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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.
261

Synthesis of Well-Defined Polymer Nanoparticles

Carl Urbani Unknown Date (has links)
The synthesis of well-defined polymer nanoparticles will have immediate applications in the biomedical industry as nanocontainers for the controlled delivery and release of water insoluble drugs. The ability to control molecular weight, particle morphology and chemical functionality and to obtain polymeric nanoparticles with narrow molecular weight and particle size distributions is paramount for their application-specific design. Two synthetic approaches were investigated in the synthesis of well-defined polymer nanoparticles, emulsion polymerization and self assembly. The successful implementation of Reversible Addition-Fragmentation Chain Transfer (RAFT) in emulsion polymerization was the first challenge faced when controlling nanoparticle molecular weight and size. Initially we showed that successful ‘living’ emulsion polymerizations of styrene could be carried out using a non-ionic surfactant. The success was achieved when preparing polymers of low molecular weight (5 and 9 K targeted Mn’s with polydispersities (PDIs) below 1.2). Deviation from ideal ‘living’ behavior occurred when targeting Mn’s greater than 20 K (at 100 % conversion). The ‘degassing technique’ was then investigated as an avenue to generate stable polystyrene nanoparticles by emulsion polymerization without the addition of surfactant (residual surfactant can result in detrimental effects on product quality). The polymerization of this emulsion system in the presence of a low reactive RAFT agent was ‘living’ in nature. In the presence of a high reactive RAFT agent the emulsion system showed ‘living’ nature, however, secondary nucleation occurred, which resulted in broad molecular weight distribution (MWD). Thus, the emulsion polymerization approach to preparing well-defined polymer nanoparticles was giving less than desirable results. An alternative method to prepare polymer nanoparticles with controlled chemical composition and morphology is to self assemble pre-synthesized block copolymers in water. This approach has several significant advantages over the emulsion systems: (i) all polymer chains are of near uniform chain length and chemical composition, (ii) the ratio between the hydrophobic and hydrophilic polymers can easily be controlled, (iii) chemical functionality can be located in different morphological regions, (iv) a wide range of 3-dimensional structures apart from spheres can be prepared (i.e. rods and vesicles), and (v) additives such as surfactant, stabilizers and residual monomer usually found after an emulsion polymerization are not required in the self assembly methodology. These advantages justify our shift in strategy. The only disadvantage of the self assembly process is that one cannot reach high weight fractions of polymer in water and is usually limited to below 2 wt-%, where as emulsion polymerizations can allow weight fractions of polymer close to 50 wt-%. Well-defined amphiphilic 4-arm star polyacrylic acid-block-polystyrene (PAA-b-PSTY) copolymers, prepared by RAFT solution polymerization, were dispersed in water to form core-shell micelles, in which the shell consisted of tethered PAA loops. The entropic penalty for having such loops resulted in a less densely packed PSTY core when compared to linear diblock copolymers of the same arm length. The surface of the shell was irregular due to the tethering points, but when cleaved the PAA chains extended to form a regular and relatively uniform corona. Controlling the polymer architecture enabled the synthesis of polymer micelles with tethered PAA loops, which could be opened to form uniform corona when desired. Three-miktoarm star and dendrimers with miktoarms consisting of PSTY, polytert-butyl acrylate (PtBA), polymethyl acrylate (PMA) and PAA were then synthesized using a combination of Atom Transfer Radical Polymerization (ATRP) and Huisgen 1,3-dipolar cycloaddition ‘click’ reactions. In all reactions, the stars and dendrimers were well-defined with PDIs lower than 1.09. This was the first step in the synthesis of well-defined highly ordered polymer structures. The synthesis of such structures demands high level of purity at each synthetic step eliminating the possibility of side reactions, which as of consequence lowers product yields. The synthesis and use of reactive solid supports to remove excess linear polymer to increase the yields of polymeric 3-arm stars and dendrimers was employed. These supports are a cheap approach to scavenge polymeric species with either azido or alkynyl functionality, after which the solid support can be filtered away from the product. These supports aided the synthesis of 3rd generation polymeric dendrons and dendrimers consisting of homopolymer PSTY with either solketals or alcohols at the periphery, diblock PSTY and PtBA, and amphiphilic diblock. The methodology used to construct these structures was a combination of ATRP to produce linear polymers with telechelic functionality, with the subsequent use of this functionality to join the polymers together via ‘click’ reactions. Micellization of the amphiphilic structures in water produced polymer nanoparticles of uniform size. The dendrimer nanoparticles were 18 nm in diameter, consisting of 19 individual dendrimers. The dendrimers most probably have no mutual interpenetration and thus pack uniformly to form the micelles. The dendron nanoparticles were 21 nm with an aggregation number of 43 dendrons per micelle, which suggests they form cone-like structures and self-assemble to form crew-cut micelles. Using a convergent approach polymer structures with unprecedented chemical diversity (hydrophobic or amphiphilic) and complexity (G2 miktoarm dendrimers with a degradable core) consisting of PSTY, PMA, PtBA and PAA were then synthesized with high purity using copper wire as the ‘click’ catalyst.
262

