• Refine Query
  • Source
  • Publication year
  • to
  • Language
  • 33
  • 8
  • 7
  • 4
  • 2
  • 2
  • 1
  • 1
  • Tagged with
  • 65
  • 26
  • 24
  • 12
  • 12
  • 10
  • 9
  • 8
  • 7
  • 7
  • 7
  • 7
  • 6
  • 5
  • 5
  • 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.
1

Obtenção de sistemas de PCL com subproduto da cultura algodoeira.

BEZERRA, Elieber Barros. 02 February 2018 (has links)
Submitted by Gustavo Nascimento (gustavo.diniz@ufcg.edu.br) on 2018-02-02T14:58:07Z No. of bitstreams: 1 ELIEBER BARROS BEZERRA - DISSERTAÇÃO PPGCEMAT 2014.pdf: 7994493 bytes, checksum: 4a404e61a81ba68d735ac09a14b80f8a (MD5) / Made available in DSpace on 2018-02-02T14:58:07Z (GMT). No. of bitstreams: 1 ELIEBER BARROS BEZERRA - DISSERTAÇÃO PPGCEMAT 2014.pdf: 7994493 bytes, checksum: 4a404e61a81ba68d735ac09a14b80f8a (MD5) Previous issue date: 2014-08-19 / Estudos têm sido realizados com o intuito de criar processos que utilizem matérias-primas renováveis, gerando assim produtos não agressivos ao meio ambiente, sem perder em qualidade ou desempenho. Este trabalho teve como objetivo a obtenção de sistemas de poli(ε-caprolactona) (PCL) com subproduto da cultura algodoeira, a fim de avaliar a influência dos componentes línter e nanolínter de algodão nas propriedades finais dos compósitos poliméricos. Os sistemas de PCL com 1, 3 e 5% de cargas foram obtidos em extrusora e, processados em injetora, caracterizados quanto à composição lignocelulósica, tamanho de partícula e potencial zeta, difração de raios-X (DRX), termogravimetria (TG), calorimetria exploratória diferencial (DSC), microscopia eletrônica de varredura (MEV), propriedades mecânicas e temperatura de deflexão térmica (HDT). Por meio da caracterização lignocelulósica foi observado um alto teor de celulose para a fibra vegetal e, por medida do tamanho de partícula e potencial zeta, foram observadas partículas com diâmetro médio na faixa nanométrica. Por DRX, foi vista a presença dos picos característicos da PCL pura, do línter e da nanocelulose. Para os sistemas PCL/Línter e PCL/Nano não foram visualizadas alterações nos picos característicos da matriz. Por TG, foi verificada que a presença da carga não influenciou no comportamento térmico dos sistemas. Por DSC, não foram observadas alterações na cristalinidade dos sistemas com a presença do línter e do nanolínter. Por meio das fotomicrografias de MEV, foi observada a má adesão da matriz polimérica ao línter e ao nanolínter. Por meio dos ensaios de tração e flexão, foi observado que os sistemas com línter apresentaram um pequeno aumento no módulo e na resistência. Para os sistemas contendo nanolínter, os valores de módulo e de resistência foram similares aos da matriz. Por meio do ensaio de resistência ao impacto, foi observado que as cargas utilizadas diminuíram a resistência dos compósitos. Um aumento na temperatura de deflexão térmica (HDT) dos sistemas foi visto com a presença das cargas. / Estudos têm sido realizados com o intuito de criar processos que utilizem matérias-primas renováveis, gerando assim produtos não agressivos ao meio ambiente, sem perder em qualidade ou desempenho. Este trabalho teve como objetivo a obtenção de sistemas de poli(ε-caprolactona) (PCL) com subproduto da cultura algodoeira, a fim de avaliar a influência dos componentes línter e nanolínter de algodão nas propriedades finais dos compósitos poliméricos. Os sistemas de PCL com 1, 3 e 5% de cargas foram obtidos em extrusora e, processados em injetora, caracterizados quanto à composição lignocelulósica, tamanho de partícula e potencial zeta, difração de raios-X (DRX), termogravimetria (TG), calorimetria exploratória diferencial (DSC), microscopia eletrônica de varredura (MEV), propriedades mecânicas e temperatura de deflexão térmica (HDT). Por meio da caracterização lignocelulósica foi observado um alto teor de celulose para a fibra vegetal e, por medida do tamanho de partícula e potencial zeta, foram observadas partículas com diâmetro médio na faixa nanométrica. Por DRX, foi vista a presença dos picos característicos da PCL pura, do línter e da nanocelulose. Para os sistemas PCL/Línter e PCL/Nano não foram visualizadas alterações nos picos característicos da matriz. Por TG, foi verificada que a presença da carga não influenciou no comportamento térmico dos sistemas. Por DSC, não foram observadas alterações na cristalinidade dos sistemas com a presença do línter e do nanolínter. Por meio das fotomicrografias de MEV, foi observada a má adesão da matriz polimérica ao línter e ao nanolínter. Por meio dos ensaios de tração e flexão, foi observado que os sistemas com línter apresentaram um pequeno aumento no módulo e na resistência. Para os sistemas contendo nanolínter, os valores de módulo e de resistência foram similares aos da matriz. Por meio do ensaio de resistência ao impacto, foi observado que as cargas utilizadas diminuíram a resistência dos compósitos. Um aumento na temperatura de deflexão térmica (HDT) dos sistemas foi visto com a presença das cargas.
2

