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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.
131

Etude chimiotaxonomique et activité biologique des métabolites secondaires des plantes du genre Eryngium / Chemotaxonomic study and biological activity of secondary metabolites of Eryngium species

Landoulsi, Ameni 20 December 2016 (has links)
Le genre Eryngium L. (Apiaceae, Saniculoideae) comprend plus de 250 espèces utilisées en médecine traditionnelle à travers le monde. En Tunisie il existe seulement huit espèces : E. barrelieri Boiss., E. campestre L., E. dichotomum Desf., E. glomeratum Lamk., E. ilicifolium Lamk., E. maritimum L., E. tricuspidatum L. et E. triquetrum Vahl. ; ces espèces sont en majorité peu étudiées du point de vue phytochimique. La présente étude a été effectuée sur la totalité des Eryngium qui poussent en Tunisie dans le but d’évaluer leurs activités biologiques, essentiellement antimicrobienne contre des microorganismes multirésistants et producteurs de béta-lactamases à spectres étendus (BLSE), mais aussi phototoxique et cytotoxique ainsi que la variabilité chimique par analyse par GC-FID et GC-MS des extraits les plus actifs.Toutes les espèces étudiées étaient dotées d’un pouvoir antimicrobien (1,25 à 0,07 mg/mL) et cytotoxique (24,4 à 0,32 µg/mL) considérable. Le criblage de l’activité phototoxique a permis de mettre en évidence la richesse de ces plantes en composés photoréactifs antimicrobiens potentiellement intéressants pour leur efficacité d’action et l’élargissement du spectre d’activité antimicrobienne.L’analyse des extraits actifs apolaires a permis d’étudier la variabilité chimique entre les différentes espèces et la mise en évidence de la présence majoritaire de composés antimicrobiens notamment des sesquiterpènes oxygénés tels que le spathulénol, le lédol, l’α-bisabolol et le cubénol, et des sesquiterpènes hydrocarbonés comme le β-bisabolène et le copaène ; et cytotoxiques tel que le falcarinol.Une étude phytochimique approfondie a été réalisée sur les racines d’E. triquetrum afin d’extraire, isoler par des essais bio-guidés et identifier les composés actifs. Le fractionnement a été optimisé par des chromatographies sur colonnes, CPC et CLHP. Parmi les composés identifiés deux polyacétylènes, le panaxydiol et le falcarinol, ont montré un fort pouvoir antimicrobien et une spécificité d’action notamment contre les souches de Pseudomonas aeruginosa BLSE et multirésistantes, avec des CMI allant jusqu’à 0,25 ng/mL et une activité en majorité bactéricide. / The genus Eryngium L., (Apiaceae, Saniculoideae) comprises more than 250 flowering plant species, which are commonly used as medicinal plants in different countries. Only eight species are growing in Tunisia: E. barrelieri Boiss., E. campestre L., E. dichotomum Desf., E. glomeratum Lamk., E. ilicifolium Lamk., E. maritimum L., E. tricuspidatum L. et E. triquetrum Vahl. These species are used in traditional medicine and there are relatively few papers on the phytochemical investigations of most of them. This study was performed on all Eryngium species growing in Tunisia in order to evaluate their chemical variability using GC-FID and GC-MS analyses and their biological activities, mainly antimicrobial against multiresistant microorganisms and extended spectrum beta-lactamase producing bacteria (ESBL), and also phototoxic and cytotoxic effects.All investigated species showed considerable antimicrobial effect with MIC value ranging between 1,25 and 0,07 mg/mL and important cytotoxic activity against J774 tumoral cells with IC50 from 24,4 to 0,32 µg/mL. Phototoxic investigation demonstrated a significant photoactive inhibitory effects against tested pathogenic microorganisms.GC–MS analysis of the most active crude extracts (petroleum ether extracts) revealed their high content of antimicrobial agents particularly oxygenated sesquiterpenes such as spathulenol, ledol, α-bisabolol and cubenol, and hydrocarbon sesquiterpenes such as β-bisabolene and copaene; and cytotoxic components such as falcarinol.The chemical investigation and bio-guided isolation of active compounds of the selected crude extract of E. triquetrum roots were performed using column chromatography, centrifugal partition chromatography (CPC) and preparative high-performance liquid chromatography (HPLC). among purified components, two bioactive polyacetylenes, panaxydiol and falcarinol, showed a great antimicrobial activity mainly against multiresistant and ESBL producing Pseudomonas aeruginosa with MIC value up to 0,25 ng/ml and a mostly bactericidal effect.
132

