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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.
191

Oxidação quimiluminescente do luminol em meios micelares: desenvolvimento de uma ensaio para determinação da capacidade anti-radicalar / Chemiluminescent oxidation of luminol in micellar media: development of an anti-radical capacity assay

Cerize da Silva Santos 16 October 2008 (has links)
Neste trabalho foi desenvolvida uma metodologia para a determinação da capacidade anti-radicalar de substâncias hidrofílicas e lipofílicas baseada na quimiluminescência do luminol em meio micelar. A reação de luminol, hemina e peróxido de hidrogênio foi estudada na presença de tensoativos carregados (CTAB/CTAC e SDS). Variou-se independentemente a concentração de cada reagente de forma a avaliar seu papel sobre a intensidade inicial de emissão (I0), que é proporcional à velocidade inicial da reação. Em solução aquosa de SDS, a I0 apresentou correlação linear com a concentração de H2O2 entre 5,0 10-6 e 6,0 10-5 mol/L e com a concentração de hemina no intervalo de 8,0 10-9 a 4,0 10-7 mol/L. O aumento da concentração de luminol no intervalo de 5,0 10-7 a 1,0 10-3 provocou aumento na I0 até 5,0 10-5 mol/L, permanecendo constante para concentrações maiores. Na presença de CTAB, o valor de I0 variou linearmente com a concentração de H2O2 no intervalo estudado (2,0 10-5 a 6,7 10-4 mol/L). A I0 aumentou com o aumento da concentração da hemina entre 8,0 10-8 e 8,0 10-6 mol/L. A variação da concentração de luminol de 5,0 10-7 a 5,0 10-5 também provocou aumento na I0, a qual ficou constante para concentrações maiores. Para este tensoativo foram realizadas também medidas de cmc nas condições de reação (tampão fosfato pH 11,6 e µ = 0,1), obtendo-se um valor de 2 10-4 mol/L, cinco vezes menor do que a cmc em água. As mudanças espectrais de hemina e luminol em diferentes concentrações de CTAB foram avaliadas, obtendo-se evidências da interação destes reagentes com o tensoativo. Destes estudos, foi possível compreender melhor o comportamento do sistema e foram encontradas condições nas quais se obtêm decaimento lento da intensidade de emissão e I0 alto. Estas condições são ideais para a realização de um ensaio de determinação da capacidade anti-radicalar. O efeito do antioxidante trolox, utilizado como padrão, foi avaliado nestas condições nos sistemas baseados nos três tensoativos. Em todos os casos, observou-se correlação linear entre a concentração de trolox e a área suprimida na cinética de emissão, a qual é proporcional ao número de radicais seqüestrados pelo antioxidante. Os limites de detecção para trolox ficaram abaixo de 1,0 10-7 mol/L, e a faixa de linearidade é de no mínimo uma ordem de grandeza (não foram testadas concentrações superiores a 2,0 10-6 mol/L). No meio de reação com CTAB foram determinadas as capacidades anti-radicalares (n) dos seguintes antioxidantes: vitamina E (n=3,5 ± 0,1), rutina (n=4,0 ± 0,2), quercetina (n=3,8 ± 0,4) e ácido úrico (n=1,3 ± 0,1). Os valores de n determinados com este método foram muito similares com aqueles medidos utilizando-se o ensaio com o radical estável DPPH. Portanto, o ensaio desenvolvido com luminol em meio micelar se mostrou adequado para testar tanto substâncias hidrossolúveis como lipossolúveis. Foram testadas condições para a realização de ensaios consecutivos com injeções repetidas de várias alíquotas de antioxidante na presença de CTAB. Os valores encontrados com o