantification of anthocyanins and phenolic content.
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Lenartová, Radka. "Solubilizační schopnosti polysacharidů." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2008. http://www.nusl.cz/ntk/nusl-216402.
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In this diploma thesis were studied solubilization properties of polysaccharides by using hydrophobic solutes (Sudan Orange G, Sudan Red G, (±)-alpha-Tocopherol, Pyrene, Perylene, Nile red), which were represented by alkyl derivates of hyaluronan. At first, a behaviour of individual hydrophobic solutes was investigated in variously polar solvents (Methanol, 1 Propanol, Chloroforme, Cyklohexane, n Heptane) and in the environment of varying ionic strength (water, 0.1 M and 0.4 M NaCl). Afterwards, solubilization properties of Sodium Dodecyl Sulfate model solubilizated the hydrophobic solutes into a core of micelles was examinate. We were interested in the solubilization capacity as the mol of solubilized molecules per mol micelles of surfactant corresponding with a state of micelles saturation. In the case of the solubilization of (±)-alpha-Tocopherol into the core of micelles, it was not possible to determine the solubilization capacity. So we changed the determination of universally solubilization power. The solubilization power is defined as mol of molecules solubilized per mol surfactant relative to the quantity solubilizate at the micelles saturation. Model system of Sodium Dodecyl Sulfate as a simple surfactant carrying a negative charge as the alkyl derivates of hyaluronan was selected bacause of its characteristics.The surfactant forms unimolar micelles and its critical micelle concentrations and aggregation numbers are tabelated for the investigated microenvironment. The main aim of the study was investigating of hydrophobic domains of alkyl derivates of hyaluronan as free places for incorporation hydropbobic solutes in the microenvironment of varying ionic strength. The critical aggregation concentrations were determined by the Pyrene 1:3 ratio method. For the research of micropolarity of alkyl derivates hyaluronan’s domains were selected two concentrations of derivates for the next research of solubilization experiments - the first concentration near the critical aggregation concentration and the second concentration above it. The effect of concentration of Pyrene on a core polarity of derivates was investigated. We discovered the influence of the concentration and the other we found a stationary area of the concentration. In the end we investigated the influence of preparation of solutions of derivates of hyaluronan on the core polarity by the concentration of pyrene which corresponds to the stationary area. The study of solubilization properties of alkyl derivates of hyaluronan is not a simple case as we assumed. When we measured spectra of the absorbance, higher concentration of derivates of hyaluronan belittle absorbance of solubilizates. At the experiment of solubilization with Sudan Red G we found out that Sudan Red G is not able to solubilizate into the hydrophobic core of micelles of hyaluronan’s derivates because of lipophilic or steric effects. We had to change Perylene as a new solubilizate. From the measured emission spectra we found saturation micelles. We can express the solubilization power of hyaluronan’s derivates for the concentration of Perylene. The main aim of the diploma thesis was to determine optimal way of the preparation of hyaluronan’s derivates solutions with required degree of solubilization.
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Bauer, Matthias. "Investigations of alkoxide precursor solutions and homogeneous catalyzed reactions by X-ray absorption and multi dimensional spectroscopy." Berlin mbv, Mensch-und-Buch-Verl, 2008. http://d-nb.info/995894655/04.
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Postal, Victor. "Estudo da degradação térmica de emulsões via espectroscopia UV-Vis aplicado a fluidos de corte." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/3/3137/tde-23012017-113619/.
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O monitoramento de emulsões utilizadas na indústria metalmecânica compõe uma importante atividade para o controle da qualidade das peças trabalhadas, proporcionando também o aumento da vida útil de ferramentas e maquinários utilizados neste setor através da lubrificação e refrigeração da região de corte. Em grande parte dos casos, estas emulsões são preparadas pela diluição de um fluido de corte em meio aquoso, constituindo assim um conjunto de gotículas estabilizadas em um meio contínuo devido à presença de compostos emulsificantes, estando constantemente sujeitas a ciclos de aquecimento e resfriamento durante os processos de usinagem. Apesar do acompanhamento deste material ser realizado através de análises periódicas usuais, não há um método eficiente estabelecido para verificar sua qualidade em tempo real e em linha de processo. Neste contexto, torna-se possível aplicar técnicas relacionadas à espectroscopia UV-Vis para se obterem informações sobre a estabilidade destes sistemas, correlacionando intensidades de espalhamento de luz com as dimensões das gotas presentes no meio. Dessa forma, tornou-se possível o estudo da desestabilização térmica de emulsões de um fluido de corte comercial, a qual mostrou-se, através do acompanhamento do cálculo do expoente do comprimento de onda, dependente do tempo de exposição ao aquecimento e de sua temperatura média temporal, não sendo influenciada pela perda de meio contínuo por processos evaporativos ou sua posterior reposição. Também se verificou que parâmetros típicos do processo de preparo de emulsões, como a temperatura do meio dispersante e o tempo de repouso do fluido de corte sobre a superfície do mesmo, apresentam fundamental importância para a definição do tamanho médio de gota inicial destes sistemas, o que forneceu evidência da possibilidade de se relacionar a área sob espectros de extinção de luz com tamanhos médios de gota.The monitoring of emulsions used in the metal-mechanical industry comprise an important activity to the quality control of the products manufectured, also providing an increase in the working life of the tools and machinery employed in this sector through the lubrication and refrigeration of the cutting zone. In the majority of cases, these emulsions are prepared diluting a metalworking fluid in an aqueous media, constituting a collection of particles stabilized by emulsifiers and undergoing heating and cooling cycles during metalworking processes. Currently, monitoring routines are based on regular analyses of samples taken from the process fluid, and an effective in-line method is not available to monitor emulsion quality in real time. In this context, it is possible to apply techniques related to UV-Vis spectrocopy in order to obtain information concerning the stability of those systems, correlating light scattering intensities to the droplet dimensions. In this study, it was possible to investigate the thermal destabilisation of a commercial metalworking fluid emulsion, which showed, through the evaluation of the wavelength exponent, to be dependant on the exposure time to heating and its time-averaged temperature. It was also noted that the loss of continuous phase by evaporation and its reposition do not affect the emulsion stability. Moreover, it was observed that important emulsion preparation parameters, such as continuous phase temperature and the time span between the addition of the metalworking fluid on the water surface and the stirring, have fundamental roles in defining the initial average droplet size, which made possible to correlate the area under the light extinction spectra with average droplet sizes.
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Gerlach, Daniela. "Neuartige höherkoordinierte Siliciumkomplexe mit Pyrrol-2-carbaldimin-Liganden." Doctoral thesis, Technische Universitaet Bergakademie Freiberg Universitaetsbibliothek "Georgius Agricola", 2013. http://nbn-resolving.de/urn:nbn:de:bsz:105-qucosa-104526.
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Im Rahmen dieser Arbeit wurden Siliciumkomplexe mit dianionischen Pyrrol-2-carbaldimin-funktionalisierten N,N,O- und N,N,N,N-Chelatliganden synthetisiert und kristallografisch, NMR- und UV/Vis-spektroskopisch und mittels quantenchemischer Berechnungen charakterisiert. Die pentakoordinierten Si-Komplexe mit N,N,O-Ligandrückgraten wiesen in Abhängigkeit von den weiteren Si-gebundenen Substituenten unterschiedlich konfigurierte verzerrt trigonal-bipyramidale Si-Koordinationssphären auf. Die Ursache der Farbigkeit dieser Verbindungen konnte mittels quantenchemischer Berechnungen detailliert erklärt werden. – Die Si-Komplexe mit N,N,N,N-Ligandrückgraten liegen in Abhängigkeit von den weiteren Si-gebundenen Substituenten als 5-fach koordinierte kationische oder neutrale 6-fach koordinierte Si-Komplexe vor. Deren Farbigkeit wurde mittels UV/VIS-Spektroskopie untersucht. Von ausgewählten Komplexen wurden die Tensoren der 29Si-NMR-Verschiebung rechnerisch und CP/MAS-NMR-spektroskopisch bestimmt.
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Franco, González Olga. "Structural and spectroscopical study of crystals of 1,3,4-oxadiazole derivatives at high pressure." Phd thesis, Universität Potsdam, 2002. http://opus.kobv.de/ubp/volltexte/2005/53/.
