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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
321

Analyse chimique des matières résineuses employées dans le domaine artistique pré-hispanique au Mexique : application aux échantillons archéologiques aztèque et maya

Lucero, Paola 14 September 2012 (has links) (PDF)
Dans le present travail de recherche notre équipe s'est interessé à l'étude de la composition chimique -au niveau moléculaire- d'un groupe d'échantillons résineuses provenant d'objects Aztecs et Mayas. Le but ultime de cette étude a été d'établir l'origin botanique de ces résines et d'avoir une vue d'ensemble des formulations utilisées dans les adhésifs ou les figurines, afin de mieux comprendre leurs propriétes physiques.Pour aboutir à cet objectif une stratégie analytique très spécifique a été créeé et mise en oeuvre. Cette stratégie a inclus l'analyse d'échantillons des résines archéologiques mais aussi de résines d'origine botanique certifiée et de résines commerciales, achetées dans des marchés traditionels au Mexique dans une région qui correspond a la one géographique occupée autre fois par l'empire aztèque.L'étude des matériaux a fait appel à des techniques tels que l'observation a l'échelle microscopique, la spectroscopie infrarouge (IRTF), la chromatographie liquide-DAD (HPLC-UV/Vis) et la chromatographie en phase gazeuse couplée à la spéctroscopie de masse (CPG-SM).L'étude moléculaire de ces échantillons, et plus précisement, l'étude leur fraction tritérpenique a permis de : Établir un profil moléculaire des résines pour chaque origine botanique étudiée Idéntifier précisement certain composées tritérpeniques présents dans toutes les échantillons Réperer les molécules tritérpeniques susceptibles d'être utilisées dans l'avenir comme des marqueurs moléculaires d'origine botanique pour les résines frais des espèces étudiées Suggèrer une origine botanique pour les échantillons archéologiques Aztèques Écarter des origines botaniques possibles pour l'échantillon Maya Avoir une vue d'ensemble de l'origine botanique des résines commercialisées au territoire mexicain sous le nom de "copal" Créer un protocole d'analyse simple pour permettre aux professionnels de la conservation et des biomatériaux d'établir l'origine botanique et un profil moléculaire des résines utilisées dans des expériences diverses Caractériser le comportement du copal lors du vieillisement naturel et artificiel Établir des molécules susceptibles de devenir marqueurs moléculairs pour les deux types de vieillisement Établir que l'origine botanique d'un échantillon résineux peut être retrouvée malgré son âge (archéologique)
322

Décoration de réseaux linéaires de défauts smectiques par des nanoparticules d'or

Delphine, Coursault 22 March 2013 (has links) (PDF)
Nous créons des films minces smectiques de défauts topologiques linéaires sur substrats de polymère grâce au savoir faire acquis sur substrats cristallins. Le transfert de ce système sur polymère permet d'étudier l'influence du substrat sur la structure du film, et de mener un nouveau type d'étude par diffraction des rayons X en adoptant deux configurations couplées en réflexion et en transmission. D'autre part, en mélangeant des nanoparticules (NPs) à ces films, on transmet leur anisotropie aux auto-assemblages NPs d'or pour obtenir des propriétés optiques définies et activables par variation de la polarisation de la lumière. Dans le cas de films hybrides faiblement concentrés, nous créons des chaînes de NPs individuelles piégées par les dislocations smectiques, sur plusieurs dizaines de microns. En fonction de la concentration, les NPs peuvent être isolées ou en condition de couplage électromagnétique, permettant d'obtenir une anisotropie de la résonance de plasmon jusqu'à 40 nm. A plus grande concentration, le réseau linéaire de NPs se transforme en réseau bidimensionnel, toujours anisotrope, dont une direction dense est imposée le long des défauts. Pour le film smectique pur, un modèle avec un joint de grain tournant est retrouvé et interprété comme minimisant la présence de dislocations. Nous identifions deux sites de dislocations capables de piéger les nanoparticules : le premier site, préférentiel, piège les NPs dans un environnement ordonné situé près du substrat ; le second est en haut du joint de grain tournant plus proche de l'interface avec l'air, il mobilise une assemblée de dislocations reconstruites en fonction de la concentration en NPs. Finalement, cette auto-organisation dirigée de nanoparticules, ouvre la voie pour l' étude de systèmes hybrides de particules plus grandes ou de formes anisotropes pour exalter les effets d'anisotropie de l'auto-assemblage.
323