ATP synthase mitochondriale : fonction de la sous-unité ε et biogenèse du F0 / Mitochondrial ATP synthase : function of the ε subunit and biogenesis of F0

Godard, Francois 25 June 2014 (has links)
Dans un premier temps, je me suis intéressé à la sous-unité ε de l’ATP synthase mitochondriale chez la levure, un organisme qui se prête bien à l’étude des fonctions mitochondriales. Cette protéine fait partie d’un élément de l’ATP synthase appelé la tige centrale. Celui-ci permet de coupler le domaine translocateur de protons de cette enzyme (FO) à son secteur catalytique (F1) où l’ATP est synthétisé. En utilisant un système d’expression régulable (répressible par la doxycycline), j’ai montré qu’en l’absence de la sous-unité ε les secteurs F1 et FO ne sont plus couplés, avec pour résultat des fuites massives de protons à travers la membrane interne des mitochondries. J’ai ensuite montré que l’absence de la sous-unité ε peut être compensée par des mutations ralentissant l’activité du FO. Ces données permettent de conclure que la sous-unité ε est nécessaire au maintien de l’intégrité physique de l’ATP synthase lors de son fonctionnement. Dans un second temps, j’ai cherché à identifier de nouveaux facteurs intervenant dans la biogenèse du FO. Pour cela, j’ai utilisé un crible génétique où la survie des cellules de levure est conditionnée à des mutations inactivation le FO. Un millier d’isolats a été analysé. Les mutations ont été localisées dans les génomes mitochondrial et nucléaire. Dix-huit clones, issus de mutations n’affectant pas des facteurs connus pour être nécessaires à l’expression de l’ATP synthase, ont été entièrement séquencés. Plusieurs nouveaux systèmes cellulaires potentiellement impliqués dans la biogenèse du FO ont été identifiés. / At first, I am interested in the ε subunit of mitochondrial ATP synthase in yeast, an organism that is well suited for the study of mitochondrial functions. This protein is a part of the ATP synthase called central stalk. This allows the coupling of proton translocator domain of this enzyme (FO) to its catalytic domain (F1) where ATP is synthesized. Using a tetO expression system, I showed that in the absence of the ε subunit, F1 and FO domains are no longer coupled. It results in a massive proton leakage across the inner membrane of mitochondria. I then showed that the absence of the ε subunit can be compensated by mutations slowing the activity of FO. These data allow to conclude that the ε subunit is necessary to maintain the physical integrity of the ATP synthase for oxydative phosphorylation. Later, I tried to identify new factors involved in the biogenesis of the FO. For this, I used a genetic screen where the survival of yeast cells is conditioned by mutations inactivating the FO. About a thousand clones were analyzed. The mutations were localized in mitochondrial and nuclear genomes. Eighteen clones with mutations in genes encoding not yet known ATP synthase expression factors were completely sequenced. Several new cellular systems that are potentially involved in the biogenesis of FO were identified.
3

Desenvolvimento e caracterização de nanopartículas poliméricas contendo itraconazol / Development and characterization of polymeric nanoparticles itraconazole