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Die Suche nach neuen Materialien von technischem Interesse hat in den letzten Jahren neue Antriebe zu der Untersuchung organischer Verbindungen gegeben. Organische Substanzen haben viele Vorteile wie z.B. die Möglichkeit, ihre Eigenschaften durch verschiedene chemische und physikalische Techniken im Herstellung-Prozess für ein bestimmtes Ziel zu modifizieren. Oxadiazolverbindungen sind interessant aufgrund ihrer Nutzung als Material für Licht emittierende Dioden und Scintillatoren. Die physikalischen Eigenschaften eines Festkörpers hängen von seiner Struktur ab. Unterschiedliche Strukturen entwickeln unterschiedliche intra- und intermolekülare Wechselwirkungen. Eine ausgezeichnete Weise, um sowohl die intra- als auch die intermolekularen Wechselwirkungen eines bestimmtes Stoffes zu beeinflussen, ohne seine chemischen Charakteristiken zu ändern, ist die Verwendung von hohem Druck.
Wir haben den Einfluss von hohem Druck und hoher Temperatur auf die super-molekulare Struktur einiger Oxadiazolverbindungen im kristallinem Zustand untersucht. Aus diesen Untersuchungsergebnissen wurde eine Zustandsgleichung für diese Kristalle bestimmt. Überdies wurden die spektroskopischen Eigenschaften dieser Materialien unter hohem Druck charakterisiert.
In recent years the search for new materials of technological interest has given new impulses to the study of organic compounds. Organic substances possess a great number of advantages such as the possibility to adjust their properties for a given purpose by different chemical and physical techniques in the preparation process. Oxadiazole derivatives are interesting due to their use as material for light emitting diodes (LED) as well as scintillators.
The physical properties of a solid depend on its structure. Different structures induce different intra- and intermolecular interactions. An advantageous method to modify the intra- as well as the intermolecular interactions of a given substance is the application of high pressure. Furthermore, using this method the chemical features of the compound are not influenced.
We have investigated the influence of high pressure and high temperature on the super-molecular structure of several oxadiazole derivatives in crystalline state. From the results of this investigation an equation of state for these crystals was determined. Furthermore, the spectroscopical features of these materials under high pressure were characterized.
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Solanský, Pavel. "Využití chromatografie na tenké vrstvě k frakcionaci a charakterizaci organické hmoty izolované z alginitu." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2021. http://www.nusl.cz/ntk/nusl-445143.
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This diploma thesis is focused on the study of structure and physicochemical properties of organic fractions of humic substances, which were obtained by the method of thin-layer chromatography. Humic substances, which were used in this study, were isolated from a sample of Slovak alginite based on the procedure of the International Humic Substances Society (IHSS). The following analytical techniques were selected for the characterization of isolated humic substances: thermogravimetric and elemental analysis, molecular absorption spectroscopy (UV/Vis), Fourier transform infrared spectroscopy (FTIR) and steady-state fluorescence spectroscopy. Each organic fraction of humic substances were characterized by molecular absorption spectroscopy (UV/Vis) and steady-state fluorescence spectroscopy. Using steady-state fluorescence spectroscopy, humic substances were found to be composed of fluorophores of humic and non-humic (protein) character. Organic fractions corresponding to the humic fluorophores were characterized by a higher content of oxygen substituents on the aromatic nukleus, a higher degree of aromaticity and also a higher molecular weight. The aim of this diploma thesis was to design and optimize the process of organic matter fractionation for the purpose of detailed understanding of the structure and properties of humic substances, which were isolated from the sedimentary rock alginite. Based on this, the practical applicability of the thin layer chromatography method to significantly reduce the molecular heterogenity of the studied humic substances was evaluated.
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Jiang, Yijiao. "Mechanistic studies of the methanol-to-olefin (MTO) process on acidic zeolite catalysts by in situ solid-state NMR-UV/Vis spectroscopy." Berlin Logos-Verl, 2007. http://deposit.d-nb.de/cgi-bin/dokserv?idn=987022326.
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Friebe, Nadine, Katja Schreiter, Joachim Kübel, Benjamin Dietzek, Norbert Moszner, Peter Burtscher, Alexander Oehlke, and Stefan Spange. "Fluorosolvatochromism of furanyl- and thiophenyl-substituted acetophenones." Universitätsbibliothek Chemnitz, 2016. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-197572.
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A series of para-substituted acetophenones bearing a furanyl or a thiophenyl moiety show a large Stokes-shift, which is a function of various solvent properties. Photophysical properties such as emission lifetime of the compounds have been determined using time-correlated-single photon counting to secure the intrinsic fluorescence behaviour. The solvent dependent position of the UV/Vis emission band [small nu, Greek, tilde]max,em of the compounds has been measured in 26 various solvents. The influence of the solvent on [small nu, Greek, tilde]max,em is of very complex nature and mathematically analysed by multiple square linear solvation energy (LSE)-correlation analysis using Catalán's four-solvent parameter set. Solvent acidity has a strong influence on the bathochromic shift of 2,5-disubstituted furan derivatives compared to the non-5-substituted furan and thiophene derivatives, which show a contrary behaviour. Therefore, the 5-cyanofuranyl-substituted acetophenone derivative is useful as a probe for measuring environmental properties by fluorescence spectroscopyDieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich
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Hendel, Thomas. "Synthese und Charakterisierung von Halbleiter- und Metall-Nanopartikeln und deren Selbstassemblierung in 3-dimensionale Netzwerkstrukturen." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät, 2016. http://dx.doi.org/10.18452/17571.
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Aus CdTe- und Edelmetallnanopartikeln werden 3-dimensionale Netzwerkstrukturen aufgebaut, welche durch einen überkritischen Trocknungsprozess zu hochporösen, weitverzweigten Halbleiter-Metall-Nanokompositen, sogenannten Aerogelen, umgewandelt werden. Zunächst werden Thiol-stabilisierte CdTe- und Edelmetallnanopartikel im wässrigen Milieu hergestellt und deren Morphologie und optischen Eigenschaften umfangreich mittels UV-Vis-Spektroskopie, Fluoreszenzspektroskopie und -lebensdauermessung, ICP-OES, TEM, STEM-EDX und AFM charakterisiert. Als Metallkomponente kamen Gold-, Palladium- sowie bimetallisch gemischte Gold-Palladium-Nanopartikel zum Einsatz. Die Gelierung der Nanopartikellösungen erfolgt durch Vermischen der Kolloide und anschließender kontrollierter Destabilisierung mithilfe einer Xe-Dampflampe oder der Zugabe von Wasserstoffperoxid. Neben einer mechanistischen Beschreibung der Gelbildungsmethoden wurden die resultierenden Hydrogele und die aus der überkritischen Trocknung erhaltenen Aerogele bezüglich Zusammensetzung, Morphologie und optischen Eigenschaften mithilfe von TEM und REM jeweils gekoppelt mit EDX-Analyse, Stickstoff-Porosimetrie, diffuser Reflexionsspektroskopie, Fluoreszenzspektroskopie und Fluoreszenzlebensdauermessungen untersucht. Weiterhin wird die UV-Vis-Spektroskopie als Methode zur Konzentrationsbestimmung von Gold in Lösungen kolloidaler Gold-Nanopartikel validiert. Dabei wird die Absorption der Kolloide bei einer Wellenlänge von 400 nm als Maß verwendet. Die NP-Lösungen werden anhand der Parameter Partikelgröße, Oberflächenfunktionalität und der Oxidationsstufe des enthaltenen Goldes variiert.3-dimensional network structures are formed combining CdTe and noble metal nanoparticles. A supercritical drying process allows production of highly porous and widely branched semiconductor-metal nanohybrids, so-called aerogels. Primarily, thiol-capped CdTe and noble metal nanoparticles are synthesized in aqueous media and their morphology and optical properties are studied extensively using UV-Vis and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, ICP-OES, TEM, STEM-EDX and AFM. The metal entity involves gold and palladium nanoparticles as well as bimetallic mixed Au/Pd nanoparticles. After mixing of the different colloids gelation is induced by a controlled destabilization process using a Xenon lamp irradiation or the addition of hydrogen peroxide. Gelation techniques are described mechanistically. Resulting hydrogels and aerogels which are obtained by supercritical drying approach are characterized concerning composition, morphology and optical properties using TEM and SEM each coupled with EDX, nitrogen porosimetry, diffuse reflection spectroscopy, fluorescence spectroscopy and time-resolved fluorescence spectroscopy. Moreover, the UV-Vis spectroscopy is validated as a method to determine the gold concentration in gold nanoparticle solutions using the colloids absorbance at 400 nm as a measure. Gold nanoparticle solutions are varied concerning the parameters particle size, surface functionality and oxidation state of contained gold.