Le Tellurure de Cadmium amorphe oxygéné a - CdTe:O Synthèse et étude de quelques propriétés physico-chimiques

El Azhari, Youssef 14 October 2003 (has links) (PDF)
Le travail présenté dans cette thèse s'inscrit dans le cadre de l'étude des propriétés des couches minces de matériaux semi-conducteurs à base de tellurure de cadmium CdTe. L'étude de l'influence de différents paramètres de dépôt sur les propriétés des couches minces de CdTe nous a permis de mettre au point une méthode de préparation d'un nouveau matériau à base de CdTe. Il s'agit du tellurure de cadmium amorphe oxygéné aCddTe:O. Le dépôt de couches minces de a-CdTe:O à partir d'une cible polycristalline de CdTe nécessite l'utilisation d'un plasma à haut pouvoir oxydant. Le plasma que nous avons utilisé est obtenu à partir d'un mélange d'argon Ar, de dioxygène et de diazote soumis à un champ électrique radiofréquence de 13,56 MHz. Nous avons montré que le diazote joue un rôle de catalyseur de l'oxydation de CdTe dans le plasma de déposition dont la composition détermine celle des couches minces de a-CdTe:O. En effet, la teneur en oxygène de ces couches peut avoisiner les 60 % lorsque les conditions d'oxydation sont poussées à l'extrême. Les propriétés optiques des couches minces de a-CdTe:O dépendent beaucoup de la teneur des couches en oxygène. C'est ainsi que l'énergie Eg du gap optique varie entre 1,45 eV et 1,85 eV pour une teneur en oxygène variant entre 0 et 40 % en pourcentage atomique. La valeur extrapolée à l'infrarouge de l'indice de réfraction de ces couches varie, quant à elle, entre 2,15 et 2,75. L'étude par XPS montre que l'oxygène incorporé dans les couches minces de a-CdTe:O se lie aussi bien aux atomes de tellure qu'à ceux de cadmium. En utilisant la réfléctométrie des rayons X, nous avons pu mettre en évidence l'influence du plasma oxydant précédent sur les couches minces de CdTe. Nous avons réussi ainsi à mettre au point une méthode qui permet de réduire considérablement la rugosité de surface des couches minces de CdTe. Lorsque l'on pousse à l'extrême les conditions d'oxydation, on peut obtenir des couches minces amorphes de l'oxyde stable CdTeO3. L'étude des propriétés électriques de ces couches permet de mettre en évidence leur caractère isolant. Nous avons pu ainsi déterminer leur résistivité électrique continue 3x10^6 ohm.m et leur constante diélectrique relative (16). Les mesures de transmission optique ont permis de déterminer leur énergie de gap optique Eg=3,91 eV ainsi que la valeur extrapolée à l'infrarouge de leur indice de réfraction (1,90). Des couches minces amorphes de CdTeO3 ont aussi été déposées sur CdTe en couche mince. Un recuit approprié des structures ainsi obtenues permet de faire croître du CdTeO3 polycristallin sur du CdTe polycristallin.
324

Protein phosphatase biosensor for the detection of cyanotoxins associated with algal bloom