ensaio realizado desta forma foram iguais aos obtidos com o ensaio onde as injeções são feitas individualmente. Este método permite automação e resulta na economia de reagentes e redução do tempo de ensaio / In this work, a methodology to evaluate the anti-radical capacity of hydrophilic and lipophilic compounds based on luminol chemiluminescence in micellar media was developed. The reaction of luminol, hemin and hydrogen peroxide was studied in the presence of charged surfactants (CTAB/CTAC and SDS). The concentration of each reagent was independently varied in order to evaluate its influence on the initial emission intensity (I0), which is proportional to the initial reaction rate. In aqueous SDS solution, I0 showed a linear correlation with the H2O2 concentration between 5,0 10-6 and 6,0 10-5 mol/L, and with the hemin concentration between 8,0 10-9 and 4,0 10-7 mol/L. An increase in the luminol concentration between 5,0 10-7 and 1,0 10-3 mol/L led to an increase in I0 up to 5,0 10-5 mol/L, higher luminol concentrations do not further increased I0. In the presence of CTAB, I0 increased linearly with the H2O2 concentration in the interval studied (2,0 10-5 to 6,7 10-4 mol/L). An increase in I0 was also observed on increasing the hemin concentration from 8,0 10-8 to 8,0 10-6 mol/L. An increase of the luminol concentration from 5,0 10-7 to 5,0 10-5 increased the observed I0, which did not change for higher luminol concentrations. The cmc of CTAB was measured in the reaction conditions (phosphate buffer pH 11,6 and µ= 0,1), and the value determined, 2 10-4 mol/L, was five times lower than the cmc in water. The absorption spectra of hemin and luminol in different CTAB concentrations showed significant variation with the surfactant concentration, indicating an interaction between these reagents and the surfactant. With these studies it was possible to understand well the behavior of the system and to establish experimental conditions which lead to kinetic curves with a slow emission intensity decay and relatively high I0, ideal conditions for the performance of the anti-radical capacity assay. The effect of trolox, the antioxidant used as reference, was evaluated in this conditions in the systems based on the three surfactants. In all the cases a linear correlation between the trolox concentration and the suppressed area in the emission kinetics was observed. This area is proportional to the number of radicals trapped by the antioxidant. Detection limits for trolox were below 1,0 10-7 mol/L, and the linear range was at least one order of magnitude (concentrations higher than 2,0 10-6 mol/L were not evaluated). The antioxidant capacity (n) was determined in the reaction medium containing CTAB for vitamin E (n= 3,5 ± 0,1), rutin (n=4,0 ± 0,2), quercetin (n=3,8 ± 0,4) and uric acid (n=1,3 ± 0,1). The n values determined by this method were very similar to those measured with the DPPH assay. Hence, the assay developed with luminol in micelar media was adequate to evaluate the anti-radical capacity of hidrosoluble as well as liposoluble compounds. The assay conditions established in the presence of CTAB allowed the consecutive injection of antioxidant samples during the same kinetic run. The values determined in this consecutive injection assay proved to be very similar to those obtained in the assay where injections were made individually. This method allows automation, economy of reagents and reduction of assay time
192