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Ferizovic, Dino. "Development of Materials and Structures for p-type Contacts in CdTe Solar Cells." Scholar Commons, 2012. http://scholarcommons.usf.edu/etd/4320.
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Solar cells based on CdTe absorbers are attractive due to the optimal direct band gap energy and large absorption coefficient of CdTe, however, their performance and commercialization is hindered by the lack of reliable p-type contacts. CdTe has a low carrier concentration and a large electron affinity, which results in a requirement of non-realistic work functions for metals to be used as back contacts in the solar cell. Even noble metals such as Ag present a significantly large potential barrier for holes, thereby reducing the hole current through the semiconductor/metal interface. Several attempts to resolve this challenge have been tried, however, many drawbacks have been encountered.
Two particular systems, namely Cu2Te thin films and CdTe/ZnTe strained-layer superlattices, are investigated for their potential use as ohmic contacts in CdTe solar cells. A detailed analysis of the optical, electrical, and structural properties of Cu2Te thin films deposited by magnetron sputtering is presented. It is shown that these films have an indirect band gap and highly degenerate semiconductor behavior. The large p-type carrier concentration of Cu2Te films is highly desirable for the application of Cu2Te as a p-type contact to CdTe.
In-depth studies of optical transitions and miniband transport in strained-layer CdTe/ZnTe superlattices are presented as well. The band offsets between CdTe and ZnTe were determined by comparison of measured and calculated optical transitions. Superlattice structures that offer best contact performance have been identified by use of tunneling probability simulations.
Characterization of CdTe solar cells with above mentioned contacts indicated that contacts based on CdTe/ZnTe superlattices are a viable Cu free option for stable and reliable p-type contacts in CdTe solar cell. The contact performance of Cu2Te thin films was comparable to that of CdTe/ZnTe superlattices and both demonstrated an advantage over contacts based on ZnTe:N thin films which were used a standard.
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Čuboň, Tomáš. "Studium optických vlastností tenkých vrstev organických fotovoltaických článků." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2017. http://www.nusl.cz/ntk/nusl-316198.
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This master´s thesis is focused on measurement of optical properties of thin layer of materials used in organic solar cells (OSC). The usage of graphene oxides and its reduced forms as parts of hole transport layer (HLT) in OSC were studied. At the beginning of the thesis, there is described basic theory necessary to understand the optical properties of thin layers. The thin layer deposition and reduction of GO are discussed too. The experimental part is aimed to the optical characterization of prepared thin films. The results from optical microscopy, UV-VIS spectroscopy, FT-IR spectroscopy and spectroscopic ellipsometry were obtained. At the end of the thesis, the results are concluded and compared with already published literature.
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Day, Aaron M. "Characterization of Azobenzene Derivatives with Respect to Photoswitching and Aggregation Properties." University of Dayton / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1608140810691289.
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Andrade, NÃdia Ferreira de. "O efeitos da temperatura sobre a oxidaÃÃo de nanotubos de carbono." Universidade Federal do CearÃ, 2010. http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=5424.
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Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgicoOs nanotubos de carbono apresentam extraordinÃrias propriedades fÃsico-quÃmicas que tÃm sido exploradas para aplicaÃÃes que vÃo desde a ciÃncia de materiais atà a biologia. No entanto, a maioria das aplicaÃÃes requer modificaÃÃes quÃmicas dos nanotubos de modo a explorar ao mÃximo seu potencial. Neste contexto, o desenvolvimento de protocolos de tratamento e de purificaÃÃo à muito importante. O objetivo deste estudo à contribuir para o entendimento de como a mudanÃa de uma variÃvel especÃfica, a temperatura, afeta as propriedades fÃsico-quÃmicas dos nanotubos de carbono de paredes mÃltiplas (MWNTs) durante a purificaÃÃo. Um grama (1g) de MWNTs (Ctube 100, CNT Co. Ltd., Incheon - CorÃia do Sul) foram submetidos a um refluxo de Ãcido nÃtrico 9 mol/L por 12 horas em temperaturas de 25ÂC, 75ÂC, 125ÂC e 175ÂC. ApÃs o refluxo, as amostras foram resfriadas em um banho tÃrmico, filtradas em condiÃÃes de vÃcuo com uma membrana de PTFE de 0, 2 Âm e lavadas com Ãgua deionizada atà que o pH neutro do filtrado foi atingido. Por Ãltimo, os MWNTs oxidados foram secos em vÃcuo durante 48 h. As tÃcnicas utilizadas neste trabalho para a realizaÃÃo das caracterizaÃÃes forneceram resultados que tratam desde caracterÃsticas macro e de superfÃcie atà as associadas ao nÃvel atÃmico. A estabilidade tÃrmica foi analisada por meio de medidas de TGA, uma vez que muitos dos grupos funcionais criados no tratamento sÃo termicamente instÃveis. A oxidaÃÃo resultante do tratamento introduz grupos polares na superfÃcie dos MWNTs e assim cria a estabilidade eletrostÃtica necessÃria para uma dispersÃo estÃvel em meio aquoso. A estabilidade foi avaliada para cada amostra por meio de medidas de potencial zeta. A quantidade e o tipo de resÃduos catalÃticos presentes nas amostras antes e depois do tratamento foram analisados atravÃs de medidas de EDX e UV-VIS. Medidas de espectroscopia Raman Confocal permitiram a anÃlise especÃfica dos defeitos estruturais criados sobre a superfÃcie dos tubos, em conseqÃÃncia do processo de oxidaÃÃo. Constatou-se que os experimentos Raman devem ser realizados sobre muitos pontos para poder acessar as propriedades mÃdias das amostras. A capacidade de adsorÃÃo da superfÃcie de cada amostra apÃs o tratamento foi inspecionada atravÃs de medidas de Ãrea superficial especÃfica (mÃtodo BET). Ao comparar os resultados de diferentes tÃcnicas, foi possÃvel acessar os efeitos da temperatura do tratamento sobre as propriedades fÃsico-quÃmicas relevantes, permitindo assim a obtenÃÃo de amostras bem caracterizadas que serÃo Ãteis para futuros estudos em Ãreas bio-relacionadas.
Carbon nanotubes exhibit remarkable physico-chemical properties which have been exploited for applications ranging from materials science to biology. However, most of the aplications requires the chemical modification of the nanotubes in order to exploit their maximum potential. In this context, the development of protocols for treatment and purification is very important. The purpose of this study is to contribute for the understand on how the change of a particular purification parameter, temperature, affects the physico-chemical properties of multi-walled carbon nanotubes (MWNTs) during the purification. One gram (1g) of MWNTs (Ctube 100, CNT Co. Ltd., Incheon - South Korea) were subjected to a reflux with nitric acid 9 mol/L for 12 hours at temperatures 25ÂC, 75ÂC, 125ÂC and 175ÂC. After refluxed, the samples were cooled down in a heat bath, filtered in vacuum condition using a PTFE membrane of 0, 2 Âm and washed with deionized water until the neutral pH of the filtrate was reached. Afterwards, the oxidized MWCNTs were dried in vacuum for 48 h. The experimental techniques used in this work to perform the samples characterization provide results that allow to get information from macro and surface characteristics to those associated with the atomic level. Thermal stability was analyzed by TGA measurements, since many of the functional groups created during the treatment are thermally unstable. Oxidation resulting from treatment introduces polar groups on the surface of MWNTs thus creating the electrostatic stability required for a stable dispersion in aqueous medium. The stability was evaluated for each sample by zeta potential measurements. The amount and type of catalytic residues present in the samples before and after treatment were analyzed by means of EDX and UV-VIS. Techniques confocal Raman spectroscopy measurements allowed the specific analysis of the structural defects created on the surface of the tubes as a consequence of oxidation process. It was found that Raman experiments should be performed on may points of the sample in order to access their average properties. The adsorption capacity of the surface of each sample after treatment, were inspected through specific surface area measurements (BET method). By comparing the results of different techniques it was possible to access the effects of temperature on the treatment on the relevant physico-chemical properties thus allowing us to have well characterized samples that will be useful for further studies in biorelated areas.