Potentialité de stockage de carbone dans les sols par apport de matières organiques exogènes

Peltre, Clément 19 November 2010 (has links) (PDF)
L'apport aux sols de matières organiques exogènes (MOEs) d'origine résiduaire issues d'activités agricoles, urbaines ou industrielles permet d'augmenter les teneurs en matière organique des sols (MOS) et d'améliorer leur fertilité. De plus ces apports de MOEs pourraient contribuer à la limitation des émissions nettes de gaz à effet de serre en stockant du C dans les sols. Le développement d'outils de prédiction est nécessaire pour une meilleure estimation du devenir à long terme des MOEs apportées. De plus, il est important de savoir sous quelles formes la matière organique (MO) des MOEs est incorporée dans la MO du sol, ceci conditionnant la pérennité des accumulations de C après apports répétés de MOEs. Cette étude vise à mieux comprendre et prédire la dynamique d'incorporation de la MO de matières organiques exogènes dans la matière organique du sol. Elle s'est déroulée en trois étapes : (i), le développement et l'amélioration de méthodes de caractérisation de laboratoire permettant d'estimer le devenir des MOEs dans le sol (ii) le paramétrage du modèle RothC pour simuler l'accumulation de C dans les sols suite à l'apport de MOEs et (iii) l'étude des changements de composition chimique de la MOS suite à des apports répétés de MOEs.<br />L'étude de la composition chimique de la fraction dite soluble du fractionnement biochimique Van Soest a révélé que la nature chimique de cette fraction de MO change lors du traitement par compostage des MOEs: elle est très riche en polysaccharides en début de compostage et s'enrichit en MO riche en composés azotés stabilisés au cours du compostage.<br />Le potentiel d'utilisation de la spectroscopie proche infra-rouge (SPIR) pour caractériser les MOEs et leur devenir dans le sol a été étudié. Des prédictions satisfaisantes ont été obtenues pour les teneurs en C et N des MOEs ainsi que pour les fractions biochimiques Van Soest des MOEs. L'indicateur de stabilité de la MO (ISMO), estimateur de la fraction résiduelle de la MO des MOEs à long terme dans les sols, a été prédit de manière satisfaisante.<br />La potentialité de stockage de C à long terme dans un sol soumis à des apports répétés de MOEs a été étudiée en utilisant des résultats de 4 essais au champ de moyenne et longue durées. les apports répétés de MOEs ont entrainé des augmentations significatives des stocks de C dans les sols qui ont pu être reproduites de façon satisfaisante avec le modèle RothC qui a été ainsi paramétrés pour pouvoir simuler des apports de MOEs de types divers.<br />L'étude des changements dans la composition de la MOS suite à ces apports répétés de MOEs dans l'essai Qualiagro a révélé une modification préférentielle de la fraction de MOS particulaire de taille > 50 µm, en particulier par un enrichissement en lignine. La composition de la fraction de taille 0-50 µm est également modifiée mais dans une moindre mesure et de façon moins directement liée à la composition des MOEs apportées.
133

A VFX ocean toolkit with real time preview

Rydahl, Björn January 2009 (has links)
No description available.
134

Gravity Control System: Realistic Balanced Poses and Animations

Remmers, Tobias January 2007 (has links)
<p>The Gravity Control for Maya will be extraordinary</p><p>beneficial to an animator trying to create realistic</p><p>animation, by calculating the center of gravity and area</p><p>of balance. This control will provide the animator with</p><p>the ability to rotate around the center of gravity and</p><p>keep the character in a balanced pose. With that ability,</p><p>the animator can easily create accurate poses and</p><p>animation, such as mid-air flips. The system also</p><p>supports a vast number of characters with different</p><p>shapes, sizes and number of limbs.</p>
135