Mniki, Nontle Catherine January 2013 (has links)
Magister Scientiae - MSc / The toxicity of microcystin is associated with the inhibition of serine/threonine protein phosphatases 1 and 2A, which can lead to hepatocyte necrosis and haemorrhage. Analysis of microcystin is most commonly carried out using reversed-phase high performance liquid chromatographic methods (HPLC) combined with ultra-violet (UV) detection .The ability of these techniques to identify unknown microcystin in environmental samples is also restricted by the lack of standard reference materials for the toxins. Highly specific recognition molecules such as antibodies and molecularly imprinted polymers (MIPs) have been employed in the pre-concentration of trace levels of microcystin from water and show great potential for the clean-up of complex samples for subsequent analysis. New biosensor technologies are also becoming available, with sufficient sensitivity and specificity to enable rapid ‗on-site‘ screening without the need for sample processing. In this work we constructed a Protein phosphatase biosensor for detection of microcystin-LR in aqueous medium, onto polyamic acid/graphene oxide (PAA: GO) composite electrochemically synthesised in our laboratory. The composites were synthesised at three different ratios i.e. 50:50, 80:20 and 20:80 to evaluate the effect of each component in the search to produce highly conductive mediator platforms. The electrochemistries of the three different composites were evaluated using CV and SWV to study interfacial kinetics of the materials as thin films at the glassy carbon electrode. The phosphatase biosensor parameters were evaluated using CV, SWV, EIS and Uv-vis spectroscopy. The affinity binding of the microcystin-LR to protein phosphatase 2A was investigated using electrochemical impedance spectroscopy which is a highly sensitive method for measuring interfacial kinetics of biosensor systems.
325

CARACTERIZAÇÃO DE EXTRATOS DE Connarus perrottetii var. angustifolius RADLK E AVALIAÇÃO DO COMPORTAMENTO ANTIOXIDANTE FRENTE A ESPÉCIES RADICALARES / CHARACTERIZATION OF Connarus perrottetii var. angustifolius RADLK EXTRACTS AND EVALUATION OF THE ANTIOXIDANT BEHAVIOR AGAINST FREE RADICAL SPECIES

Müller, Larissa Sabo 31 July 2013 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This paper describes the development of methodology for capillary electrophoresis with UV detection for the determination of 14 polyphenolic antioxidants in extracts of Connarus perrottetii var. angustifolius Radlk, a native plant of the Amazon forest. The method using capillary zone electrophoresis (CZE) allows simultaneous determination of 3-acetyilcoumarine, resveratrol, 6-hydroxycoumarin, catechin, rutin, ferulic acid, quercitrin, kaempferol, fisetin, myricetin, quercetin, caffeic acid, gallic acid and 4 hydroxicinnamic acid in the optimized conditions: borate buffer 20 mmol L-1 (pH 9.2) as work electrolyte containing 15% methanol (v /v), -20 kV potential separation, temperature 25 °C; hydrodynamic injection gravity 20 cm for 60 s. The method was validated on parameters of linearity, limit of detection, quantification limit, precision and accuracy, and was used in the analysis of aqueous infusion and ethanol, butanol and ethyl acetate plant fractions. The method was capable of identifying the antioxidants present in samples with high selectivity and sensitivity. In infusion and in ethanol and butanol fractions was found the presence of catechin and rutin as major compounds, which makes up about 0.5% of the total mass of medicinal plant. The obtained dry extracts (ethanol and butanol) allowed the concentration of rutin and catechin around 20 times compared to the dry plant. In addition, tests were performed to measure the antioxidant activity of the extracts against DPPH radical, superoxide anion radical, hydroxyl and peroxyl. A sample of aqueous infusion of 10% showed the highest activity against most free radicals. It corroborates the results of characterization by capillary electrophoresis, where catechin and rutin were determined in relatively high concentrations in the aqueous infusion. But all treatments of the samples showed good antiradicalar behavior with the methodologies applied. Against DPPH, for example, the ethyl acetate fraction showed a potential of 94,43%. Against superoxide and hydroxyl radicals, the butanol fraction showed the best performance: 64,23% and 74,97%, respectively. / Este trabalho descreve o desenvolvimento de metodologia em eletroforese capilar com detecção UV para a determinação de 14 antioxidantes polifenólicos em extratos de Connarus perrottetii var. angustifolius Radlk, planta nativa da Amazônia brasileira. O método empregando eletroforese capilar de zona (CZE) permite a determinação simultânea de 3-acetilcumarina, resveratrol, 6-hidroxicumarina, catequina, rutina, ácido ferúlico, quercitrina, canferol, fisetina, miricetina, quercetina, ácido cafeico, ácido gálico e ácido 4-hidroxicinâmco nas condições otimizadas: eletrólito de trabalho tampão borato 20 mmol L-1 (pH 9,2) contendo metanol 15% (v/v), potencial de separação -20 Kv, temperatura 25 °C; injeção hidrodinâmica por gravidade em 20 cm durante 60 s. O método foi validado nos parâmetros de linearidade, limite de detecção, limite de quantificação, precisão e exatidão e foi aplicado na análise da infusão aquosa e frações etanólica, butanólica e acetato de etila da planta. O método foi capaz de identificar os antioxidantes presentes nas amostras com alta seletividade e sensibilidade. Na infusão e nas frações etanólica e butanólica foi encontrada a presença de catequina e rutina como compostos majoritários, os quais compõe cerca de 0,5% da massa total de planta medicinal. Os extratos secos obtidos (etanólico e butanólico) possibilitaram a concentração de rutina e catequina em torno de 20 vezes em relação à planta seca. Além disso, foram realizados testes para mensurar a atividade antioxidante dos extratos frente aos radicais DPPH, ânion radical superóxido, hidroxila e peroxila. A amostra de infusão aquosa a 10% foi a que apresentou maior atividade frente à maioria dos radicais livres. Esse resultado corrobora os resultados de caracterização por eletroforese capilar, onde catequina e rutina foram determinadas em concentrações relativamente altas na infusão aquosa. Porém, todos os tratamentos das amostras apresentaram bom comportamento anti-radicalar com as metodologias aplicadas. Frente ao radical DPPH, por exemplo, a fração acetato de etila demonstrou um potencial de 94,43%. Frente aos radicais superóxido e hidroxila, a fração butanólica apresentou o melhor desempenho: 64,23% e 74,97%, respectivamente.
326