Lucena, Percília de Andradea 19 March 2014 (has links)
Submitted by Marlene Santos (marlene.bc.ufg@gmail.com) on 2014-12-16T19:58:48Z No. of bitstreams: 2 Dissertação - Percília de Andrade Lucena - 2014.pdf: 1506404 bytes, checksum: c895c029b3a1ac62acf42cd19fad7214 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2014-12-22T10:32:36Z (GMT) No. of bitstreams: 2 Dissertação - Percília de Andrade Lucena - 2014.pdf: 1506404 bytes, checksum: c895c029b3a1ac62acf42cd19fad7214 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2014-12-22T10:32:36Z (GMT). No. of bitstreams: 2 Dissertação - Percília de Andrade Lucena - 2014.pdf: 1506404 bytes, checksum: c895c029b3a1ac62acf42cd19fad7214 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-03-19 / Polymeric nanoparticles have been used as carriers of drugs that are able to increase the efficacy of many active ingredients. Among the nanocarriers include nanocapsules (NCs), which are vesicular structures containing oil inside surrounded by a polymer wall and nanospheres (NSs) that are impregnated with polymer matrices drug throughout its surface. These structures have many applications such as optimizing drug delivery and reducing the toxic potential of drugs. Itraconazole family of a drug Azole has a broad spectrum of action against fungi and has appropriate pharmacokinetic characteristics for a drug. Thus, this study aims to develope and characterize nanostructured systems containing Itraconazole. Polymeric nanoparticles were obtained by the nanoprecipitation technique, lyophilized, characterized, and evaluated physical-chemically incorporated into mucoadhesive topical formulation. Nanocapsules containing Itraconazole showed encapsulation efficiency rate of 99 ± 6.9%, a mean diameter of 190 ± 10.1 nm, PDI 0.1 ± 0:06 and zeta potential -15 ± 2.5 mV. The nanospheres exhibited rate of encapsulation efficiency of 97 ± 2.8%, mean diameter 120 ± 0.8 nm, 0.1 ± 0.01 PDI and zeta potential -10 ± 3.5 mV. Lyophilization was carried out with 10% trehalose + 10% sucrose, achieving satisfactory results. The drug release after 30 days at 37 °C was 99% for the NCs and 92% for the NEs. The mucoadhesive topical formulation has in its composition 60% Poloxamer 188, 20% polyethylene glycol 400 and 5mg nanostructured itraconazole were incorporated homogeneously. The results indicate that the formulation of Itraconazole in polymeric nanoparticles has potential for in vivo use in the topical treatment of fungal infections. / Nanopartículas poliméricas têm sido utilizadas como carreadores de fármacos capazes de aumentar a eficácia de muitos insumos ativos. Dentre os nanocarreadores, destacam-se: nanocápsulas (NCs), que são estruturas vesiculares, contendo óleo no interior, circundadas por uma parede polimérica e nanoesferas (NEs) que são matrizes poliméricas impregnadas com fármaco por toda sua superfície. Essas estruturas possuem diversas aplicações como otimizar a entrega de fármacos e reduzir o potencial tóxico. O Itraconazol um fármaco da família dos azóis possui um amplo espectro de ação contra fungos e apresenta características farmacocinéticas apropriadas para um fármaco. Sendo assim, o presente trabalho tem como objetivo desenvolver e caracterizar sistemas nanoestruturados contendo Itraconazol. As nanopartículas poliméricas foram obtidas através da técnica da nanoprecipitação, liofilizadas, caracterizadas, avaliadas físicoquimicamente e incorporadas em formulação tópica mucoadesiva. As nanocápsulas contendo Itraconazol apresentaram taxa de eficiência de encapsulação de 99±6.9%, diâmetro médio de 190±10.1 nm, PDI 0.1±0.06 e potencial zeta -15±2.5 mV. As nanoesferas exibiram taxa de eficiência de encapsulação de 97±2.8%, diâmetro médio de 120±0.8 nm, PDI 0.1±0.01 e potencial zeta -10±3.5 mV. A liofilização foi realizada com 10% de trealose + 10% de sacarose, alcançando resultados satisfatórios. A liberação do fármaco após 30 dias a 37°C foi de 99% para as NCs e 92% para as NEs. A formulação tópica mucoadesiva possui em sua composição 60% Poloxamer 188 e 20% de Polietilenoglicol 400 e 5mg de itraconazol nanoestruturado foram incorporados homogeneamente. Os resultados indicam que a formulação de itraconazol em nanopartículas poliméricas apresenta potencial para utilização in vivo no tratamento tópico de infecções fúngicas.
4