Analog and Digital Approaches to UWB Narrowband Interference Cancellation

Omid, Abedi 02 October 2012 (has links)
Ultra wide band (UWB) is an extremely promising wireless technology for researchers and industrials. One of the most interesting is its high data rate and fading robustness due to selective frequency fading. However, beside such advantages, UWB system performance is highly affected by existing narrowband interference (NBI), undesired UWB signals and tone/multi-tone noises. For this reason, research about NBI cancellation is still a challenge to improve the system performance vs. receiver complexity, power consumption, linearity, etc. In this work, the two major receiver sections, i.e., analog (radiofrequency or RF) and digital (digital signal processing or DSP), were considered and new techniques proposed to reduce circuit complexity and power consumption, while improving signal parameters. In the RF section, different multiband UWB low-noise amplifier key design parameters were investigated like circuit configuration, input matching and desired/undesired frequency band filtering, highlighting the most suitable filtering package for efficient UWB NBI cancellation. In the DSP section, due to pulse transmitter signals, different issues like modulation type and level, pulse variety, shape and color noise/tone noise assumptions, were addressed for efficient NBI cancelation. A comparison was performed in terms of bit-error rate, signal-to-interference ratio, signal-to-noise ratio, and channel capacity to highlight the most suitable parameters for efficient DSP design. The optimum number of filters that allows the filter bandwidth to be reduced by following the required low sampling rate and thus improving the system bit error rate was also investigated.
136

Platform Independent Real-Time X3D Shaders and their Applications in Bioinformatics Visualization

Liu, Feng 12 January 2007 (has links)
Since the introduction of programmable Graphics Processing Units (GPUs) and procedural shaders, hardware vendors have each developed their own individual real-time shading language standard. None of these shading languages is fully platform independent. Although this real-time programmable shader technology could be developed into 3D application on a single system, this platform dependent limitation keeps the shader technology away from 3D Internet applications. The primary purpose of this dissertation is to design a framework for translating different shader formats to platform independent shaders and embed them into the eXtensible 3D (X3D) scene for 3D web applications. This framework includes a back-end core shader converter, which translates shaders among different shading languages with a middle XML layer. Also included is a shader library containing a basic set of shaders that developers can load and add shaders to. This framework will then be applied to some applications in Biomolecular Visualization.
137

Développement et validation d'une méthode d'échantillonnage et d'analyse des nitrosamines dans l'air par CLHP-MS

Nechadi, Amina 11 1900 (has links) (PDF)
Les nitrosamines constituent une famille de composés posant un risque pour la santé des gens. Depuis la fin des années cinquante, 90% des nitrosamines ont été prouvées ou suspectées cancérogènes pour l'homme. Ces substances peuvent être retrouvées dans l'air, entre autres dans les milieux de travail. Les concentrations les plus importantes de nitrosamines volatiles ont été retrouvées dans les procédés de fabrication du caoutchouc. La valeur d'exposition admissible (VEA) recommandée par l'Institut national de santé publique du Québec (INSPQ) dans une revue de littérature récente est de 1 μg/m3 de nitrosamines. Les faibles concentrations à analyser demandent donc des outils et des méthodes d'analyse hautement spécifiques et sensibles. Depuis 2007, les laboratoires de l'IRSST ont effectué un important développement qui a permis de mettre au point une méthode d'analyse de huit nitrosamines dans l'air par chromatographie gazeuse avec détecteur azote phosphore (CG-DAP). Cependant, cette méthode peut parfois présenter des limitations quant à sa spécificité. Le spectromètre de masse étant très sélectif et sensible à la fois, une méthode couplant la chromatographie liquide à la spectrométrie de masse (CLHP-MS) a été développée dans le but de doser de basses concentrations de nitrosamines dans l'air. L'échantillonnage s'effectue avec le tube adsorbant développé par l’INRS (France). La méthode de désorption mise au point permet une récupération moyenne de 96,00 ± 0,08 %. Les limites de quantification obtenues lors des validations préliminaires de la méthode d'analyse par CLHP-MS varient de 0,03 μg/m3 à 0,09 μg/m3 selon la nitrosamine. Les valeurs obtenues représentent respectivement 3 % à 9 % de la norme recommandée par l'INSPQ pour 800 L de volume d'air échantillonné (400 minutes d'échantillonnage à 2 L/min). Le domaine d'applicabilité de la méthode est de 0,07 μg/m3 à 1,75 μg/m3 ce qui couvre les concentrations visées par l'INSPQ. Les résultats démontrent une détection spécifique et sensible des nitrosamines. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Nitrosamines, CLHP-MS, Analyse de l'air, Caoutchouc, GC-DAP.
138