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Iliopoulou, Ioanna. "Improving the stability of the black carrot (Daucus carota L.) colourant." Thesis, University of Edinburgh, 2016. http://hdl.handle.net/1842/17975.
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The replacement of artificial with natural dyes is one of the most challenging research fields in the food production area. Recent studies have shown that some frequently used synthetic colours, called the “Southampton 6 Colours” may be linked with hyperactivity in children. The purpose of this work is to analyse the degradation behaviour of black carrot, a natural, red dye commonly used for colouring food products, and subsequently improve its stability during heat and storage conditions. The stability of the black carrot mixture to heat exposure was investigated at a range of pH values by heat-treating aqueous solutions in a domestic oven at around 180oC to maintain the temperature at 100oC and the powdered material in a furnace at 180oC (typical baking conditions). 1H NMR (800 MHz) spectroscopy was used for the assignment of the aromatic chemical shifts of the black carrot mixture by overlaying them with the characterised 1H NMR chemical shifts of the individual components separated by RP-HPLC. Integration of high-resolution 1H NMR (800 MHz) spectra was used to follow the relative degradation of each of the components. Different procedures for the complexation of black carrot with metal oxides were developed, for which colourants of different colour shades were prepared. Spectroscopic techniques were used to follow the degradation of the complexes which were heat-treated at 180oC. Nano-scale investigation of the metal oxide powders was also carried out. The optimised colourants were tested on a bench scale and subsequently on an industrial scale in food pilot procedures. The successful complexes produced were found to be more heat stable compared to the commercial black carrot dye. The developed technologies are cheap and easy-to-produce methods to create intense heat and storage stable coloured pigments which can be used for the replacement of existing artificial dyes during food processing.
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Cline, Taylor Scott. "Investigation of Water-Molecule Complexes and Their Catalytic Effect on Important Atmospheric Reactions." BYU ScholarsArchive, 2013. https://scholarsarchive.byu.edu/etd/3990.
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This dissertation is a collection of works that investigates issues related to environmental chemistry. The first portion of this research explores the role of water vapor on the kinetics of important atmospheric reactions. Work is presented on the self-reaction of β-hydroxyethyl peroxy radical (β-HEP) and the catalytic increase in reaction rate by water vapor. β-HEP serves as a model system for investigating the possible role of water vapor in perturbing the kinetics and product branching ratio of atmospheric reactions of other alkyl peroxy radicals. The self-reaction rate coefficient of β-HEP was investigated between 276-296 K with 1.0 × 10^15 to 2.5 × 10^17 molecules cm^-3 of water vapor at 200 Torr total pressure by slow-flow laser flash photolysis coupled with UV time-resolved spectroscopy and long-path, wavelength-modulated, diode-laser spectroscopy. The overall disproportionation rate constant is expressed as the product of temperature-dependent and water vapor-dependent terms giving k(T,H2O) = 7.8 × 10^-14 (e^8.2 ^(±2.5) ^kJ/RT)(1 + 1.4 × 10^-34 × e^92 ^(±11) ^kJ/RT[H2O]). The results suggest that formation of a β--HEP-H2O complex is responsible for the observed water vapor enhancement of the self-reaction rate coefficient. Complex formation is supported with computational results identifying three local energy minima for the β--HEP-H2O complex. Both the temperature range and water vapor concentrations used were chosen because of their significance to conditions in the troposphere. As the troposphere continues to get warmer and wetter, more complexes with water will form, which in turn may perturb the kinetics and product branching ratios of atmospheric reactions. Future studies are proposed for the reaction of β-HEP + NO leading to NO2 formation. A laser-induced fluorescence cell was designed, built, and tested in preparation for studies of NO2 formation. Additionally Harriott-cell optics were manufactured and tested to detect HO2 using two-tone frequency-modulated diode-laser spectroscopy. In a related work, the breakdown of the environmental contaminants polychlorinated biphenyls (PCB's) was investigated using a new method. A new method for analyzing anaerobic digestion is also presented. The degradation rate and efficiency of digestion processes are typically measured by introducing a substrate or pollutant into a digester and then monitoring the effluents for the pollutant or substrate, a costly and slow process. A new method for rapid measurement of the rates and efficiencies of anaerobic degradation of pollutants and lignocellulose substrates from various pretreatments is described. The method uses micro-reactors (10-30 mL) containing a mixed culture of anaerobic bacteria obtained from a working anaerobic digester. The rates of degradation and metabolism of pollutants are measured in parallel sets of micro-reactors. Measurements of metabolic rate and pollutant degradation simultaneously is an effective means of rapidly examining pollutant degradation on a micro-scale. Calorimetric measurements alone allow rapid, relative evaluation of various substrate pretreatment methods. Finally calorimetric and electrophoretic methods were used to further knowledge in analytical techniques applied to important problems. In the last section of this dissertation the thermal and photolytic breakdown of promethazine hydrochloride is reported. Promethazine hydrochloride is a mediation that is commonly used as an antihistamine, a sedative, and an antiemetic, and to treat motion sickness. Perivascular extravasation, unintentional intra-arterial injection and intraneuronal or perineuronal infiltration may lead to irreversible tissue damage if the drug is not properly diluted or is administered too quickly. Data on the stability of promethazine hydrochloride diluted in sodium chloride 0.9% are lacking. This study evaluates the thermal and photolytic degradation of promethazine hydrochloride concentrations of 250 µg/mL and 125 µg/mL diluted in sodium chloride 0.9% over a period of 9 days. Degradation rates of promethazine hydrochloride were determined under UV-light, fluorescent light, and no light at various temperatures and concentrations to determine medication stability. The shelf-life (<10% degradation) at 25°C under normal fluorescent lights is 4.9 days, at 25°C protected from light, 6.6 days, and at 7°C in the dark, 8.1 days. These results may increase patient safety by improving current protocols for intravenous promethazine administration
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Müller, Tobias. "Untersuchungen zum „Controlled SBU Approach“ an metall-organischen Gerüstverbindungen und Syntheseversuche metallsubstituierter MOF-5- und MOF-177-Homologer." Master's thesis, Technische Universitaet Bergakademie Freiberg Universitaetsbibliothek "Georgius Agricola", 2012. http://nbn-resolving.de/urn:nbn:de:bsz:105-qucosa-89799.
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Die potentiellen Precursor Magnesiumoxobromid bzw. Mangan(II,III)-oxopivalat für die noch unbekannten metallsubstituierten IRMOF-Homologen MOF-5(Mg) bzw.
MOF-5(Mn) konnten erfolgreich synthetisiert und Charakterisiert werden.
Deren experimenteller Einsatz zur Synthese der IRMOF-Homologen schlug jedoch fehl. Es konnte gezeigt werden, dass unter den klassischen CSA-Reaktionsbedingungen sowie unter modifizierten Parametern keine Synthese der IRMOF-Homologen möglich ist. Diese Feststellung wurde mit der Diskussion um die Eigenschaften der Komplexe, der Metallionen sowie mit einer Aufarbeitung der dazu zugänglichen Literatur begründet.
Es ist mit der Synthese der neuen MOF-177-Homologen MOF-177(Co) und
MOF-177(Be) gelungen, die bereits bei MOF-5-Homologen eingesetzten Precursor und Parameter auf ein System anzuwenden, das nicht zu den Yaghi\\\\\\\\\\\\\\\'schen IRMOFs gehört. Die Festkörper weisen mit ihren Oberflächenwerten SBET(MOF-177(Co)) = 3742 m²/g bzw. SBET(MOF-177(Be)) = 1816.4 m²/g klar mikroporöses Adsorptionsverhalten auf. Eine erste vereinfachte Anpassung der Kristallstrukturen an die experimentellen PXRDs konnte für beide MOFs vorgenommen werden. MOF-177(Co) zeigt wie auch MOF-5(Co) eine leicht vergrößerte Gitterkonstante. MOF-177(Be) konnte aufgrund der Verdrehung der Carboxylatgruppen am Berylliumoxocluster ausschließlich in röntgenamorpher Form hergestellt werden.