Desenvolvimento de método para determinação de agrotóxicos (perturbadores endócrinos) em água / Development of method for determination of pesticides (endocrine disruptive) in water

Santos, Ruyanne Andreza Camilo 26 February 2016 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The water pollution causes changes in physical, chemical and biological water, which interfere with their quality, preventing its use for human consumption. Most chemical contaminants in surface water are related to industrial and agricultural sources. Since, with farming the Brazil pollute existing water resources making use of pesticides and fertilizers. This study aims to develop a fast and efficient method based on extraction techniques in solid phase (SPE) and high-performance liquid chromatography with UV detection in the ultraviolet and visible with diode array (HPLC UV-Vis / DAD) for the determination of pesticides, endocrine disruptors, epoxiconazole, fenarimol, fenbuconazole, flusilazole, flutriafol, and vinclozolin in water using biocarvões produced from agro-industry waste as an alternative sorbent for SPE. Tests with the analytes allowed the adjustment of the chromatographic conditions for simultaneous analysis of five selected pesticides. The optimal condition for the extraction of analytes was performed using 0.5 g of adsorbent to 50 mL of ultrapure water and eluted with 5 mL of acetonitrile. The biochar produced from coconut waste was tested as an adsorbent for the extraction by SPE and showed good recovery results between 75% ± 9 - 119 ± 12% for the concentration levels of 0.5 to 1 ug mL-1. The parameters studied to validate the method were: linearity and sensitivity, obtaining a good sensitivity and linear response with 0.9998 coefficients in the range of 0.01 to 10 ug mL-1; precision based on the precision of measurements (Intra) and intermediate precision (interday), obtaining results of 0.1-1%, 0.6-1%, respectively; accuracy with recovery values of 60 ± 37% - 117 ± 3% to the concentration levels of from 0.025 to 0.1 mg L-1 and 75 ± 9% - 119 ± 12% for levels 0.5 to 1 ug mL- 1 related to the biochar and C18, respectively. The LD 0.01 to 0.025 in range and LQ from 0.025 to 0.5 ug mL-1. The method developed was adequate for the determination of pesticides in water samples. / A poluição aquática provoca mudanças nas características físicas, químicas e biológicas das águas, as quais interferem na sua qualidade, impossibilitando o seu uso para o consumo humano. A maioria dos contaminantes químicos presentes em águas superficiais estão relacionados às fontes industriais e agrícolas. Uma vez que, com a atividade agrícola o Brasil polui os recursos hídricos existentes fazendo uso de agrotóxicos e fertilizantes. O presente trabalho tem como objetivo desenvolver um método rápido e eficiente baseado nas técnicas de extração em fase sólida (SPE) e cromatografia líquida de alta eficiência com detector espectrofotométrico na região do ultravioleta e visível com arranjo de diodos (HPLC UV-Vis/DAD) para a determinação dos agrotóxicos, perturbadores endócrinos, epoxiconazol, fenarimol, fenbuconazol, flusilazol, flutriafol, e vinclozolina, em água, utilizando biocarvões produzidos a partir de rejeitos de agroindústria, como adsorvente alternativo para a SPE. Testes realizados com os analitos permitiram o ajuste das condições cromatográficas para análise simultânea de cinco agrotóxicos selecionados. A condição ótima de extração dos analítos consistiu em utilizar 0,5 g do adsorvente para 50 mL de água ultrapurificada e eluição com 5 mL de acetonitrila. O biocarvão produzido a partir de rejeitos de coco foi testado como adsorvente para a extração por SPE e apresentou resultados satisfatórios de recuperação entre 75 ± 9% – 119 ± 12% para os níveis de concentração 0,5 a 1 μg mL-1. Os parâmetros estudados para a validação do método foram: linearidade e sensibilidade, obtendo-se uma boa sensibilidade e resposta linear com coeficientes de 0,9998 no intervalo de 0,01 a 10 μg mL-1; precisão com base nos estudos de repetibilidade (intradia) e precisão intermediária (interdia), obtendo-se resultados de 0,1–1%, 0,6–1%, respectivamente; exatidão com valores de recuperação entre 60 ± 37% – 117 ± 3%, para os níveis de concentração 0,025 a 0,1 μg mL-1 e 75 ± 9% – 119 ± 12% para os níveis 0,5 a 1 μg mL-1, com relação ao C18 e o biocarvão, respectivamente. O LD no intervalo de 0,01–0,025 e LQ 0,025-0,5 μg mL-1. O método desenvolvido se mostrou adequado para determinação de agrotóxicos em amostras de água.
327