Oxidação quimiluminescente do luminol em meios micelares: desenvolvimento de uma ensaio para determinação da capacidade anti-radicalar / Chemiluminescent oxidation of luminol in micellar media: development of an anti-radical capacity assay

Santos, Cerize da Silva 16 October 2008 (has links)
Neste trabalho foi desenvolvida uma metodologia para a determinação da capacidade anti-radicalar de substâncias hidrofílicas e lipofílicas baseada na quimiluminescência do luminol em meio micelar. A reação de luminol, hemina e peróxido de hidrogênio foi estudada na presença de tensoativos carregados (CTAB/CTAC e SDS). Variou-se independentemente a concentração de cada reagente de forma a avaliar seu papel sobre a intensidade inicial de emissão (I0), que é proporcional à velocidade inicial da reação. Em solução aquosa de SDS, a I0 apresentou correlação linear com a concentração de H2O2 entre 5,0 10-6 e 6,0 10-5 mol/L e com a concentração de hemina no intervalo de 8,0 10-9 a 4,0 10-7 mol/L. O aumento da concentração de luminol no intervalo de 5,0 10-7 a 1,0 10-3 provocou aumento na I0 até 5,0 10-5 mol/L, permanecendo constante para concentrações maiores. Na presença de CTAB, o valor de I0 variou linearmente com a concentração de H2O2 no intervalo estudado (2,0 10-5 a 6,7 10-4 mol/L). A I0 aumentou com o aumento da concentração da hemina entre 8,0 10-8 e 8,0 10-6 mol/L. A variação da concentração de luminol de 5,0 10-7 a 5,0 10-5 também provocou aumento na I0, a qual ficou constante para concentrações maiores. Para este tensoativo foram realizadas também medidas de cmc nas condições de reação (tampão fosfato pH 11,6 e µ = 0,1), obtendo-se um valor de 2 10-4 mol/L, cinco vezes menor do que a cmc em água. As mudanças espectrais de hemina e luminol em diferentes concentrações de CTAB foram avaliadas, obtendo-se evidências da interação destes reagentes com o tensoativo. Destes estudos, foi possível compreender melhor o comportamento do sistema e foram encontradas condições nas quais se obtêm decaimento lento da intensidade de emissão e I0 alto. Estas condições são ideais para a realização de um ensaio de determinação da capacidade anti-radicalar. O efeito do antioxidante trolox, utilizado como padrão, foi avaliado nestas condições nos sistemas baseados nos três tensoativos. Em todos os casos, observou-se correlação linear entre a concentração de trolox e a área suprimida na cinética de emissão, a qual é proporcional ao número de radicais seqüestrados pelo antioxidante. Os limites de detecção para trolox ficaram abaixo de 1,0 10-7 mol/L, e a faixa de linearidade é de no mínimo uma ordem de grandeza (não foram testadas concentrações superiores a 2,0 10-6 mol/L). No meio de reação com CTAB foram determinadas as capacidades anti-radicalares (n) dos seguintes antioxidantes: vitamina E (n=3,5 ± 0,1), rutina (n=4,0 ± 0,2), quercetina (n=3,8 ± 0,4) e ácido úrico (n=1,3 ± 0,1). Os valores de n determinados com este método foram muito similares com aqueles medidos utilizando-se o ensaio com o radical estável DPPH. Portanto, o ensaio desenvolvido com luminol em meio micelar se mostrou adequado para testar tanto substâncias hidrossolúveis como lipossolúveis. Foram testadas condições para a realização de ensaios consecutivos com injeções repetidas de várias alíquotas de antioxidante na presença de CTAB. Os valores encontrados com o ensaio realizado desta forma foram iguais aos obtidos com o ensaio onde as injeções são feitas individualmente. Este método permite automação e resulta na economia de reagentes e redução do tempo de ensaio / In this work, a methodology to evaluate the anti-radical capacity of hydrophilic and lipophilic compounds based on luminol chemiluminescence in micellar media was developed. The reaction of luminol, hemin and hydrogen peroxide was studied in the presence of charged surfactants (CTAB/CTAC and SDS). The concentration of each reagent was independently varied in order to evaluate its influence on the initial emission intensity (I0), which is proportional to the initial reaction rate. In aqueous SDS solution, I0 showed a linear correlation with the H2O2 concentration between 5,0 10-6 and 6,0 10-5 mol/L, and with the hemin concentration between 8,0 10-9 and 4,0 10-7 mol/L. An increase in the luminol concentration between 5,0 10-7 and 1,0 10-3 mol/L led to an increase in I0 up to 5,0 10-5 mol/L, higher luminol concentrations do not further increased I0. In the presence of CTAB, I0 increased linearly with the H2O2 concentration in the interval studied (2,0 10-5 to 6,7 10-4 mol/L). An increase in I0 was also observed on increasing the hemin concentration from 8,0 10-8 to 8,0 10-6 mol/L. An increase of the luminol concentration from 5,0 10-7 to 5,0 10-5 increased the observed I0, which did not change for higher luminol concentrations. The cmc of CTAB was measured in the reaction conditions (phosphate buffer pH 11,6 and µ= 0,1), and the value determined, 2 10-4 mol/L, was five times lower than the cmc in water. The absorption spectra of hemin and luminol in different CTAB concentrations showed significant variation with the surfactant concentration, indicating an interaction between these reagents and the surfactant. With these studies it was possible to understand well the behavior of the system and to establish experimental conditions which lead to kinetic curves with a slow emission intensity decay and relatively high I0, ideal conditions for the performance of the anti-radical capacity assay. The effect of trolox, the antioxidant used as reference, was evaluated in this conditions in the systems based on the three surfactants. In all the cases a linear correlation between the trolox concentration and the suppressed area in the emission kinetics was observed. This area is proportional to the number of radicals trapped by the antioxidant. Detection limits for trolox were below 1,0 10-7 mol/L, and the linear range was at least one order of magnitude (concentrations higher than 2,0 10-6 mol/L were not evaluated). The antioxidant capacity (n) was determined in the reaction medium containing CTAB for vitamin E (n= 3,5 ± 0,1), rutin (n=4,0 ± 0,2), quercetin (n=3,8 ± 0,4) and uric acid (n=1,3 ± 0,1). The n values determined by this method were very similar to those measured with the DPPH assay. Hence, the assay developed with luminol in micelar media was adequate to evaluate the anti-radical capacity of hidrosoluble as well as liposoluble compounds. The assay conditions established in the presence of CTAB allowed the consecutive injection of antioxidant samples during the same kinetic run. The values determined in this consecutive injection assay proved to be very similar to those obtained in the assay where injections were made individually. This method allows automation, economy of reagents and reduction of assay time
193