Zhodnocení online marketingové komunikace vybraného subjektu / Evaluation of Online Marketing Communication in Specific Enterprise

Mocek, Tomáš January 2017 (has links)
The thesis is focused on online marketing communication tools and their effectiveness. The theoretical part focuses on the basics of online marketing and especially to the summary and characteristics of the various tools of online marketing. Those are further described their main advantages and possibilities. The practical part presents selected anonymous company for which the individual tools analyzed. Analyzed are mainly paid channels used by the company to promote its services in the period from the perspective of visitor behavior on the site and in terms of effectiveness of individual channels. Evaluation is done by monitoring key indicators using web analytics Google Analytics. The aim of the thesis is to evaluate the effectiveness of online marketing tools selected companies. Partial order is based on the analyzed data to proposing possible changes and other recommendations in this area.
263

Um estudo da configuração de campanhas de publicidade digital : variáveis que afetam a taxa de cliques

Faria, Fellipe Gomes Marques de January 2017 (has links)
Esta dissertação visa identificar as variáveis que possuem maior influência sobre os resultados de campanhas de publicidade digital. Para levantar possíveis variáveis que interferem na taxa de cliques (click-through rate) nos anúncios online, inicialmente foi realizada uma revisão da literatura disponível sobre o tema. Para tanto, utilizou-se como estrutura conceitual o modelo da Teoria da Informação para categorização dos fatores encontrados. A partir dessa categorização, foram selecionados fatores para um projeto de experimento fatorial utilizando análise de variância (ANOVA). Os fatores escolhidos foram a segmentação do público-alvo por gênero, o segmento econômico do anunciante e características do anúncio: cor, presença de animação e frase de chamada para ação (call to action). O experimento concluiu que a ausência de frase de chamada para ação (call to action), imagens estáticas sem animação e a aderência do público-alvo a ser atingido pela campanha ao publico do produto anunciante são as características que apresentam uma performance significativa para taxas de cliques. As conclusões do estudo apontam direcionamentos úteis para as empresas que investem em mídia digital e elaboram campanhas online de publicidade. Do ponto de vista acadêmico, a revisão da literatura e o projeto de experimento deste estudo fornecem evidências para o entendimento das principais variáveis de influência sobre este tipo de projeto. / This master thesis aims to identify factors that influence on the results of digital advertising campaigns. To understand what can increase the digital click-through rate in these campaings, the first part of this research addressed a literature review about academic and professional studies about the influencing factors of these campaigns. The identified factors were organized in three main categories from the information-processing theory: source, message and recipient dimensions. These factors were then analyzed by means of a factorial experiment project using analysis of variance (ANOVA). The factors chosen were target gender, the advertiser’s economic segment and the advertisment characteristics: color and presence of animation and call to action. The experiment concluded that some factors were meaningful for the increase of the click-through rate. The fit between advertising campaign and the advertiser’s product target, absence of call to action phrase and non-animated banners presented meaningful increases in the performances of the banners click-through rates. The conclusions of this study point useful directions for digital media advertisers. From academic point of view, the literature revision and the analysis of variance in this research provide evidences for the understanding the main influence factors in this kind of projects.
264