3D Numerical Modelling of Secondary Current in Shallow River Bends and Confluences

Shaheed, Rawaa January 2016 (has links)
Secondary currents are one of the important features that characterize flow in river bends and confluences. Fluid particles follow a helical path instead of moving nearly parallel to the axis of the channel. The local imbalance between the vertically varying centrifugal force and the cross-stream pressure gradient results in generating the secondary flow and raising a typical motion of the helical flow. A number of studies, including experimental or mathematical, have been conducted to examine flow characteristics in curved open channels, river meanders, or confluences. In this research, the influence of secondary currents is studied on the elevation of water surface and the hydraulic structures in channel bends and confluences by employing a 3D OpenFOAM numerical model. The research implements the 3D OpenFOAM numerical model to simulate the horizontal distribution of the flow in curved rivers. In addition, the progress in unraveling and understanding the bend dynamics is considered. The finite volume method in (OpenFOAM) software is used to simulate and examine the behavior of secondary current in channel bends and confluences. Thereafter, a comparison between the experimental data and a numerical model is conducted. Two sets of experimental data are used; the data provided by Rozovskii (1961) for sharply curved channel, and the dataset provided by Shumate (1998) for confluent channel. Two solvers in (OpenFOAM) software were selected to solve the problem regarding the experiment; InterFoam and PisoFoam. The InterFoam is a transient solver for incompressible flow that is used with open channel flow and Free Surface Model. The PisoFoam is a transient solver for incompressible flow that is used with closed channel flow and Rigid-Lid Model. Various turbulence models (i.e. Standard k-ε, Realizable k-ε, LRR, and LES) are applied in the numerical model to assess the accuracy of turbulence models in predicting the behaviour of the flow in channel bends and confluences. The accuracies of various turbulence models are examined and discussed.
5

Polyamide 6/silica hybrid materials by a coupled polymerization reaction

Kaßner, Lysann, Nagel, Kevin, Grützner, R.-E., Korb, Marcus, Rüffer, Tobias, Lang, Heinrich, Spange, Stefan 15 February 2016 (has links) (PDF)
Polyamide 6/SiO2 hybrid materials were produced by a coupled polymerization reaction of three monomeric components namely 1,1′,1′′,1′′′-silanetetrayltetrakis-(azepan-2-one) (Si(ε-CL)4), 6-aminocaproic acid (ε-ACA) and ε-caprolactam (ε-CL) within one process. Si(ε-CL)4 together with ε-ACA has been found suitable as a precursor monomer for the silica and PA6 components. The accurate adjustment of the molar ratio of both components, as well as the combination of the overall process for producing the polyamide 6/SiO2 hybrid material with the hydrolytic ring opening polymerization of ε-caprolactam is of great importance to achieve homogeneous products with a low extractable content. Water in comparison with ε-ACA has been found unsuitable as an oxygen source to produce uniformly distributed silica. The procedure was carried out in a commercial laboratory autoclave at 8 bar initial pressure. The molecular structure and morphology of the hybrid materials have been investigated by solid state 29Si and 13C NMR spectroscopy, DSC and FTIR spectroscopy and electron microscopy measurements. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
6

Polyamide 6/silica hybrid materials by a coupled polymerization reaction

Kaßner, Lysann, Nagel, Kevin, Grützner, R.-E., Korb, Marcus, Rüffer, Tobias, Lang, Heinrich, Spange, Stefan 15 February 2016 (has links)
Polyamide 6/SiO2 hybrid materials were produced by a coupled polymerization reaction of three monomeric components namely 1,1′,1′′,1′′′-silanetetrayltetrakis-(azepan-2-one) (Si(ε-CL)4), 6-aminocaproic acid (ε-ACA) and ε-caprolactam (ε-CL) within one process. Si(ε-CL)4 together with ε-ACA has been found suitable as a precursor monomer for the silica and PA6 components. The accurate adjustment of the molar ratio of both components, as well as the combination of the overall process for producing the polyamide 6/SiO2 hybrid material with the hydrolytic ring opening polymerization of ε-caprolactam is of great importance to achieve homogeneous products with a low extractable content. Water in comparison with ε-ACA has been found unsuitable as an oxygen source to produce uniformly distributed silica. The procedure was carried out in a commercial laboratory autoclave at 8 bar initial pressure. The molecular structure and morphology of the hybrid materials have been investigated by solid state 29Si and 13C NMR spectroscopy, DSC and FTIR spectroscopy and electron microscopy measurements. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
7