Couches chimiluminescentes de Langmuir­-Blodgett pour une détection sans marquage basée sur une intéraction type métal / chélate / Langmuir-Blodgett chemiluminescent layers for a label-free detection based on metal / chelate interaction

Santafe, Aurélie 08 October 2010 (has links)
Une nouvelle méthode de détection sans marquage des interactions biomoléculaires a été développée. Elle est basée sur la conception d’une couche sensible supportée innovante réalisée par la technique de Langmuir‐Blodgett. Cette couche est composée d'un lipide à tête polaire immobilisant un cation métallique divalent capable (i) de chélater une molécule possédant une affinité pour ce type de cation et (ii) de catalyser la réaction de chimiluminescence du luminol. L'intensité du signal chimiluminescent est modulée par la présence de biomolécules fixées en surface de la couche sensible, qui modifient l'environnement immédiat du cation métallique. La variation du signal chimiluminescent (issu de la catalyse par le cation immobilisé) a pu être quantifiée et corrélée à une gamme de concentration d’histamine et d’anticorps. Les potentialités de cette approche ont finalement été exploitées pour développer une puce de PMMA de type macropuce immobilisant la monocouche de lipides. / A new label‐free detection method for biomolecular interactions was developed. It is based on the development of an original sensitive layer performed with the Langmuir‐ Blodgett technique. This layer is composed of a lipid which immobilized a bivalent metallic cation on his polar head, able (i) to chelate a molecule which has an affinity for this cation and (ii) to catalyze the luminol chemiluminescent reaction. The chemiluminescent signal intensity is modulated by the presence of immobilized biomolecules on the sensitive layer surface, which modifies the immediate environmentof the metallic cation. The chemiluminescent signal variation (from catalysis by the metallic cation) has been quantified and correlated to a histamine and antibody concentration range. The potentialities of this approach have finally been employed to achieve a PMMA chip (macroarray type), immobilizing the lipid monolayer.
194

Salt stress in rice : adaptive mechanisms for cytosolic sodium homeostasis /

Kader, Md. Abdul, January 2006 (has links) (PDF)
Diss. (sammanfattning) Ultuna : Sveriges lantbruksuniv., 2006. / Härtill 4 uppsatser.
195

Determinação quimiluminescente de ferro em óleos baseado em pontos quânticos de CdTe usando um sistema fluxo-batelada com extração em fase única e imagens digitais