Isolamento de cumarinas de espécies de Pterocaulon (Asteraceae) e síntese de 4-metilcumarinas / Isolation of coumarins from Pterocaulon balansae and synthesis of 4-methylcoumarins

Torres, Fernando Cidade January 2014 (has links)
As cumarinas são estruturas interessantes aos olhos da química medicinal, apresentando diversas atividades biológicas sobre os mais variados alvos. Neste trabalho, em um primeiro momento, realizamos a extração com CO2 em meio supercrítico das cumarinas de Pterocaulon balansae, planta nativa do Rio Grande do Sul que apresenta em sua composição grandes quantidades destes compostos. A extração com CO2 supercrítico apresentou rendimentos satisfatórios em massa de sete cumarinas previamente descritas para estas espécies. Dentre estes se destacam os compostos majoritários 7-(2,3-epoxi-3-metil-3-butiloxi)-6-metoxicumarina e 5,6-dimetoxi-7-(2’,3’-epoxi-3-metilbutiloxi) cumarina. Realizamos também a síntese de 4-metilcumarinas através de reação de Pechmann, obtendo o composto LaSOM 77 (7-hidroxi-4-matilcumarina) com excelentes rendimentos, onde realizamos uma diversificação estrutural através da adição de um linker e posteriormente a síntese de triazóis através de “Click Chemistry”. Para tanto, utilizamos uma biblioteca de 35 alcinos disponíveis comercialmente e outros 3 sintetizados em nosso laboratório. Sendo assim, obtivemos uma biblioteca de 38 híbridos cumarina-triazol que apresentaram excelentes rendimentos, em tempos reacionais que variaram entre 20 e 50 minutos de reação sob irradiação de microondas. Os testes biológicos preliminares frente a linhagens cancerígenas indicaram que os compostos sintetizados apresentam potencial utilização como anticancerígenos, sendo ativos frente a linhagens celulares de câncer de pulmão, fígado e mama, apresentando baixa toxicidade em células sadias. A partir das investigações teóricas e experimentais relacionadas à este trabalho foi produzido um artigo de revisão, intitulado “New insights into the chemistry and antioxidante activity of coumarins” está aceito pelo periódico Current Topics in Medicinal Chemistry. / Coumarins are interesting structures for the medicinal chemistry, because present several biological activities. At first, we performed the supercritical CO2 extraction from Pterocaulon balansae, a plant native from Rio Grande do Sul, which has in its composition large amounts of these compounds. The extraction with supercritical CO2 showed satisfactory yields of seven coumarins previously described for this species. Among these compounds the coumarins 7-(2,3-epoxy-3-methyl-3-butyloxy)-6-methoxycoumarin e 5,6-dimethoxy-7-(2’,3’-epoxy-3-methylbutyloxy) coumarin are the majority compunds. We also performed the synthesis of 4-methylcoumarins using Pechmann reaction, obtaining the compound LaSOM 77 (7-hydroxy-4-methyl-coumarin) in excellent yield and perfomed the structural diversification trougth the addition of a linker and subsequentely synthesis of 1,2,3-triazoles by Click Chemistry. Therefore, was used a colection of 35 commercialy available alkynes and other 3 synthesized in our laboratory to obtain a colection of 38 coumarin-triazole hybrids in excellent yields and time of reaction ranging betwenn 20 and 50 minutes under microwave radiation. Preliminary biological tests against cancerous strains indicated that the synthesized compounds have potential use as anticancer agents against cell lines of lung, liver and breast cancer. From the theorical and experimental data from this work, one review paper was produced: The article is intitled “New insights into the chemistry and antioxidante activity of coumarins” is accepted to the journal "Current Topics in Medicinal Chemistry".
265