Structural and Mechanistic Studies on α-Amino β-Carboxymuconate ε-Semialdehyde Decarboxylase and α-Aminomuconate ε-Semialdehyde Dehydrogenase

Huo, Lu 12 August 2014 (has links)
α-Amino-β-carboxymuconate-ε-semialdehyde decarboxylase (ACMSD) and α-aminomuconate-ε-semialdehyde dehydrogenase (AMSDH) are two neighboring enzymes in the L-tryptophan and 2-nitrobenzoic acid degradation pathways. The substrates of the two enzymes, α-amino-β-carboxymuconate-ε-semialdehyde (ACMS) and α-aminomuconate-ε-semialdehyde (2-AMS), are unstable and spontaneously decay to quinolinic acid and picolinic acid, respectively. ACMSD utilizes a divalent zinc metal as cofactor and is a member of the amidohydrolase superfamily. In this dissertation work, we have identified an important histidine residue in the active site that plays dual roles in tuning metal selectivity and activating a metal bound water ligand using mutagenesis, resonance Raman, EPR, crystallography, and ICP metal analysis techniques. The crystal structures of ACMSD from Pseudomonas fluorescens (PfACMSD) have been solved as homodimers in our laboratory while human ACMSD (hACMSD) was annotated as a monomer by another group. To resolve this structural difference, we used two conserved active site arginine residues as probes to study the oligomeriztion state of ACMSD and demonstrated that these two arginine residues are involved in substrate binding and that both Pf- and h- ACMSD are catalytically active only in the dimeric state. Subsequently, we solved the crystal structure of hACMSD and found it to be a homodimer in both catalytically active and inhibitor-bound forms. AMSDH is an NAD+ dependent enzyme and belongs to the aldehyde dehydrogenase superfamily. Due to the high instability of its substrate, AMSDH has not been studied at the molecular level prior to our work. We have cloned and expressed PfAMSDH in E. coli. The purified protein has high activity towards both 2-AMS and 2-hydroxymuconate semialdehyde (2-HMS), a stable substrate analog. We have successfully crystallized AMSDH with/without NAD+ and solved the crystal structure at up to 1.95 Å resolution. Substrate bound ternary complex structures were obtained by soaking the NAD+ containing crystals with 2-AMS or 2-HMS. Notably, two covalently bound catalytic intermediates were captured and characterized using a combination of crystallography, stopped-flow, single crystal spectroscopy, and mass spectrometry. The first catalytic working model of AMSDH has been proposed based on our success in structural and spectroscopic characterization of the enzyme in five catalytically relevant states in this dissertation work.
8

Preparation and properties of bio-based polyurethane made from natural rubber and poly(ε-caprolactone) / Synthèse et étude des propriétés d’un polyuréthane biosourcé obtenu du caoutchouc naturel et du poly(ε-caprolactone)