Die Untersuchung der auftretenden Co-Spezies in reinen und mit Zinkprecursor gemischten Lösungen an Cobaltoxopivalat in den Lösungsmitteln Toluol brachte folgende Erkenntnisse:
• Der im Feststoff dimere achtkernige Cobaltprecursor zerfällt während des Lösens in die vierkernige monomere Form und ist strukturanalog dem basischen Zinkcarboxylaten (Typ I).
• Der Komplex unterliegt einem solvensabhängigem Komplexstabilitäts-gleichgewicht. Dieses ist aufgrund der koordinierenden Eigenschaften des DEF, in den DEF-Lösungen weiter in Richtung der Zersetzungsprodukte verschoben. In beiden Lösungen ist der Komplex zu über 90% undissoziiert.
• Nur in DEF treten bei dem Zumischen verschiedener Zinkprecursor Metallaustauschreaktionen auf. Es ist somit die Existenz von vierkernigen
Zn-Co-Mischclustern der allg. Form [CoyZn(4-y)O] bewiesen worden.
• Es wurde nachgewiesen, dass beim Vorhandensein von Acetat und Pivalat Anionenaustauschreaktionen stattfinden und Komplexe der Form
[CoyZn(4-y)O(Piv)xAc(6-x)] auftreten. Die Bedeutung für das Stattfinden des CSAs unter Berücksichtigung der empirischen Erkenntnisse aus der Literatur wurde erörtert.
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Schmiedová, Veronika. "Studium optických a interferenčních jevů na tenkých vrstvách organických materiálů." Doctoral thesis, Vysoké učení technické v Brně. Fakulta chemická, 2016. http://www.nusl.cz/ntk/nusl-256591.
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Ph.D. thesis is focused on the study and determination of layer thickness and optical properties, such as the dispersion dependence of the refractive index of various materials prepared in the form of thin layer. In the first part of this work the theoretical findings in the field of spectroscopic ellipsometry are summarised. These findings are followed by the description and characterization of the light polarization, evaluation of experimental data and determination of the physical properties of studied materials. Experimental and result section of this work is devoted to the preparation and characterization of thin films of the studied materials: titanum dioxide (TiO2), new organic materials (MDMO-PPV, PCDTBT, PCBTDPP, PC60BM, PC70BM) and reduced graphene oxide (rGO). These were all selected with respect to their potential use in the organic photovoltaics.
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Pflanz, Michael. "A methodical approach for non-destructive estimation of plant pigments by means of remission spectroscopy applied in fruit and vegetable analyses." Doctoral thesis, Humboldt-Universität zu Berlin, Landwirtschaftlich-Gärtnerische Fakultät, 2014. http://dx.doi.org/10.18452/17074.
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Anbaubegleitende spektral-optische Analysen direkt an der Pflanze haben zunehmend Bedeutung für die gartenbauliche Produktion. Veränderungen individueller Pflanzeninhaltsstoffe können mit Hilfe optischer Sensoren unmittelbar und beliebig oft erfasst werden, wodurch Pflanzenreaktionen auf veränderte Umgebungs- und Kulturbedingungen instrumentell messbar sind. Im Konzept eines Präzisionsgartenbau könnten diese zusätzlichen Informationen adaptiven Kulturmaßnahmen dienen und zur effizienten Nutzung von Ressourcen in der Produktion von Obst und Gemüse beitragen. Die wellenlängenspezifische Lichtabsorption pflanzlicher Gewebe ermöglicht zerstörungsfreie Reflexions- oder Transmissionsmessungen und die Adressierung von Pigmentgruppen im ultravioletten und sichtbaren Bereich des elektromagnetischen Spektrums. Auf Grund veränderlicher Gehalte während des Wachstum und der Entwicklung pflanzlicher Gewebe, sind Pigmente zudem wichtige Indikatoren für den physiologischen Zustand von Obst und Gemüse. Präzise zerstörungsfreie Spektralanalysen werden allerdings durch komplexe optische Eigenschaften biologischen Materials, besonders im Hinblick auf die Reifeentwicklung von Obst und Gemüse erschwert. Zur Lösung dieser Problematik wurde ein neuer iterativer Ansatz (iMLR) entwickelt, der überlagerte in-situ und in-vivo Spektren individueller Pigmente aus einem Summenmessspektrum separiert. Dieser Algorithmus wurde in eine eigenständige Applikation überführt. Eine Datenbank enthält spektrale Signaturen von Chlorophyll a und b, Lycopin, β-Carotin, α-Carotin, Lutein und Violaxanthin. Obwohl die spektrale Analyse einzelner Pigmente durch optische Störgrößen in komplex aufgebauten biologischen Geweben und Pigmentgemischen erschwert ist, konnte ein neuer Ansatz erarbeitet und validiert werden. Diese Methode minimiert spektrale Überlagerung von in-situ und in-vivo aufgezeichneten Messsummensignalen und analysiert Pigmentgehalte in Farbstoffgemische zuverlässig.Spectral measurements on plants have already been introduced in practice through extensive research and through the recent increase in the availability of low-cost devices. It can be expected that optical sensor systems may contribute to an economic and sustainable use of natural resources as a part of the concept for precision horticulture. In terms of phytomonitoring approaches, such technologies which address variable amounts of individual chromophoric plant components become more important. Their wavelength-selective light absorption makes pigments specifically responsive to reflection or transmission recordings in the ultraviolet and visible range of the electromagnetic spectrum. Additionally, pigments serve as indicators for physiological stages of leaf and fruit. Consequently, the instrumental recording of variable pigment contents has high potential with regards to dynamic plant-adapted processes during the production of fruit and vegetables. Solving the known issues of non-destructive spectroscopy, a new approach was figured out in the present work to obtain a more precise analysis of individual pigment contents, which vary during the cultivation of horticultural crops. The tool is based on an iterative algorithm (iMLR), that separates coinciding in-situ and in-vitro spectra from sum signals of individual pigments. Finally, the algorithm was integrated into a stand-alone application containing a library of chlorophyll a and b, as well as signatures of lycopene, β-carotene, α-carotene, lutein and violaxanthin. It can be pointed out that individual pigment compositions are suitable indicators of the physiological stage of horticultural products. However, the spectral analysis of single pigment levels is challenging due to complex interactions of coinciding absorption and diffuse light scattering in natural pigment mixtures or in fruit extracts. From this, an improved method for the reliable decomposition of spectral signals was developed.
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Sunday, Christopher Edozie. "The design of ultrasensitive immunosensors based on a new multi-signal amplification gold nanoparticles-dotted 4-nitrophenylazo functionalised graphene sensing platform for the determination of deoxynivalenol." Thesis, University of Western Cape, 2014. http://hdl.handle.net/11394/3361.
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Philosophiae Doctor - PhDA highly dispersive gold nanoparticle-dotted 4-nitrophenylazo functionalised graphene nanocomposite (AuNp/G/PhNO2) was successfully synthesised and applied in enhancing sensing platform signals. Three label-free electrochemical immunosensors for the detection of deoxynivalenol mycotoxin (DON) based on the systematic modification of glassy carbon electrodes (GCE) with AuNp/G/PhNO2 was effectively achieved. General electrochemical impedance method was employed for the sensitive and selective detection of DON in standard solutions and reference material samples. A significant increase in charge transfer resistance (Rct) of the sensing interface was observed due to the formation of insulating immune-complexes by the binding of deoxynivalenol antibody (DONab) and deoxynivalenol antigen (DONag). Further attachments of DONab and DONag resulted in increases in the obtained Rct values, and the increases were linearly proportional to the concentration of DONag. The three immunosensors denoted as GCE/PDMA/AuNp/G/PhNH2/DONab, GCE/Nafion/[Ru(bpy)3]2+/AuNp/G/PhNH2/DONab and GCE/Nafion/[Ru(bpy)3]2+/G/PhNH2/DONab have detection range of 6 – 30 ng/mL for DONag in standard samples. Their sensitivity and detection limits were 43.45 ΩL/ng and 1.1 pg/L; 32.14ΩL/ng and 0.3 pg/L; 9.412 ΩL/ng and 1.1 pg/L respectively. This result was better than those reported in the literature and compares reasonably with Enzyme Linked Immunosorbent Assay (ELISA) results. The present sensing methodology represents an attractive alternative to the existing methods for the detection of deoxynivalenol mycotoxin and other big biomolecules of interest due to its simplicity, stability, sensitivity, reproducibility, selectivity, and inexpensive instrumentation. And they could be used to develop high-performance, ultra-sensitive electrochemiluminescence, voltammetric or amperometric sensors as well.