Lima, Marcelo Batista de 25 April 2014 (has links)
Made available in DSpace on 2015-05-14T13:21:34Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4173293 bytes, checksum: b97bdde9738a247557cc099fc80a29af (MD5) Previous issue date: 2014-04-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, a novel chemiluminescence method using flow-batch analysis for the determination of iron in viscous samples (edible oil, lubricating oil and biodiesel) employing cadmium telluride quantum dots (CdTe QDs) with detection by digital images from webcam was developed. The analytical method proposed a novel strategy includes a pretreatment of the sample that constitutes on-line availability of total iron by acid extraction in one step. In the automatic pre-treatment, a new strategy was developed for chemiluminescent emission, whereby the available analyte was oxidized to Fe(III) in the presence of dichromate ions and reduced to Fe(II) by direct oxidation of CdTe QDs, allowing promote chemiluminescent emission of these nanocrystals. The influence of the size and concentration QDs in this system was estimated revealing a higher sensitivity and selectivity for the small crystals obtained (1.65 nm). Concerning the flow-batch analysis a new mixing chamber was developed in polytetrafluoroethylene (PTFE) provided with quartz windows in order to allow luminescent probes online. A novel management program the automatic system was developed enabling rapid acquisition and efficient handling of digital images without the need to use another program to tratamendo the information obtained. For the construction of the analytical curve-based mathematical model in the RGB color values was used, therefore, considered the norm of vectors in response. The limit of detection and relative standard deviation were calculated to be 0.66 μg mL 1 and < 1.5 % (n = 3), respectively. The analysis of interfering was successful for the major ions present in solution, revealing significant percentage interference (≤ 5 %). The precision of the method was evaluated by recovery test (97.5 to 103.3 %). The robustness of the method was evaluated by intra- and inter- day comparison of the results obtained and using the reference method with detection by atomic absorption graphite furnace at a 95% level of statistical confidence. Finally, the system showed quite satisfactory analytical frequency (43 h 1) and considerably reducing the consumption of chemicals. Thus, it is demonstrated appreciably the viability of new chemiluminescent method, thus allowing the development of new analytical strategies employing potentially useful quantum dots, automation and digital images. / Neste trabalho de pesquisa foi desenvolvido um novo método quimiluminescente em fluxo-batelada para determinação de ferro total em matrizes viscosas (óleo comestível, óleo lubrificante e biodiesel) empregando pontos quânticos de telureto de cádmio (PQs de CdTe) com detecção por imagens digitais via webcam. O método analítico proposto inclui uma nova estratégia de pré-tratamento da amostra que consiste na disponibilização on-line do ferro total por meio de extração ácida em fase única. Além do pré-tratamento automático, uma nova estratégia para emissão quimiluminescente foi desenvolvida, através da qual todo o analito disponível foi oxidado para Fe(III) na presença de íons dicromato e reduzido para Fe(II) mediante o processo de oxidação direta dos PQs de CdTe, o que permitiu promover a emissão quimiluminescente desses nanocristais. A influência do tamanho e concentração dos PQs nesse sistema foi avaliada revelando uma maior sensibilidade e seletividade para os cristais obtidos de menor dimensão (1,65 nm). Concernente ao sistema automático fluxo-batelada uma nova câmara de mistura foi desenvolvida em politetrafluoretileno (PTFE) provida de janelas de quartzo com o objetivo de permitir detecções luminescentes on-line. Um novo programa de gerenciamento do sistema automático foi desenvolvido permitindo uma rápida aquisição e eficiente tratamento das imagens digitais, sem a necessidade de empregar qualquer outro programa para o tratamento da informação obtida. Para a construção da curva analítica foi utilizado um modelo matemático baseado nos valores de cor RGB, sendo assim, considerada a norma dos vetores como resposta. O limite de detecção e o desvio padrão relativo foram calculados em 0,66 μg L 1 e < 1,5 % (n = 3), respectivamente. A análise de interferentes foi realizada com êxito para os principais íons presentes em solução, não revelando interferência percentual significativa (≤ 5%). A exatidão do método foi avaliada através do teste de recuperação (97,5 103,3 %). A robustez do método foi avaliada por comparação intra- e inter-dia dos resultados obtidos e empregando o método de referência com detecção por absorção atômica em forno de grafite em um nível de 95% de confiança estatística. Por fim, o sistema apresentou frequência analítica bastante satisfatória (43 h 1) e redução considerável do consumo de produtos químicos. Desta forma, é demonstrado de modo apreciável a viabilidade do novo método quimiluminescente, permitindo assim, o desenvolvimento de novas estratégias analíticas potencialmente úteis empregando pontos quânticos, automação e imagens digitais.
196

Estudo dos mecanismos de quimi-excitação na decomposição induzida de peróxidos: uma comparação entre sistemas inter e intramoleculares / Studies on the chemiexcitation mechanisms in induced peroxide decomposition: a comparison of inter and intramolecular systems