Uso da modelagem molecular na solução de problemas em química / The use of molecular modelling in solving problems in chemistry

Madureira, Lucas Sousa 29 August 2014 (has links)
Made available in DSpace on 2016-06-02T20:34:57Z (GMT). No. of bitstreams: 1 6269.pdf: 8614736 bytes, checksum: a96a25f33487faa72f57cbe4d7b8e01b (MD5) Previous issue date: 2014-08-29 / Universidade Federal de Sao Carlos / The studies presented herein show the use of molecular modelling coupled to spectroscopic data to tackle four different problems in organic chemistry. In the first study, the sulfonylation of the primary hydroxyl group of the compound (2R,3S,6S)-2-(hydroxymethyl)-6-(1-phenyl-1H-1,2,3-triazol-4-yl)-3,6-dihydro-2Hpyran- 3-ol was addressed. The results show that the occurrence of the reaction depends on the stability of the S Cl secondary interactions and of the C-H Cl hydrogen bonds along the reaction pathway. The second investigation was the cycloaddition between benzyl azide and (organotelanil) alkynes. This reaction has a high driving force towards the products and generates fast and selectively a triazole with a n-butyltelluride substituent attached at position 5, which is stabilized by CH...Te interactions. So this cycloaddition fits the requirements of Click Chemistry. In third place, the conformations and relative configurations of 7 and 9 membered rings were elucidated by evaluating steric strain. The 7 membered ring shows a twisted chair conformation (TC) with C1, C7 and C10 having relative configurations S, R and S. The 9 membered ring has a twisted chair-chair conformation (TCC) and relative configurations R, S of C7 and C10. The fourth study was the optimization of rotational conformations of 1- (arylsulfonyl)indole derivatives. The different optimized conformations have the same stability and low rotational energy barrier, so that in the solid state the number of independent molecules in the asymmetric unit essentially depends on the packing intermolecular interactions. Regarding the stability of sulfonamide bonds the importance of hyperconjugative effects were showed, and the origin of the rotational barrier in the S-N bond is explained by the difference in steric hindrance and electrostatic interactions in the transition and the fundamental states. / As pesquisas aqui apresentadas mostram o uso da modelagem molecular acoplada a dados espectroscópicos em quatro problemas diferentes de química orgânica. No primeiro estudo abordou-se a sulfonilação da hidroxila primária do composto (2R,3S,6S)-2-(hidroximetil)-6-(1-fenil-1H-1,2,3-triazol-4- il)-3,6-dihidro-2H-piran-3-ol. Os resultados mostram que a ocorrência da reação depende da estabilidade de interações secundárias S...Cl e de ligações de hidrogênio C-H...Cl ao longo do caminho reacional. O segundo sistema investigado foi a cicloadição entre a benzil azida e (organotelanil)alcinos. Essa reação possui elevada driving force na direção dos produtos e gera seletiva e rapidamente o triazol com o substituinte n-butiltelureto ligado na posição 5, o qual é estabilizado por interações C-H...Te. De modo que essa cicloadição ajusta-se aos requisitos da proposta Click Chemistry. No terceiro trabalho, as conformações e configurações relativas de anéis de 7 e 9 membros foram elucidadas avaliando tensões estéricas. O anel de 7 membros apresenta a conformação cadeira torcida (TC) e configuração relativa S,R,S para C1, C7 e C10. Já o de 9 membros possui conformação cadeira-cadeira torcida (TCC) e configuração relativa R, S para C7 e C10. O quarto problema abordado foi a otimização de conformações rotacionais de derivados de 1-(arilsulfonil)indol. As diferentes conformações otimizadas possuem a mesma estabilidade e baixa barreira energética rotacional, de forma que no estado sólido o número de moléculas independentes na unidade assimétrica depende essencialmente das interações intermoleculares no empacotamento. Com relação à estabilidade das ligações sulfonamidas mostrou-se a importância dos efeitos hiperconjugativos, e a origem da barreira rotacional na ligação S-N é explicada pela diferença nos impedimentos estéricos e interações eletrostáticas entre os estados de transição e o fundamental.
266