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Guedes, Adriana Pereira Mundim. "Estudo espectroscópico da interação entre as proteínas séricas humanas Albumina e transferrina com o potencial agente quimioterapêutico cloreto de cis-tetraminodiclorutênio (III)." Universidade Federal de Goiás, 2013. http://repositorio.bc.ufg.br/tede/handle/tede/3363.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
Motivated by the perspective of ruthenium complexes to be used in cancer treatment, our research group has tested the hipotesis that some complexes of Ru (III) are able to interact with serum proteins, particularly albumin and transferrin. The Complex cis- [RuCl2(NH3)4]Cl (CTRu(III)) have been tested against different kind of tumor cells, obtaining good results. Starting from promising results obtained with this compound, subsequent studies are required to understanding the mechanism by which it exerts specificity for tumor cells. In this article, we report the first application of absorption UV-Vis, Fluorescence and Electron Paramagnetic Resonance (EPR) spectroscopy, to study the complex CTRu(III) interaction with human serum albumin (hsA) and bovine serum albumin (bsA). Fluorescence measurements revealed strong proteinsbound complex with Ksv of 1.32 x 105 and 3.71 x 105 for hsA and bsA, respectively. EPR spectra from mono-nuclear Ru(III) complexes in buffer, showed a significant decrease in the overall signal intensity following the first aquation step, is consistent with the formation of oxo-bridged Ru(III) dimers. EPR spectra revealed that the BSA very rapid binding to the protein via covalent binding through ligand-exchange with protein side chains, likely with histidine imidazoles. On the other hand, the complex binds non-covalently in hsA, probably as a product of the oligomerization of the complex in hemin-biding pocket. Furthermore, two species are slowly formed by covalent binding of the complex with the histidine residues, producing a species of axial symmetry and the other rhombic symmetry. These bonds seem to arise from the interaction of the complex with the histidine residue located in the binding Sudlow’s site II.
Motivado pela perspectiva de complexos de rutênio podem ser utilizados no tratamento do câncer, o nosso grupo de pesquisa testou a Hipótese que alguns complexos de Ru (III) são capazes de interagir com as proteínas do soro, particularmente albumina e transferrina. O complexo de cis-[RuCl2(NH3)4]Cl (CTRu(III)) foi testado contra diferentes tipos de células tumorais, obtendo bons resultados. A partir de resultados promissores obtidos com este composto, estudos subsequentes são necessários para a compreensão do mecanismo pelo qual ele exerce sua especificidade para células de tumor. Neste artigo, apresentamos a aplicação de espectroscopia de absorção UV-vis, fluorescência e ressonância paramagnética eletrônica (RPE), para estudar a interação do complexo CTRu(III) com albumina sérica humano (hsA) e a albumina sérica bovina (bsA). Medidas de fluorescência revelaram uma forte ligação do complexo com as proteínas com Ksv de 1,32 x 105 e 3,71 x 105 para hsA e bsA, respectivamente. Espectros de RPE de complexos de Ru (III) mono-nucleares em tampão mostraram um decréscimo significativo na intensidade do sinal global após a primeira passo de aquação, que é consistente com a formação de dímeros de oxo complexos de Ru (III). Os espectros de RPE revelaram que a ligação à bsA é muito rápida, a ligação covalente à proteína ocorre através de troca dos ligantes com cadeias laterais de proteínas, provavelmente com o imidazol da histidina. Por outro lado, o complexo se liga não covalentemente na hsA, provalente como produto da oligomerização do complexo no bolso de ligação hemin. Além disso, duas espécies são formadas lentamente por ligação covalente do complexo com os resíduos histidina, produzindo uma espécie de simetria axial e a outra de simetria rômbica. Essas ligações parecem surgir pela interação do complexo com o resíduo histidina localizado no sítio de ligação Sudlow II.
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Kazmin, Roman. "FTIR-spektroskopische Untersuchungen zum Aktivierungsmechanismus von bovinem und humanem Rhodopsin." Doctoral thesis, Humboldt-Universität zu Berlin, Lebenswissenschaftliche Fakultät, 2015. http://dx.doi.org/10.18452/17279.
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Das aus dem Apoprotein Opsin und dem kovalent gebundenen Liganden bestehende Rhodopsin dient als Modellsystem für den Aktivierungsmechanismus der größten Klasse von G-Protein-gekoppelten Rezeptoren (GPCR). Infolge einer photochemischen Reaktion vollführt Rhodopsin eine Bewegungsabfolge von Sekundärstrukturelementen, wodurch es aktiviert wird, das G-Protein bindet und den Stimulus auf zellinterne Signalwege überträgt. Mithilfe der ortsspezifischen Mutagenese wurden Mutanten des bovinen Rhodopsins erzeugt, in eine künstliche Lipidumgebung eingelagert und hauptsächlich mittels FTIR-Spektroskopie untersucht. Anhand der Y191F- und Y192F-Mutanten konnte die Translokation des transienten Gegenions der Schiffschen Base Glu181 während der Aktivierung bestimmt werden. Die Interaktionen des Tyr206 sind für die gekoppelte Bewegung von EL2 und TM5 mitbestimmend, was mittels Y206F-Mutante gezeigt wurde. Eine Anhäufung von Methioninen auf der cytoplasmatischen Seite des Rezeptors ist u.a. für das Ausklappen der TM6 zuständig. Diese Bewegung ist wichtige Determinante der Rezeptoraktivierung. Hierfür wurden insgesamt fünf Mutanten verwendet. Im zweiten, hauptsächlichen Teil der Arbeit wird das bislang kaum untersuchte humane Rhodopsin mit dem bovinen Rezeptor verglichen. Ausgehend von verschiedenen Dunkelzuständen, konnte gezeigt werden, dass die Aktivierungsmechanismen beider Rezeptoren voneinander divergieren, um letztlich bei der Bildung der aktiven Spezies wieder zu konvergieren. Über die Analyse der Aminosäuresequenzen der Mammalia-Rhodopsine wurden zwei Bereiche hoher Variabilität identifiziert, die u.a. die molekulare Ursache für diese Diskrepanzen liefern. Diese Feststellung wurde mit human-bovinen-Rhodopsinchimären bewiesen. Ergänzend zu dieser Studie wurde Schafsrhodopsin einem Vergleich sowohl mit bovinem als auch mit humanem Rezeptor unterzogen. Es zeigte, als eine weitere natürlich vorkommende Variante des Lichtrezeptors, einen eigenständigen Weg der Aktivierung.Rhodopsin, which consists of the apoprotein opsin and its covalently bound ligand, is used as a model system to understand the activation mechanism of the large family of G protein coupled receptors (GPCRs). As a result of a photochemical reaction, rhodopsin undergoes activating structural changes, enabling it to bind the G protein and transmitting the stimulus to intracellular signaling pathways. In the first part of this work, site-directed mutants of bovine rhodopsin were produced, incorporated into an artificial lipid environment, and studied mainly by FTIR spectroscopy. The translocation of the transient Schiff base counterion (Glu181) during the activation process was determined using the Y191F- and Y192F-mutants. The interactions of Tyr206 contributed to the coupled movement of EL2 and TM5, which was shown by Y206F-mutant. A striking accumulation of methionines on the cytoplasmic side of the receptor was observed to be a key-player for the activating outward motion of TM6. In the second and primary part of this work, human rhodopsin, which has been rarely studied, was compared with the bovine receptor. Starting from various dark states, it was shown that the activation mechanisms of both receptors diverge from each other and yet ultimately converge in the formation of the active species. By analyzing the amino acid sequences of mammalian rhodopsins, two regions of high variability were identified, which provide the molecular basis for these discrepancies. This finding was verified by the investigation of human/bovine rhodopsin chimeras. In addition to this study, ovine rhodopsin was compared with both the bovine and human forms. It showed, as another naturally occurring variant of the light receptor, an independent pathway of activation.
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Elijošiutė, Erika. "Spectroscopic studies and theoretical modeling of iron(III) and mercury(II) thiocyanate complexes." Doctoral thesis, Lithuanian Academic Libraries Network (LABT), 2015. http://vddb.library.lt/obj/LT-eLABa-0001:E.02~2014~D_20150102_134423-02364.