Marcelo Almeida de Oliveira 18 May 2007 (has links)
Foram sintetizados, purificados e caracterizados os peróxidos cíclicos: peróxido de difenoíla (1), dimetil-1,2-dioxetanona (2), e spiro-adamantil &#945;-peróxi lactona (3), e determinados seus parâmetros de quimiluminescência. Foram redeterminados os rendimentos quânticos singlete na decomposição catalisada de 1 e 2 em condições análogas as utilizadas anteriormente na literatura, obtendo-se valores várias ordens de grandeza menores que os inicialmente relatados para estes sistemas padrão para a formulação do mecanismo Luminescência Iniciada Quimicamente por Troca de Elétron (Chemically Initiated Electron Exchange Luminescence - CIEEL). O efeito de gaiola de solvente, utilizando-se o sistema binário tolueno/difenilmetano, sobre o rendimento quântico na decomposição de 1 catalisada por rubreno, mostrou-se consideravelmente menor para este sistema intermolecular do que o observado no sistema intramolecular da decomposição induzida de 1,2-dioxetanos fenóxi-substituidos. Foram determinados pela primeira vez os parâmetros de quimiluminescência na decomposição unimolecular e catalisada da spiro-adamantil &#945;-peróxi lactona (3), mostrando que esta é a &#945;-peróxi lactona mais estável sintetizada e estudada até o momento. Este peróxido é sujeito à decomposição catalisada por ativadores adequados, envolvendo transferência de elétron, porém, com eficiência baixa devido a um impedimento estérico exercido pelo substituinte spiro-adamantila sobre a interação do peróxido com o ativador. O rendimento quântico singlete máximo obtido na decomposição catalisada de 3 é de 1%, valor consideravelmente menor que os determinados para sistemas intramoleculares. A decomposição dos peróxidos cíclicos 1 a 3 é catalisada por fenolatos como ativadores, porém, os rendimentos singlete obtidos nesta reação são baixos, entre 10-3 e 10-7 E mol-1. Os resultados obtidos com este sistema modelo intermolecular para a decomposição induzida por transferência intramolecular de elétron de 1,2-dioxetanos fenóxi-substituidos, demonstram claramente que esta última transformação quimiluminescente de alta eficiência deve ocorrer por uma retro-transferência de elétron intramolecular e não intermolecular como proposto na literatura, e como é necessariamente o caso no sistema modelo estudado no presente trabalho. / The cyclic peroxides diphenoyl peroxide (1), dimethyl-1,2-dioxetanone (2) and spiro-adamantyl &#945;-peroxy lactone (3) were synthesized, purified and characterized, as well as its chemiluminescence parameters determined. The singlet quantum yields in the catalyzed decomposition of 1 and 2 were re-determined in experimental conditions equivalent to those formerly utilized in the literature, obtaining values various orders of magnitude lower than the ones initially reported for these model systems for the formulation of the Chemically Initiated Electron Exchange Luminescence\" (CIEEL) mechanism. The solvent-cage effect on the singlet quantum yields in the rubrene catalyzed decomposition of 1, using the binary system toluene / diphenylmethane, showed to be considerably lower for this intermolecular system than the one observed in the intramolecular system of the induced phenoxy-substituted 1,2-dioxetane decomposition. The chemiluminescence parameters in the unimolecular and catalyzed spiro-adamantyl &#945;-peroxylactone (3) decomposition were determined for the first time, showing that 3 is the most stable &#945;-peroxylactone synthesized and studied up to now. This peroxide is subject to catalyzed decomposition by appropriate activators involving electron transfer, however, with low efficiency due to the steric effect of the spiro-adamantyl substituents on the interaction of the peroxide with the activator. The maximum singlet quantum yield obtained in the catalyzed decomposition of 3 is 1 %, a value considerably lower than those determined for intramolecular systems. The decomposition of the cyclic peroxides 1 to 3 is catalyzed by fenolato ions as activators, thus the singlet quantum yields measured for this reaction are low, between 10-3 e 10-7 E mol-1. The results obtained for this intermolecular model system for the induced phenoxy-substituted 1,2-dioxetane decomposition demonstrate clearly that the latter highly efficient chemiluminescent transformation should occur by an intramolecular back-electron transfer and not by an intermolecular one as proposed in the literature, and as is necessarily the case in the model system studied in this work.
197

Ultraschallunterstützte Kupferabscheidung / Ultrasound assisted copper deposition

Kauer, Markus 26 April 2017 (has links)
No description available.
198

Immobilisation d'hydrogel redox pour la détection par électrochimiluminescence / Electrogenerated chemiluminescence detection based on advanced immobilised redox hydrogel