Determinação espectrofotométrica do teor de biodiesel metílico em misturas com óleo diesel / Spectrophotometric determination of methyl biodiesel content in blends with diesel

SILVA, Marcos Alexandro Abreu e 25 November 2009 (has links)
Made available in DSpace on 2014-07-29T15:12:44Z (GMT). No. of bitstreams: 1 Dis Marcos Alexandro Abreu e Silva.pdf: 745368 bytes, checksum: 3b66fd4dbcdf1e21df44eb1b816fde53 (MD5) Previous issue date: 2009-11-25 / In this work it was developed a quantitative analytical methodology to determine the content of methyl biodiesel in diesel fuel through the fatty acid methyl ester reaction with the hydroxylamine hydrochloride in alkaline solutions, which they were acidified and converted to hydroxamic acids, followed by treatment with ferric ion to give the colored ferric hydroxamate complex, and afterwards extract in n-heptane and were analysed by UV-visible spectroscopy. It was made the optimization of the variables that interfere in the reaction, and parameters such as accuracy, precision and the limit of detection (LOD) among other parameters to assess the quality of the method developed it was also evaluated. The results indicated that the method has shown an excellent linearity in small intervals of biodiesel blend levels, an excellent determination coefficient of the calibration curve (R2 > 0.99) at a wide range of wavelength (420-440 nm). As well as it has also shown to be applied in a wide range of methyl biodiesel blend levels in diesel fuel (B1 to B20), and it is suitable to be used in the quality control procedures for the production of BX blends. / Desenvolveu-se neste trabalho uma metodologia analítica quantitativa para determinação do teor de biodiesel metílico em óleo diesel por meio da reação dos ésteres metílicos de ácidos graxos com o cloridrato de hidroxilamina em meio alcalino, os quais são acidificados e convertidos à ácidos hidroxâmicos, seguida pelo tratamento com íons ferro (III) resultando em complexos coloridos de hidroxamato férrico, posteriormente extraídos em n-heptano e analisados por espectroscopia de UV-visível. Fez-se a otimização das variáveis que interferem na reação, e também avaliou-se a exatidão, precisão, e o limite de detecção (LD), entre outros parâmetros, no sentido de avaliar a qualidade do método desenvolvido. O método mostrou excelente linearidade em pequenos intervalos de variação volumétrica de biodiesel, excelente coeficiente de correlação para a curva de calibração (R2 > 0,99), em uma ampla faixa de comprimento de onda (420 a 440 nm). Assim como mostrou ser aplicável em uma ampla faixa de teor de biodiesel metílico em óleo diesel (B1 ao B20), sendo adequado para o controle de qualidade da produção de misturas BX.
328