A feed forward neural network approach for matrix computations

Al-Mudhaf, Ali F. January 2001 (has links)
A new neural network approach for performing matrix computations is presented. The idea of this approach is to construct a feed-forward neural network (FNN) and then train it by matching a desired set of patterns. The solution of the problem is the converged weight of the FNN. Accordingly, unlike the conventional FNN research that concentrates on external properties (mappings) of the networks, this study concentrates on the internal properties (weights) of the network. The present network is linear and its weights are usually strongly constrained; hence, complicated overlapped network needs to be construct. It should be noticed, however, that the present approach depends highly on the training algorithm of the FNN. Unfortunately, the available training methods; such as, the original Back-propagation (BP) algorithm, encounter many deficiencies when applied to matrix algebra problems; e. g., slow convergence due to improper choice of learning rates (LR). Thus, this study will focus on the development of new efficient and accurate FNN training methods. One improvement suggested to alleviate the problem of LR choice is the use of a line search with steepest descent method; namely, bracketing with golden section method. This provides an optimal LR as training progresses. Another improvement proposed in this study is the use of conjugate gradient (CG) methods to speed up the training process of the neural network. The computational feasibility of these methods is assessed on two matrix problems; namely, the LU-decomposition of both band and square ill-conditioned unsymmetric matrices and the inversion of square ill-conditioned unsymmetric matrices. In this study, two performance indexes have been considered; namely, learning speed and convergence accuracy. Extensive computer simulations have been carried out using the following training methods: steepest descent with line search (SDLS) method, conventional back propagation (BP) algorithm, and conjugate gradient (CG) methods; specifically, Fletcher Reeves conjugate gradient (CGFR) method and Polak Ribiere conjugate gradient (CGPR) method. The performance comparisons between these minimization methods have demonstrated that the CG training methods give better convergence accuracy and are by far the superior with respect to learning time; they offer speed-ups of anything between 3 and 4 over SDLS depending on the severity of the error goal chosen and the size of the problem. Furthermore, when using Powell's restart criteria with the CG methods, the problem of wrong convergence directions usually encountered in pure CG learning methods is alleviated. In general, CG methods with restarts have shown the best performance among all other methods in training the FNN for LU-decomposition and matrix inversion. Consequently, it is concluded that CG methods are good candidates for training FNN of matrix computations, in particular, Polak-Ribidre conjugate gradient method with Powell's restart criteria.
139

Determinação de hidrocarbonetos policíclicos aromáticos associados ao material particulado atmosféric