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In the recent studies thiocyanate-containing metal complexes are considered to be the most investigated systems. Such complexes exhibit specific properties which could be applied in various fields such as catalysis, photochemistry, biochemistry, pharmacology and etc. The complexes of mercury(II) and iron(III) thiocyanates are of interest since they are widely applied for analysis in the clinical or industrial laboratories. As a result these complexes received great attention, due to the fascinating properties in designing new materials with inorganic and organic ligands. Dealing with such complex system, accurate prediction of the synthesized compound properties is challenging. For this reason, researchers analyze how the replacement of certain group, modification, molar ratio of the mixed ligands and etc. may influence the structure and properties of the obtained complex. Molecular structure, vibrational and electronic spectra of aqueous mercury(II) thiocyanate and iron(III) monoisothiocyanate solutions (at the pH ~ 2) were analyzed in the dissertation by means of Raman and UV-VIS spectroscopies and quantum chemical calculations. The structure, coordination number and vibrational assignments of the titled complexes were determined. The influence of different solvation models upon spectral properties was estimated. The excited state analysis of iron(III) monoisothiocyanate was performed.Metalų tiocianatų chemija yra ypatingai sparčiai besivystanti tyrimų kryptis. Dėl specifinių metalų tiocianatų savybių šie junginiai plačiai taikomi katalizinėje chemijoje, biochemijoje, farmakologijoje, fotochemijoje ir pan. Vieni iš plačiausiai nagrinėjamų pereinamųjų metalų tiocianatų kompleksų yra geležies ir gyvsidabrio tiocianatai. Pastaruoju metu mokslininkai bando susintetinti kompleksinius geležies ir gyvsidabrio tiocianatų junginius, turinčius neorganinį ir organinį ligandus, kurie pasižymi specifinėmis savybėmis tokiomis kaip: liuminescencija, magnetizmas, katalizinis aktyvumas ir pan. Tačiau, siekiant susintetinti junginius su norimomis fizikinėmis ir cheminėmis savybėmis, reikalingos žinios apie kompleksų struktūras, kompleksavimo ypatybes ir visą tai įtakojančius veiksnius molekuliniame lygmenyje. Disertacijoje analizuota tirpių gyvsidabrio(II) tiocianatų ir geležies(III) monoizotiocianato kompleksų (esant pH ~ 2) molekulinė struktūra, virpesiniai ir elektroniniai spektrai taikant Ramano ir UV-RŠ spektroskopines analizes bei kvantinius skaičiavimus. Nustatyti kompleksų koordinacijos skaičiai ir struktūros, atlikti funkcinių grupių signalų priskyrimai, įvertinta solvatacijos įtaka kompleksų spektrinėms savybėms ir išanalizuoti geležies(III) monoizotiocianato komplekso elektroniniai perėjimai sužadintoje būsenoje.
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Mayer-Uhma, Tobias. "Von molekularen Precursoren zu Oxidphasen im System V2O5 / Nb2O5. Darstellung, Eigenschaften, katalytische Aktivität." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2004. http://nbn-resolving.de/urn:nbn:de:swb:14-1107505327269-01068.
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In this work, mixed alkoxides of general formula [V(O)Nbx(OR)(3+5x)] (R = n-C3H7 and C2H5, x = 1, 4.5 and 9) are obtained. They are used to prepare complex (V/Nb)-pentoxides. Different spectroscopic methods, for example UV/VIS, resonance raman, infrared, temperature dependant 51V NMR and two dimensional 1H or 13C NMR, are used to elucidate structural details. It can be shown that the alkoxide precursor is a mixture of monomers and dimers which exchange very quickly. 2 % [V(O)Nb(OPr)8] (Pr = propyl) exists in a 0.1 molar solution. This complex is in equilibrium with V(O)(OPr)3 and Nb(OPr)5. Nb(OPr)5 itself exchanges with [Nb(OPr)5]2. For nuclear magnetic resonance experiments the exchange has to be slowed down using low temperatures.Controlled hydrolysis at 5 °C of a mixture of V(O)(OPr)3 and [Nb(OEt)5]2 in propanol leads to a clear transparent gel. The ratio of V : Nb is 1 : 1, 1 : 4.5 or 1 : 9, and oxalic acid is used as a chelating agent. Moreover, a dried product of a frozen solution of ammonium vanadate and ammonium oxyoxalatoniobate in water is found to be an appropriate precursor for the fore-mentioned oxides. Thermal decomposition of the gels and of the freeze dried products is monitored thermoanalytically and mass spectrometrically.The compositions of the resulting phases are examined and compared with the composition obtained via conventional synthesis (sintering of powder mixtures). Phases VNbxO(2.5+2.5x) (x = 1, 4.5 and 9) are obtained through the sol-gel technique and freeze drying at distinctly lower temperatures. VNbO5 crystallizes between 400 and 650 °C and V4Nb18O55 between 550 and 750 °C. A clean, non-reduced phase, VNb9O25, crystallizes above 1100 °C in oxygen. Below this temperature, solid solutions of V2O5 in TT- or M-Nb2O5 exist. Conventionally, pure VNbO5 is not obtainable. Some sol-gel synthesized products have the advantage of a more complete phase formation. In this way, a new phase of composition VNb9O25 can be found. The phase is homöotypic to M-Nb2O5.An additional advantage of the sol-gel synthesis lies in relatively high surface areas. Adversely, carbon remaining from the alcohol groups favours the thermodynamically stable phase VNb9O25 over the phase V4Nb18O55. Consequently, the freeze drying method seems to be the best way to get metastable phases in the system V2O5/x·Nb2O5.The formation of the complex oxides is controlled through the thermodynamics at phase boundaries. Therefore, to get mixed phases, structurally similar starting materials are preferred. In other words, using V2O5 and TT-Nb2O5 as starting materials the mixed phase similar to TT-Nb2O5 can be obtained. B-Nb2O5 as precursor yields another mixed phase similar to B-Nb2O5. In this work, this effect is called the "structure directing effect". It is explained through the consumption of free enthalpy at the phase boundaries.As an additional point, catalytic activities of the complex oxides are examined. Because of a synergism of the known good activity of V2O5 and the good selectivity of Nb2O5, a strongly enhanced activity of the mixed oxides is found. Large surface areas further improve the activity. Connections between oxygen partial pressure, band gap and catalytic activity are found. A dilution of V2O5 in Nb2O5 down to 10 mol-% also causes an enhancement of catalytic activityIn der Arbeit werden durch die Synthese gemischter Alkoxide der Gesamtzusammensetzung [V(O)Nbx(OR)(3+5x)] (R = n-C3H7 und C2H5, x = 1, 4,5 und 9) sowie gefriergetrockneter Pulver Ausgangssubstanzen für gemischte, komplexe Vanadium- und Nioboxide erhalten. Untersuchungen mittels UV/VIS-, Resonanz-Raman- und IR-Spektroskopie sowie temperaturabhängiger 51V- und zweidimensionaler 1H-/13C NMR-Spektroskopie zeigen, dass es sich bei der Alkoxid-Vorstufe um ein Gemisch aus monomeren und dimeren Einheiten handelt, die in schnellem Gleichgewicht miteinander stehen. So liegt [V(O)Nb(OPr)8] als Donorkomplex vor, der im Gleichgewicht mit VO(OPr)3 und Nb(OPr)5 steht. Nb(OPr)5 steht wiederum im Gleichgewicht mit [Nb(OPr)5]2. Die Bildung und der Zerfall des Donorkomplexes erfolgen bei Raumtemperatur so schnell, dass er nur durch UV/VIS- und Resonanz-Raman-Spektroskopie sichtbar wird; bei der Kernresonanzspektroskopie muss der Austausch durch tiefe Temperaturen verlangsamt werden.Mittels kontrollierter Hydrolyse einer Mischung aus VO(OPr)3 und [Nb(OEt)5]2 in Propanol mit Oxalsäure als Chelatbildner und der Verlangsamung der Kondensation über die Erniedrigung der Temperatur wird ein homogenes, transparentes Gel aus V2O5 und Nb2O5 hergestellt. Daneben wird durch eine Lösung aus Ammoniumvanadat und Ammoniumoxyoxalatoniobat ein für die Gefriertrocknung geeigneter Precursor zur Synthese der Oxidphasen gefunden. Die Zersetzung des Gels und der gefriergetrockneten Pulver werden mittels DTA, TG und Massenspektrometrie untersucht und die Phasenausbildung mit der Reaktion von konventionellen Festkörpergemengen verglichen.Die dabei entstehenden metastabilen und thermodynamisch stabilen Phasen VNbxO(2,5+2,5x) (x = 1, 4,5 und 9) sind durch das