Photo-isomerization and photo-induced NO release in ruthenium nitrosyl compounds / Photo-isomérisation et libération photo-induite de NO radical dans de complexes de ruthénium à ligand nitrosyle

Khadeeva, Liya 13 October 2016 (has links)
Ce travail de thèse est centré sur l'étude expérimentale de deux types de transformations photo-induites observées dans différents complexes métalliques (Fe, Ru, ...) à ligand nitrosyle: (i) la photo-isomérisation au cours de laquelle le ligand NO passe d'un état lié par l'azote (M-NO, état stable GS) à un état lié par l'oxygène (M-ON, état métastable MSI). C'est un processus réversible et un second état métastable, 'side-on' MSII est observable au cours du processus inverse, MSI --> 'side-on' MSII --> GS; (ii) la libération photo-induite du radical NO°. La photo-isomérisation a été étudiée dans le système [Ru(py)_4Cl(NO)](PF_6)_2.1/2H_2O (sur monocristal) par la diffraction des RX, l'absorption visible statique et l'absorption UV-Vis résolue en temps. Nous avons pu mettre en évidence un processus d'absorption de photons (473 nm) en deux étapes, suivre la dynamique des transformations directes et inverses par l'évolution des paramètres de maille et des l'absorption optique visible, caractériser structuralement l'état 'side-on' MSII. La nature de l'état intermédiaire, MSII, lors du processus direct semble être différente de l'état 'side-on' mais la très faible population de cet intermédiaire n'a pas permis de trancher définitivement. Le rôle de la molécule d'eau dans la maille du complexe [Ru(py)_4Cl(NO)](PF_6)_2.1/2H_2O a été testé par diffraction des RX sur les échantillons hydratées, déshydratées et réhydratées. L'effet de déshydratation sur l'évolution des paramètres de maille et sur la génération d'espèces MSII au cours de la photo-commutation inverse, MSI --> MSII --> GS, est présenté. La libération photo-induite du radical NO° a été étudiée dans une solution d'acétonitrile du complexe trans-(Cl,Cl)[Ru^{II}(FT)Cl_2(NO)]PF_6 par spectroscopies d'absorption UV-Vis et Mi-IR, statiques et résolues en temps. En observant la dynamique ultra-rapide de la photo-transformation, nous avons mis en évidence un processus d'absorption de photons (406 nm) en deux étapes. La nature de l'état intermédiaire est discuté par rapport à de récents calculs théoriques et au processus de photo-isomérisation. / This Ph. D. thesis is focused on the experimental study of two photo-induced processes observed in various [ML_5NO] complexes, where M=Fe, Ru, ..., L=CN, Cl, ... : (i) photo-isomerization, where the system goes from N-bound state (M-NO, stable GS state) to O-bound state (M-ON, metastable MSI state) and a second metastable state, 'side-on' MSII is observed during the inverse photo-transformation, MSI --> 'side-on' MSII --> GS; (ii) photo-induced release of NO° radical. The photo-isomerization is investigated in single crystals of [Ru(py)_4Cl(NO)](PF_6)_2.1/2H_2O compound by means of X-Ray diffraction, steady state visible and time-resolved UV-visible absorption spectroscopies. During these experiments we observed the evidence of a two-step photon absorption process (473 nm), we followed the dynamics of direct and inverse photo-switching by the evolution of lattice parameters and absorption in the visible range and we caracterised the structure of 'side-on' MSII state. The nature of MSII in the direct photo-switching, GS --> MSI, seems to be different from the 'side-on' configuration, however, we do not have a direct access to this state due to its low population. The role of water molecule in the unit cell of [Ru(py)_4Cl(NO)](PF_6)_2.1/2H_2O complex was tested by X-Ray diffraction studies on hydrated, dehydrated and rehydrated samples. The effect of sample dehydration on the unit cell parameters evolution and MSII species generation during the MSI --> MSII --> GS inverse photo-switching is presented. The photo-induced NO° release in trans-(Cl,Cl)[Ru^{II}(FT)Cl_2(NO)]PF_6 system in acetonitrile solution is studied by the UV-visible and mid-IR absorption spectroscopies, both steady state and time-resolved. By observing the ultra-fast dynamics of photo-transformation we evidenced a two-step photon absorption process (406 nm). The nature of intermediate state is discussed within the recent theoretical calculations and the photo-isomerization process.
329