Lopes, Wilson Araújo 09 February 2007 (has links)
Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-09-06T16:08:00Z No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-08T10:48:19Z (GMT) No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / Made available in DSpace on 2016-09-08T10:48:19Z (GMT). No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / CNPq, FINEP, FAPESB e ANEEL / Os Hidrocarbonetos policíclicos aromáticos (HPA) são poluentes formados geralmente durante a combustão incompleta de petróleo e derivados, carvão mineral, biomassa e outros materiais orgânicos. São emitidos por diversas fontes naturais ou antrópicas e estão presentes na atmosfera, hidrosfera e litosfera. A atmosfera é o seu principal meio de transporte onde se encontram em fase vapor ou adsorvidos em material particulado. Em centros urbanos, sua emissão está associada principalmente aos veículos automotores, movidos a diesel e gasolina. Os HPA e seus derivados, por exemplo, os nitro-HPA e oxi-HPA, são agentes cancerígenos e/ou mutagênicos, daí a importância de estudos sobre a sua presença na atmosfera e em outras matrizes ambientais, sobre a reatividade e atividades biológicas. Neste trabalho, foram determinadas as concentrações atmosféricas para 16 HPA considerados como poluentes prioritários pela agência de proteção ambiental dos Estados Unidos da América (U. S. EPA), em amostras de material particulado atmosférico (MPA), usando o método de CG-EM com monitoramento de íons selecionados. As amostras de MPA foram coletadas em amostradores de grande volume (Hi-vol) e, em seguida, foram extraídas usando a técnica de sonicação e uma solução de acetonitrila e diclorometano (3:1) como solvente. Os extratos foram pré- concentrados (10/1) e em seguida analisados por CG-EM/SIM. Com o objetivo de assegurar uma boa separação dos 16 HPA, no menor tempo de análise, foi utilizado o planejamento multivariado para estabelecer as condições de programação de temperatura do forno (aquecimento da coluna). O processo de otimização foi realizado por meio do planejamento fatorial fracionário e através do planejamento do tipo Box-Behnken, sendo avaliados os seguintes fatores: temperatura inicial (oC), velocidade de elevação da temperatura N° 1 (°C.min-1), temperatura intermediária (oC), velocidade de elevação da temperatura N° 2 (°C.min-1) e temperatura final (oC). As condições otimizadas para a separação dos 16 HPA foram estabelecidas em: 70 °C (2 min) ? 200 °C (30 °C/min, 5 min) ? 300 °C (5 °C/min, 1,67 min). O tempo total da análise, com uma boa separação dos 16 analitos, ficou em 33 minutos. A validação da técnica de CG-EM, no modo SIM, apresentou resultados considerados satisfatórios para a repetitividade da resposta do detector, repetitividade do tempo de retenção, e linearidade das curvas de calibração. Os limites de detecção foram estabelecidos entre 0,13 e 0,34 ng mL-1 (área) e 0,18 e 0,72 ng mL-1 (altura de pico) e os limites de quantificação entre 0,38 e 1,04 ng mL-1 (área) e entre 0,61 e 2,39 ng mL-1 (altura de pico). As amostras ambientais de MPA foram coletadas em quatro diferentes locais, apresentando os seguintes resultados: i) Estação da Lapa (Salvador, BA) - Os HPA presentes em concentrações mais altas foram o criseno (CRI), pireno (PIR) e benzo[b]fluoranteno (BbF), apresentando concentrações médias de respectivamente 2,62, 1,32 e 1,30 ng m-3, e perfil compatível com emissões de veículos movidos a diesel; ii) Porto de Aratu (Candeias, BA) - Os HPA presentes em maiores concentrações foram o benzo[b]fluoranteno (BbF), benzo[g,h,i]perileno (BgP) e Indeno[1,2,3- c,d]pireno (IND), apresentando concentrações médias de respectivamente 2,53, 1,22 e 1,12 ng m-3 (AGV-PTS) e 1,74, 0,82 e 0,73 (AGV MP10); iii) Ilha de Maré, (Salvador, BA) – os valores mais altos foram observados para o benzo[b]fluoranteno (BbF), benzo[b]fluoranteno (BkF) e benzo[g,h,i]perileno (BgP), apresentando concentrações médias de respectivamente 1,62, 0,73 e 0,72 ng m-3; iv) Cidade