Panwiriyarat, Wannarat 18 December 2012 (has links)
L’objectif de ce travail de thèse était la synthèse d’un nouveau matériau polyuréthane biorsourcé composé par du caoutchouc naturel modifié chimiquement et par du poly(ε-caprolactone), (PCL), en présence ou absence d’isocyanates. Des oligoisoprènes téléchéliques hydroxylés (HTNR) ont été obtenus après époxidation du caoutchouc naturel et réduction des oligomères carbonyles. Plusieurs paramètres ont été étudiés comme la nature et la quantité relative de diisocyanate, le rapport molaire entre diisocyanate et diol (NCO:OH), l’influence de la masse molaire des diols HTNR et PCL, le pourcentage de 1,4-butane diol (BDO, extenseur de chaîne), et le rapport molaire entre les diols HTNR:PCL. Trois types de diisocyanate ont été employés : isophorone diisocyanate (IPDI), toluène-2,4-diisocyanate (TDI) et hexaméthylène diisocyanate (HDI). Masses molaires différentes ont été utilisées pour les diols HTNR et PCL: 1700, 2800 et 2900 g/mol pour HTNR et 530 et 2000 g/mol pour PCL. Le rapport molaire entre NCO:OH était entre 0,75:1,00 – 2,85:1,00. Les PU ont été préparés par la méthode « one shot » et les structures chimiques des HTNR et PU ont été identifiées par 1H-NMR et FTIR. La résistance à la traction et à la rupture ont été étudiées. La caractérisation a été conduite par DSC, DMTA, ATG et spectroscopie Raman. Une étude préliminaire a montré que la masse molaire du PU augmentait avec le rapport NCO:OH et le temps de réaction, et que le chloroforme n’était pas un bon solvant pour obtenir des films. Le tetrahydrofurane était le solvant le plus approprié et il a été utilisé par la suite pour toutes les polymérisations. Le rapport NCO:OH = 1,25:1,00 s’est révélé optimal pour obtenir des films. L’analyse FTIR a permis de vérifier la présence de liaisons uréthane, de points de réticulation et de branchements. Le polyuréthane a montré des propriétés mécaniques excellentes dépendantes de la composition chimique. Si on exclue l’utilisation de PCL2000 et de HDI, le comportement à la traction était caractéristique des élastomères. Les PU étaient amorphes sauf lorsque le HDI a été employé. Duos ce cos été obtenais un PU semi cristallin. Cette cristallinité augmente le module de Young, la résistance à la rupture, la dureté et la stabilité thermique du PU. Pour ce PU ont observé une séparation de phase entre les segments du PCL et du HTNR. Les chaînes plus longues et plus flexibles du HTNR et leur non polarité sont responsables de la diminution des propriétés mécaniques et des températures de transition. Le materiae pane d’un comportement élastomère a un comportement plastique pour un rapport NCO:OH élevé (2,85 :1,00). Le dégréé de réticulation élevé a été retenu comme la cause pour laquelle il n’y avait pas de séparation de phase entre les segments souples et durs. La liaison hydrogène entre le diol PCL et le segment hard a généré des Tg élevées. Les spectres Raman ont montré la formation de la liaison uréthane du PU contenant différents diisocyanates. La synthèse de PU sans diisocyanate a été obtenue grâce à une réaction de polyaddition entre des carbonates cycliques téléchéliques dérivés du PCL et du caoutchouc naturel, et la 1,4-butylène diamine. Les structures contenant des carbonates cycliques ont été obtenues grâce à la modification des groupes OH sur le HTNR et le PCL à groupes carboxyle, utilisant l’anhydride succinique, et a la réaction successive avec le glycérol carbonate. / The aim of this research work was to prepare a novel bio-based polyurethane (PU) composed by chemically modified natural rubber (NR) and poly(ε-caprolactone) diol (PCL), with and without isocyanate. Hydroxyl telechelic natural rubber (HTNR) was synthesized via epoxidized and carbonyl telechelic natural rubber. The parameters studied included type and relative amount of diisocyanate, molar ratio between diisocyante and diol (NCO:OH), molecular weight of HTNR and PCL diol, 1,4-butane diol (BDO, chain extender) content and molar ratio between HTNR:PCL diols. Three types of diisocyanate were employed: isophorone diisocyanate (IPDI), toluene-2,4-diisocyanate (TDI) and hexamethylene diisocyanate (HDI). The number average molecular weights of HTNR and PCL diol were selected: 1700, 2800 and 2900 g/mol for HTNR and 530 and 2000 g/mol for PCL diol. The NCO:OH molar ratio was in the range 0.75:1.00 – 2.85:1.00. PU was prepared by one-shot method. The chemical structure of HTNR, PCL and PU were identified by 1H-NMR FTIR and Raman spectroscopy. Tensile properties and tear resistance of PU were investigated. Characterization of mechanical and thermal properties was carried out using DSC, DMTA and TGA. A preliminary study showed that the molecular weight of PU increased with increasing NCO:OH molar ratio and reaction time, and chloroform was not a good solvent for polymer casting. Tetrahydrofuran was an appropriate solvent as it allowed film formation and it was used in all the other experiments. The NCO:OH molar ratio of 1.25:1.00 was suitable for preparing good PU films. FTIR analysis verified the presence of urethane linkages and crosslinking or chain branching. PU demonstrated excellent mechanical properties, which depended on the chemical composition. Excluding the use of PCL2000 and HDI, the tensile behavior seemed to have typical elastomeric characteristics. PU became amorphous except in the case of HDI, which was able to crystallize leading to the crystalline PU. The crystallinity increased the Young’s modulus, the tear strength, the hardness and the thermal stability of PU. PU showed a phase separation between the PCL and HTNR segments. The longer and more flexible chain and non-polarity of HTNR were responsible of a decrease of the mechanical properties and transition temperatures. The very high molar ratio of NCO:OH (2.85:1.00) changed the tensile characteristics from an elastomer to a plastic. The high crosslinking was attributed to there being no phase separation between the hard and the soft segment. Hydrogen bonding between the PCL diol and the hard segment produced a high Tg. Raman spectra were able to identify the urethane linkage of PU containing different diisocyanates by showing the relative absorbance peaks. Synthesis of PU without isocyanate was successfully obtained via a polyaddition polymerization between a cyclic carbonate telechelic PCL/NR and 1,4-butylenediamine. The cyclic carbonate telechelic NR and cyclic carbonate telechelic PCL were prepared via the modification of the hydroxyl end groups of HTNR and PCL diols to carboxylic acid end groups by reacting with succinic anhydride. Then, the carboxylic acid end groups were changed to the cyclic carbonate end groups by using glycerol carbonate.
9