Transfer of small molecules across membrane-mimetic interfaces

Velicky, Matej January 2011 (has links)
The presented thesis investigates the transfer of drug molecules across interfaces that mimic biological membrane barriers. The permeability of drug molecules across biological membrane mimics has been investigated in a novel artificial membrane permeation assay configuration using an in situ time-dependent approach and reproducible rotation of the membrane. A method to determine the membrane permeability from the knowledge of measured permeability and the applied stirring rate is presented. The initial transient of the permeation response, previously not observed in situ, is investigated and its importance in data evaluation is discussed. The permeability coefficients of 31 drugs are optimised for the conditions found in vivo and a correlation with the fraction absorbed in humans is presented. The evidence for ionic and/or ion-pair flux across the artificial membrane obtained from measurement of permeability at different pH is supported by the investigation of the permeation assay with external membrane polarisation. The permeability coefficient of the solute's anionic form is determined. Liquid/liquid electrochemistry has been used to study the transfer of ionized species across the interface between water and 1,2-dichloroethane. An alternative method to study the transfer of partially ionised drug molecules employing a rotating liquid/liquid interface is presented. In addition, a bipolar electrochemical cell with a rotating-disc electrode is developed and its properties investigated in order to verify the hydrodynamics of the rotating artificial membrane configuration. Finally, in support of the electrochemical techniques used is this thesis, a detailed preparation and evaluation of the silver/silver sulphate reference electrode is presented.
330

Bioflavouring piv pomocí studeného chmelení za použití českých chmelů / Beer bioflavouring by dry hopping using czech cultivars of hops

Gajdušek, Martin January 2021 (has links)
This diploma thesis deals with the influence of dry hopping on selected analytical and sensory properties of beer. The effect of dry hopping was observed using Czech hop varieties Kazbek and Uran, which were added to the wort during the main fermentation phase in doses of 3 and 6 gdm-3. The contact time of hops with wort was 3, 6 and 9 days. The experimental part describes the technology of preparation of the reference beer, in which dry hopping were subsequently performed. A parallel measurement was performed on each sample. In terms of the basic parameters of beer, the effect of dry hopping, especially its length, on the ethanol content was observed. With a longer period of dry hopping, the concentration of ethanol in beer increased. The higher alcohol concentration was also associated with a decrease in the apparent extract. In terms of color and pH of beer, the effect of dry hopping has not been proven. Elemental analysis performed by optical emission spectrometry with inductively coupled plasma revealed an increase in the concentration of calcium, magnesium, and iron due to dry hopping. No statistically significant difference was observed for manganese and barium compared to the reference. In terms of bitterness, a significant increase was identified in dry hopped beers compared to the reference, the value being dependent on the dose of hops used. The effect of the hop variety has not been proved. Concentrations of organic acids determined by ion-exchange chromatography with a conductivity detector were affected by dry hopping only in the case of lactic acid and acetic acid. An increase in lactic acid was observed compared to the reference, also related to the degree of fermentation. While in the acetic acid content the hop samples showed a lower concentration than the reference sample. The concentrations of myrcene, humulene and geraniol were determined by gas chromatography with a mass detector. These are volatile components of hop essential oils. Dry hopped samples recorded significantly higher concentrations of all aromatic substances compared to the reference. In terms of hop time, the highest concentrations were shown by samples hopped for three days. The results of the sensory analysis show that the overall best rated sample is a sample hopped with the Kazbek variety with a dose of 3 gdm-3 for three days. Beer which was dry hopped for the shortest time also showed the lowest intensity of bitterness, which was perceived positively.

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