Milutinovic, Miléna 16 December 2011 (has links)
Ce travail de thèse a pour objectif l’étude de l’électrochimiluminescence (ECL) et son application pour le développement de nouvelles techniques analytiques. De par son importante sensibilité, l’ECL est une technique performante pour des applications telles que les diagnostics cliniques ou la chimie environnementale (présence d’agents contaminants dans l’eau ou la nourriture). L’immobilisation du luminophore ECL est réalisée généralement sur une phase solide. Cette étape constitue une phase essentielle pour obtenir une méthode d’immobilisation rapide, simple, flexible et efficace de ces luminophores ECL, tout en permettant une utilisation pour des systèmes variés. La première partie de ce travail présente l’optimisation de la déposition électrochimique de films de métallopolymère de ruthénium et son application pour la détection enzymatique. Un film d'épaisseur micrométrique de cet hydrogel redox a été préparé par voltamétrie cyclique. Cet hydrogel immobilisé a permis la détection d’un substrat modèle (le glucose) en utilisant l'enzyme glucose déshydrogénase. La seconde partie se concentre sur le développement d’une nouvelle méthode de photodéposition d’un polymère. Celle-ci permet l’immobilisation de centres actifs sur des régions sélectives. En utilisant les techniques de photolithographie, les figures du masque sont projetées sur la surface des électrodes. Cela permet la réalisation de spots micrométriques dont la taille, forme et épaisseur sont modulables. Les propriétés électrochimiques des films nanométriques obtenus sont comparables à ceux obtenues par électrodéposition. De même, les spectres ECL réalisés avec polymères immobilisés par ces deux stratégies sont identiques. Ces résultats montrent que les états excités induits lors de l’ECL sont identiques avec les deux techniques d’immobilisation. Le développement d'un tel procédé constitue une alternative prometteus pour la réalisation de réseaux de spots ECL différenciés et permettant la détection multipléxée par imagerie ECL. Dans la troisième partie de ce travail, nous avons associé la spectroélectrochimie et l'imagerie ECL pour contribuer à l’étude des mécanismes ECL au niveau d'une bille micrométrique fonctionnalisée par des complexes de ruthénium. En combinant microscopie de fluorescence et imagerie ECL, la distribution des sites électroactifs et des sites ECL a pu être mise en évidence. A partir de cette étude, nous pouvons clarifier les mécanismes conduisant à l'émission ECL au niveau de ces billes fonctionnalisées. / The main goal of this thesis was to study electrogenerated chemiluminescence (ECL) and its application in development of new analytical techniques. Due to its high sensitivity, ECL presents a powerful method for applications in clinical diagnostic and environmental chemistry (presence of contaminants in water or food). The immobilisation of an ECL luminophore is usually performed on a solid phase. This step is an essential point to obtain a technique for fast, simple, flexible and effective immobilisation of ECL luminophores with possibility of applications in various configurations. The first part of this work presents the optimisation of the electrochemical deposition of a ruthenium metallopolymer and its application in enzymatic detection. A redox hydrogel film with micrometric thickness was prepared using cyclic voltammetry. This immobilised hydrogel allows the detection of model substrate (glucose) using enzyme glucose dehydrogenase. The second part of this thesis is focused on the development of a new photodeposition method for the ECL polymer immobilisation. This method allows region-selective immobilisation of active centres. Using photolithographic methods, the figures from the mask are projected on the electrode surface. This allows the formation of micrometric spots which size, shape and thickness is modulated. Electrochemical properties of obtained nanometric films are comparable with those of electrodeposited films. Also, ECL spectra recorded with both immobilisation strategies are identical. It shows that the ECL excited state is the same. The obtained photopatterns were imaged using ECL. The development of such process presents an alternative for realisation of different ECL spot arrays and allows multiplexed detection by ECL imaging. In the third part of this work we have associated spectroelectrochemistry and ECL imaging to study the ECL mechanisms at the level of a single microbead, functionalised with ruthenium complex. Combining fluorescence microscopy and ECL imaging, the distribution of electroactive and ECL sites have been highlighted. From this study we can clarify the mechanism that leads to ECL emission at the level of functionalised beads.
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Non-Lethal Methods for Assessing Reproductive Status in Bonnethead Sharks (Sphyrna tiburo)