Optimisation multiobjectif de réseaux de transport de gaz naturel / Multiobjective optimization of natural gas transportation networks

Hernandez-Rodriguez, Guillermo 19 September 2011 (has links)
L'optimisation de l'exploitation d'un réseau de transport de gaz naturel (RTGN) est typiquement un problème d'optimisation multiobjectif, faisant intervenir notamment la minimisation de la consommation énergétique dans les stations de compression, la maximisation du rendement, etc. Cependant, très peu de travaux concernant l'optimisation multiobjectif des réseaux de gazoducs sont présentés dans la littérature. Ainsi, ce travail vise à fournir un cadre général de formulation et de résolution de problèmes d'optimisation multiobjectif liés aux RTGN. Dans la première partie de l'étude, le modèle du RTGN est présenté. Ensuite, diverses techniques d'optimisation multiobjectif appartenant aux deux grandes classes de méthodes par scalarisation, d'une part, et de procédures évolutionnaires, d'autre part, communément utilisées dans de nombreux domaines de l'ingénierie, sont détaillées. Sur la base d'une étude comparative menée sur deux exemples mathématiques et cinq problèmes de génie des procédés (incluant en particulier un RTGN), un algorithme génétique basé sur une variante de NSGA-II, qui surpasse les méthodes de scalarisation, de somme pondérée et d'ε-Contrainte, a été retenu pour résoudre un problème d'optimisation tricritère d'un RTGN. Tout d'abord un problème monocritère relatif à la minimisation de la consommation de fuel dans les stations de compression est résolu. Ensuite un problème bicritère, où la consommation de fuel doit être minimisée et la livraison de gaz aux points terminaux du réseau maximisée, est présenté ; l'ensemble des solutions non dominées est répresenté sur un front de Pareto. Enfin l'impact d'injection d'hydrogène dans le RTGN est analysé en introduisant un troisième critère : le pourcentage d'hydrogène injecté dans le réseau que l'on doit maximiser. Dans les deux cas multiobjectifs, des méthodes génériques d'aide à la décision multicritère sont mises en oeuvre pour déterminer les meilleures solutions parmi toutes celles déployées sur les fronts de Pareto. / The optimization of a natural gas transportation network (NGTN) is typically a multiobjective optimization problem, involving for instance energy consumption minimization at the compressor stations and gas delivery maximization. However, very few works concerning multiobjective optimization of gas pipelines networks are reported in the literature. Thereby, this work aims at providing a general framework of formulation and resolution of multiobjective optimization problems related to NGTN. In the first part of the study, the NGTN model is described. Then, various multiobjective optimization techniques belonging to two main classes, scalarization and evolutionary, commonly used for engineering purposes, are presented. From a comparative study performed on two mathematical examples and on five process engineering problems (including a NGTN), a variant of the multiobjective genetic algorithm NSGA-II outmatches the classical scalararization methods, Weighted-sum and ε-Constraint. So NSGA-II has been selected for performing the triobjective optimization of a NGTN. First, the monobjective problem related to the minimization of the fuel consumption in the compression stations is solved. Then a biojective problem, where the fuel consumption has to be minimized, and the gas mass flow delivery at end-points of the network maximized, is presented. The non dominated solutions are displayed in the form of a Pareto front. Finally, the study of the impact of hydrogen injection in the NGTN is carried out by introducing a third criterion, i.e., the percentage of injected hydrogen to be maximized. In the two multiobjective cases, generic Multiple Choice Decision Making tools are implemented to identify the best solution among the ones displayed of the Pareto fronts.
10