Universitária da USP (São Paulo, SP) - Os HPA que apresentaram maiores concentrações médias foram o benzo[b]fluoranteno (BbF), criseno (CRI) e o benzo[g,h,i]perileno, com os valores de, respectivamente, 0,93, 0,50 e 0,49 ng m-3. Os resultados foram avaliados em termos de perfil das concentrações, prováveis fontes de emissões e, em alguns casos, por comparação com análises anteriores. / Polycyclic aromatic hydrocarbons (PAH) are ubiquitous pollutants that are emitted from several natural or anthropic sources and may be present in the atmosphere, hydrosphere and lithosphere. They usually originate during the incomplete combustion of petroleum and its derivatives, mineral coal, biomass and other organic materials. They are mainly transported in the atmosphere, being present either in the vapor phase or adsorbed in particulate material. In urban centers, emission is mainly associated with diesel- and gasoline-powered motor vehicles. Since PAH and derivatives, e.g. nitro-PAH and oxy-PAH, are carcinogenic and/or mutagenic agents, to study the effect of their presence in the atmosphere and in other environmental matrices on the biological activity and reactivity are of key relevance. In this study, the atmospheric concentrations of the 16 PAHs that are considered priority pollutants by the U.S. Environmental Protection Agency were evaluated in samples of atmospheric particulate material (APM), using gas chromatography / mass spectrometry with selected-ion monitoring mode (GC-MS/SIM). APM samples were collected in high-volume air samplers (Hi-vol) and then extracted under sonication with a solution of acetonitrile and dichloromethane (3:1) as a solvent. Extracts were pre-concentrated (10/1) and analyzed by GC-MS/SIM. In order to assure an adequate separation of the 16 PAHs, in the shortest analysis time, a multivariate design was used to set the conditions of the oven temperature program (column warming). The optimization process was carried out using factorial fractional design and Box-Behnken design. The following factors were evaluated: initial temperature (ºC), temperature rate N°1 (ºC.min-1), intermediate temperature (ºC), temperature rate N°2 (ºC.min-1) and final temperature (ºC). The optimized conditions for the separation of the 16 PAH were set at: 70 ºC (2 min) → 200 ºC (30 ºC/min, 5 min) → 300 ºC (5 ºC/min, 1.67 min). Total analysis time, with an adequate separation of the 16 analytes was 33 minutes. Validation of GC-MS in the SIM mode rendered satisfactory results for repeatability of detector response, repeatability of retention time, and linearity of calibration curves. Detection limits were established between 0.13 and 0.34 ng mL- 1 (area) and 0.18 and 0.72 ng mL-1 (peak height). Environmental samples of PMA were collected at four different locations, with the following results: i) Lapa Bus Station (Salvador, BA) - The PAH with the highest concentrations were crysene (CRY), pyrene (PYR) and benzo[b]fluoranthene (BbF), with mean concentrations of 2.62, 1.32, and 1.30 ng m-3, respectively, suggesting a profile compatible with diesel vehicle emissions; ii) Port of Aratu (Candeias, BA) – The PAH with the highest concentrations were benzo[b]fluoranthene (BbF), benzo[g,h,i]perylene (BgP) and indeno[1,2,3-c,d]pyrene (IND), with mean concentrations of 2.53, 1.22, and 1.12 ng m-3 (TSP) and 1.74, 0.82 e 0.73 (PM10), respectively; iii) Ilha de Maré, (Salvador, BA) – The PAH with the highest concentrations were benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF) and benzo[g,h,i]perylene (BgP), with mean concentrations of 1.62, 0.73 e 0.72 ng m-3, respectively; iv) University of São Paulo (São Paulo, SP) - The PAH with the highest mean concentrations were benzo[b]fluoranthene (BbF), chrysene (CRI) and benzo[g,h,i]perylene (BgP) with values of 0.93, 0.50 and 0.49 ng m-3, respectively. The results were evaluated with respect to concentration profile, probable emission sources and in some cases, were compared to prior analyses.
140