Anderson, Brenda Carol 01 January 2015 (has links)
Reproductive biology is a necessary element for the management of elasmobranch fisheries. Traditionally, characterization of elasmobranch reproduction has involved lethal sampling to examine gross reproductive structures and development of embryos. However, this method is counterproductive to the conservation of shark populations. One non-lethal alternative is the measurement of serum hormones, which often vary according to reproductive events. Radioimmunoassay (RIA) has been used to measure hormone concentrations in reproductive endocrinology, but can be problematic for researchers. Alternatively, chemiluminescence immunoassays (CLIA) are routinely used for measuring circulating hormone concentrations in low-volume, non-extracted human serum samples. However these assays have not been previously examined for use with elasmobranch blood. In the first component of this study, I examined whether CLIA was a suitable alternative for detecting seasonal profiles of these hormones in the bonnethead, Sphyrna tiburo. This was accomplished by collecting serum from sexually mature male (n = 35) and female (n = 32) bonnetheads , measuring reproductive organs for maturity and reproductive stage, and measuring concentrations of testosterone (T) in males, and 17β-estradiol (E2) and progesterone (P4) in females using RIA and CLIA. CLIA was successfully validated for use with shark serum by assessing parallelism and spike recovery. CLIA-derived measurements were significantly correlated with those obtained with RIA (r = 0.809, 0.773, and 0.908 for T, E2, and P4, respectively; p
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Développement de sondes chimiluminescentes pour la détection d'activités enzymatiques / Development of chemiluminescent probes for the detection of enzymatic actvity

Solmont, Kathleen 16 March 2018 (has links)
Depuis plusieurs années, il est devenu plus aisé de détecter et d’étudier les mécanismes biologiques in cellulo grâce aux techniques d’imagerie optique que sont la fluorescence, la bioluminescence et la chimiluminescence. Bien que la fluorescence soit la technique la plus employée de nos jours, la bioluminescence et la chimiluminescence, qui sont la conséquence d’une cascade de réactions (bio)chimiques, sont très étudiées depuis quelques décennies. En effet, elles permettent de contourner la source des problèmes rencontrés dans l’utilisation d’un fluorophore : la lumière excitatrice. La chimiluminescence est par conséquent une méthode de choix pour s’affranchir de l’auto-fluorescence tissulaire. Le 1,2-dioxétane est un des motifs chimiluminescent qui, par décomposition, peut générer un état excité sur un fluorophore auquel il est connecté, autorisant ainsi sa luminescence intrinsèque. Ainsi, le but de ce projet de thèse a été de développer et d’étudier des nouvelles sondes chémiluminescentes à motif 1,2-dioxétane à coeurs naphtolique et phénolique, compatibles avec le vivant pour une détection ciblée de complexes enzymatiques. La stratégie envisagée passait par la préparation d'une plateforme chimiluminescente comportant un motif 1,2-dioxétane thermiquement stable, sur laquelle il est possible de faire varier le déclencheur (i.e. possibilité d'adapter cette plateforme à l'analyte ou événement que l'on souhaite détecter) et d'accrocher un fluorophore NIR. Deux méthodes ont été tentées : d’une part une greffe d’une version hydrosoluble d’un fluorophore connu (i.e. le Nile red) pour réaliser un transfert d’énergie à travers les liaisons (i.e. TBET), et d’autre part un couplage à un complexe de lanthanide permettant un transfert d’énergie à travers l’espace (i.e. CRET). / Since several years, it is easier to exploit biological phenomena in cellulo through technologies dealing with bioimaging. This method gathers fluorescence, bioluminescence and chemiluminescence. Even though fluorescence is the most employed technic, bioluminescence and chemiluminescence, being the consequence of (bio)chemical reaction, have been widely studied for decades. In fact, they can avoid the main problems encountered in fluorophore use: exciting light. Chemiluminescence is thus the appropriate approach to avoid biological autofluorescence. 1,2-dioxetane is one of the moieties that, upon decomposition, can generate an excited state on a connected fluorophore, giving rise to its intrinsic luminescence. The aim of our project was to develop and study new 1,2-dioxetan chemiluminescent probes based on phenol or naphthol moieties, for targeted enzymatic complexes detection with in cellulo and in vivo bioimaging. The strategy relied on the synthesis of chemiluminescent scaffolds comprising thermally stable 1,2-dioxetan, on which the trigger and the connected NIR fluorophore can be easily diversified. Two methods have been attempted: 1) coupling to a water-soluble version of a known fluorophore (i.e. Nile red) allowing an energy transfer through bonds (i.e. TBET) 2) connection with a lanthanide complex giving rise to an energy transfer through space (i.e. CRET).

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