Sol-Gel-Verfahren sowie durch die Gefriertrocknung bei deutlich niedrigeren Temperaturen und mit geringerem Fremdphasenanteil als bei der konventionellen Synthese erhältlich. VNbO5 existiert bis 650 °C, V4Nb18O55 bis 750 °C, darüber wandelt sich jede Zusammensetzung in VNb9O25 bzw. in verschiedene Nb2O5-Modifikationen und V2O5 um. Die Sol-Gel-Methode liefert im Vergleich zur Gefriertrocknung bei 900-1100 °C den Vorteil der schnelleren Phasenausbildung durch die größere Homogenität der Vorstufe. So erhält man Zwischenstufen, die sonst nur mit Beimengungen zu synthetisieren sind. In diesem Zusammenhang kann erstmalig eine zu M-Nb2O5 homöotype Verbindung der Zusammensetzung VNb9O25 erhalten werden. Ein weiterer Vorteil der Sol-Gel-Synthese ist der Erhalt größerer Oberflächen nach der Zersetzung. Nachteilig erscheinen jedoch bei einer Synthese bei tiefen Temperaturen (500-800 °C) die Alkoholatreste. So entstehen wesentlich eher die thermodynamisch begünstigten Phasen, z. B. VNb9O25 vor V4Nb18O55 und V4Nb18O55 vor VNbO5. Weiterhin macht sich die komplizierte Präparation der Gele bemerkbar; daher stellt im Allgemeinen die Gefriertrockung die Methode der Wahl dar.Die Ausbildung der komplexen Oxide erfolgt stark geprägt durch die Thermodynamik an den Phasengrenzen. Daher erfolgt eine bevorzugte Ausbildung strukturähnlicher Mischphasen. Diese erstmalig in diesem Ausmaß festgestellte Tatsache wird in der Arbeit der Strukturdirigierende Effekt genannt. Eine Erklärung dieses Effektes erfolgt anhand des Verbrauchs der Freien Enthalpie an den Phasengrenzen.Aufgrund eines Synergismus der Eigenschaften von V2O5 und Nb2O5 bei der oxidativen Dehydrierung von Propan zu Propen (relativ hohe katalytische Aktivität von V2O5 und hohe Selektivität von Nb2O5) wird eine überproportional hohe katalytische Aktivität bei den Mischoxiden erhalten. Die durch die unkonventionellen Methoden erhaltenen großen Oberflächen verbessern die Aktivität weiter. Es können Zusammenhänge festgestellt werden zwischen der Sauerstoffabgabetendenz, der Redoxkraft, der Bandlücke der Mischoxide und der katalytischen Aktivität. Die Einzigartigkeit des Nb2O5-Wirtsgitters bewirkt bei der Verdünnung von V2O5 darin eine hohe katalytische Leistungssteigerung
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Colzato, Marina. "Transformações na matéria orgânica nos sedimentos e águas eutrofizados da Represa Ibirité (Ibirité-Sarzedo, MG) tratados com nitrato de cálcio em microcosmos." Universidade Federal de São Carlos, 2010. https://repositorio.ufscar.br/handle/ufscar/6481.
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Previous issue date: 2010-11-19Financiadora de Estudos e Projetos
Due to the growing concern with the environment and the welfare of future generations the search for the restoration of degraded areas and the reestablishment of equilibrium between the anthropogenic and natural environments are nowadays highlighted. The Ibirité Reservoir (Ibirité-Sarzedo, MG) is an example of water body impacted by the disorganized urbanization and strong industrial development in the metropolitan Belo Horizonte, MG, SE Brazil. The reservoir, built by the REGAP-Petrobras in the sixties to supply water to its industrial processes, is a eutrophic water body due to the continuous contribution of urban sewage (external loading) and the consequent internal loading of nutrients (mainly of phosphorus), the primary element responsible for the eutrophication process. Among the existing technologies for the treatment of eutrophic sediment focusing on the P immobilization is the artificial supply of nitrate as an electron acceptor to the stimulation of the natural denitrification process. In this stimulation process, the different geochemical forms of reduced iron are oxidized to iron (III) oxi-hidroxides that adsorbs the phosphorus present in the sediment pore water. In addition to that, the metallic sulfides and the organic matter are oxidized as well. This work aimed at the development of laboratory experiments in a bench scale (microcosms) in which sediments and water of the Ibirité reservoir were treated with nitrate addition in order to evaluate the organic matter transformations from caused this treatment. The results indicate that there was, in the treatment microcosms, an increase in the redox potential, an almost complete abatement of the acid volatile sulfide (AVS) of the sediments, and a significant reduction of available phosphorus in the water. The UVvis spectroscopy indicated differences in the spectral profiles between the control and treatment microcosms, but uniform trends along the experiment were not identified. The elemental analysis showed agreement with the results of AVS and nitrogen species in sediment pore water data, with the reduction of sulphur and nitrogen contents.
Diante da crescente preocupação com o meio ambiente e o bem estar das futuras gerações, destacam-se cada vez mais a busca pela recuperação das áreas degradadas e o restabelecimento do equilíbrio nas relações entre os meios natural e antrópico. A Represa Ibirité (Ibirité-Sarzedo, MG) é um exemplo de corpo de água impactado pela urbanização desorganizada e crescimento industrial da região metropolitana de Belo Horizonte, MG. A represa, construída pela REGAP-Petrobrás na década de 60 para suprimento de água em seus processos industriais, encontrase eutrofizada devido ao contínuo aporte de esgotos urbanos não tratados (carga externa) e à conseqüente carga interna de nutrientes, principalmente o fósforo, o principal responsável pelo processo de eutrofização. Dentre as tecnologias existentes para o tratamento de sedimentos eutrofizados, visando a imobilização do P, figura a adição de nitrato como um receptor de elétrons para o estímulo do processo natural de desnitrificação. Nesta estimulação, as diferentes formas geoquímicas de ferro reduzido são oxidadas a óxi-hidróxido de ferro (III) que adsorve o fósforo presente nas águas intersticiais, promovendo também, a oxidação dos sulfetos metálicos e a matéria orgânica presentes nos sedimentos. Neste trabalho o tratamento dos sedimentos e águas eutrofizados da Represa Ibirité foi avaliado em escala de bancada, utilizando microcosmos, onde se estudou a transformação da matéria orgânica presente nas águas de coluna, nos sedimentos e suas águas intersticiais. Os resultados indicam que houve, nos microcosmos-tratamento, um aumento do potencial redox do meio, um quase total abatimento do SVA dos sedimentos e uma redução do fósforo disponível nas águas em um nível bastante expressivo. As espectroscopias na região do UV-vis indicaram alterações nos perfis espectrais entre os microcosmos-controle e tratamento, sem, no entanto, identificar uma tendência uniforme ao longo dos períodos do experimento. A análise elementar foi concordante com os resultados de SVA e de espécies nitrogenadas nas águas intersticiais, pois mostram uma redução do teor de enxofre e de nitrogênio.
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Procházková, Michaela. "Studium působení plazmatu na roztoky chininu." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2020. http://www.nusl.cz/ntk/nusl-414084.
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This diploma thesis focuses on quinine solutions and quality of these solutions after applying plasma discharge. These electric discharges can be used to destroy some substances from the water. The theoretical part is focused on description of electric discharges in liquids and on the properties of quinine. In the experimental part, the properties of quinine solutions containing different electrolytes were analysed by UV-VIS spectrophotometer and fluorescence spectroscopy. Two different types of configurations of plasma discharges in liquids were used. Solutions were compared on the base of different concentration of quinine, different electrolytes, different configurations of plasma discharges and pH values of the solutions. Furthermore, the experimental work focuses on quinine solutions with the sodium nitrate. The time instability of the solutions was analysed. Also, the influence of the solution age and different types of the plasma discharge on the excitation and emission spectra of quinine were investigated.