Estudo de permeação cutânea “in vitro” de micropartículas poliméricas contendo adapaleno por espectroscopia fotoacústica

Macenhan, William Roger 12 November 2018 (has links)
Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-02-14T11:29:36Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) William Roger Macenhan.pdf: 3712226 bytes, checksum: a7520ccd10d2cb5efa8ebec928e1f80c (MD5) / Made available in DSpace on 2019-02-14T11:29:36Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) William Roger Macenhan.pdf: 3712226 bytes, checksum: a7520ccd10d2cb5efa8ebec928e1f80c (MD5) Previous issue date: 2018-11-12 / O adapaleno (ADAP) é uma importante droga amplamente utilizada no tratamento tópico da acne. É um retinoide de terceira geração e fornece ação queratolítica, antiinflamatória e antiseborreica. No entanto, alguns efeitos adversos tópicos, como eritema, secura e descamação foram relatados com sua fórmula comercial. Nesse sentido, a microencapsulação desse fármaco usando poliésteres pode contornar seus efeitos colaterais tópicos e pode levar ao aumento da liberação de fármaco nas glândulas sebáceas. O objetivo deste trabalho foi obter micropartículas de poli (εcaprolactona) (PCL) carregadas com ADAP, preparadas pelo método de emulsão simples / evaporação do solvente. Formulações contendo 10 e 20% de ADAP foram obtidas com sucesso e caracterizadas por estudos morfológicos, espectroscópicos e térmicos. Valores de eficiência de encapsulação acima de 98% foram alcançados. As micropartículas apresentaram forma esférica e superfície lisa. Os resultados de espectroscopia no infravermelho por transformada de Fourier (FTIR) não apresentaram ligação química do fármaco-polímero e a técnica de calorimetria exploratória diferencial (DSC) mostrou uma parcial amorfização do fármaco. A permeação do ADAP na membrana Strat-M® para teste de difusão transdérmica foi avaliada por espectroscopia fotoacústica (PAS) na região espectral entre 225 e 400 nm após 15 min e 3 h da aplicação de formulações de PCL carregadas com ADAP. A PAS foi utilizada com sucesso para investigar a penetração de micropartículas de poliéster. Além disso, a microencapsulação diminuiu a difusão transmembrana in vitro do ADAP. / Adapalene (ADAP) is an important drug widely used in topical treatment of acne. It is a third generation retinoid and provides keratolytic, anti-inflammatory, and antiseborrhoic action. However, some topical adverse effects such as erythema, dryness, and scaling have been reported with its commercial formula. In this sense, the microencapsulation of this drug using polyesters can circumvent its topical side effects and can lead to the enhancement of drug delivery into sebaceous glands. The goal of this work was to obtain ADAP-loaded poly(ε-caprolactone) (PCL) microparticles prepared by simple emulsion/solvent evaporation method. Formulations containing 10 and 20% of ADAP were successfully obtained and characterized by morphological, spectroscopic and thermal studies. Values of encapsulation efficiency above 98% were achieved. Microparticles showed spherical shape and smooth surface. Fourier transform infrared spectroscopy (FTIR) results presented no drug-polymer chemical bond and differential scanning calorimetry (DSC) technique showed a partially amorphization of drug. ADAP permeation in Strat-M® membrane for transdermal diffusion testing was evaluated by photoacoustic spectroscopy (PAS) in the spectral region between 225 and 400 nm after 15 min and 3 h from application of ADAP-loaded PCL formulations. PAS was successfully used for investigating the penetration of polyester microparticles. In addition, microencapsulation decreased in vitro transmembrane diffusion of ADAP.

Page generated in 0.4006 seconds