Extração em ponto nuvem com derivatização do surfactante: uma alternativa para a determinação de hidrocarbonetos policíclicos aromáticos em águas naturais por cromatografia gasosa

Rocha, Sarah Adriana do Nascimento 10 1900 (has links)
Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2014-09-19T18:04:41Z No. of bitstreams: 1 Tese_Sarah_Rocha_LSGT.pdf: 3229640 bytes, checksum: af1acce9c5d43271ea20530b0fd1f510 (MD5) / Approved for entry into archive by Fatima Cleômenis Botelho Maria (botelho@ufba.br) on 2014-09-22T12:43:20Z (GMT) No. of bitstreams: 1 Tese_Sarah_Rocha_LSGT.pdf: 3229640 bytes, checksum: af1acce9c5d43271ea20530b0fd1f510 (MD5) / Made available in DSpace on 2014-09-22T12:43:20Z (GMT). No. of bitstreams: 1 Tese_Sarah_Rocha_LSGT.pdf: 3229640 bytes, checksum: af1acce9c5d43271ea20530b0fd1f510 (MD5) / Um método de extração em ponto nuvem de hidrocarbonetos policíclicos aromáticos foi desenvolvido, utilizando tensoativos octilfenol polietoxilados com derivatização do coacervato, como etapa que antecede a detecção por cromatografia a gás acoplada à espectrometria de massa. Foi realizado um estudo da influência da presença de aditivos na redução da temperatura de ponto nuvem do OPEO30 e do OPEO35, surfactantes com temperaturas de ponto nuvem superiores a 100 oC, através adição de sais, álcoois, OPEO7.5 e misturas de sais e álcoois. Observou-se em todos os casos diminuição da temperatura, sendo o sulfato de sódio o aditivo que resultou maior redução da temperatura. Selecionou-se o OPEO30 para as demais etapas do trabalho. Fez-se a otimização das condições da reação de derivatização do coacervato por meio de planejamento fatorial 23, utilizando-se a resposta global para avaliar os resultados. Selecionou-se as condições do ponto central do planejamento fatorial, ou seja, 125 L de BSTFA, 100 L de piridina e banho de água à 70 oC por 45 min, para a derivatização de 30 L de fase rica em surfactante. O procedimento de ponto nuvem foi otimizado, sendo avaliadas as variáveis concentração de surfactante, temperatura e tempo de banho de água, sendo proposta a seguinte metodologia: 1,0 mL de OPEO30 10% m v-1, 10,0 mL de amostra, 1,25 g de sulfato de sódio anidro, banho de água à 70 oC por 10 min, centrifugação à 3000 rpm por cinco min. O método mostrou-se seletivo, sendo observado efeito de matriz intenso, o qual foi corrigido. Os limites de quantificação obtidos estão entre 39 e 176 ng L-1. O método proposto também foi comparado com o método USEPA 3510C, estando as concentrações obtidas, quando analisada uma amostra real de água subterrânea, bem próximas, com recuperações variando entre 90,0 e 97,5 %. O método proposto foi aplicado a amostras de água subterrânea coletadas em poços localizados em postos de revenda de combustíveis. Em todas as amostras foram detectados HPA. / A method for cloud point extraction of polycyclic aromatic hydrocarbons was developed using surfactants octylphenol polyethoxylated with the coacervate derivatization as step prior to gas chromatography-mass spectrometry detection. An influence of additives study on the reduction of cloud point temperature OPEO30 and OPEO35, surfactants with cloud point temperatures above 100 ° C, was conducted, by addition of salts, alcohols, and mixtures OPEO7.5 salts and alcohols. It was observed in all cases cloud point reduction and sodium sulfate was the additive that result in a most effective. The OPEO30 was selected for others work steps. The factorial design 23 was used to optimize the reaction of derivatization, using the global response to evaluate the results. Were selected the central point experimental design condition, 125 L of BSTFA, 100 L of pyridine and water bath at 70 oC for 45 min for 30 L of surfactant-rich phase derivatization. The cloud point extraction procedure was optimized and surfactant concentration, heating bath temperature and time variables, were evaluated. Was proposed the following method: 1,0 mL of OPEO30 10% v m-1 solution, 10,0 mL of sample, 1,25 g of anhydrous sodium sulfate, water bath at 70 °C for 10 min. The centrifugation was performed at 3000 rpm for five min, removing the aqueous layer after each centrifugation step. A 30L coacervate aliquot was withdrawn, and performed derivatization and subsequent GC-MS analysis. The method was validated. The method was selective, an intense matrix effect was observed and was corrected. The quantification limits obtained were between 39 and 176 ng L-1.

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