Mise en forme et caractérisation de nano-fibres fonctionnalisées par chimie click pour l'ingénierie tissulaire / Processing and characterization of click-functionalized electrospun nano-fibers toward tissue engineering applications

Lancuski, Anica 20 December 2013 (has links)
Le procédé d’électro-filage est devenu une technique privilégiée pour la préparation des matériaux nano-fibreux, grâce à sa simplicité de mise en oeuvre, la polyvalence des matières premières utilisées, ainsi que la diversité des structures obtenues. Sa capacité à produire des réseaux fibrillaires, proches de ceux du vivant ont ouvert la voie à d’importantes applications en ingénierie tissulaire. Cette étude a porté sur i) l'élaboration de nano-fibres à base de biopolymères commerciaux par un procédé d’électro-filage, pour des applications en ingénierie tissulaire, ii) leur fonctionnalisation et, iii) l’étude par SANS de la stabilité des chaînes de polymères constituant ces fibres. La stabilité d’un polymère est un facteur important pour la dégradation contrôlée dans les systèmes biologiques. Des études de la stabilité de polystyrène, utilisé ici comme un modèle simple, dans le milieu confiné des nanofibres, ont été élaborés avec la technique de diffusion de neutrons aux petits angles. L’investigation de la conformation des chaînes de polymère dans les nanofibres montre une anisotropie remarquable, en suggérant une forte déformation des chaînes dans la direction axiale des fibres d’au cours de procédé d’électro-filage. La dynamique de relaxation des chaînes a permis d’évaluer leur stabilité et vieillissement dans le milieu confiné des nanofibres. Des fibres biocompatibles à base de poly(-caprolactone) (PCL) ont été électro-filées et optimisées pour obtenir des matériaux nano-structurés et fonctionnalisés en vue d’applications biomédicales. L’introduction par chimie click azide-alcyne de groupes saccharidiques dans le coeur ou en surface des fibres de PCL a été réalisée très efficacement selon deux approches distinctes avant ou après électro-filage. Les caractérisations physico-chimiques et biologiques réalisées sur les différents systèmes ont notamment permis de mettre en évidence la biodisponibilité des sucres à la surface des fibres ainsi que leur capacité à rendre la PCL hydrophile. Ces résultats attestent du potentiel de la chimie click à permettre la fonctionnalisation de fibres de polyesters sans altération de leur structure ouvrant ainsi d’importantes perspectives dans le domaine de l’ingénierie tissulaire. / Electrospinning process has become a leading technique for producing nano-fibrous scaffolds that are highly porous, lighter, and with superior mechanical properties than their bulk equivalents. Structural properties of electrospun fibers closely resemble to the connective cell tissue, making these nonwovens readily employed in medicine and pharmacy. The research study of this thesis focused on bridging the commercially available biopolymers with the tissue engineering applications through multifunctional aspects of carbohydrates and click chemistry coupling. Biocompatible fibers were electrospun from poly(-caprolactone) and further optimized into clickable azido-PCL scaffolds. Their surface-activity was visualized after click coupling of a fluorescent dye onto PCL-based electrospun fibers, while hydrophilicity and bioactivity were achieved by covalent bonding of carbohydrates, enabling specific cell adhesion possibilities of these nonwovens. Selective lectin surface-immobilization revealed the potential of these scaffolds for specific protein adhesion and therefore controlled cell-material interactions. Polymer stability is an important factor for controlled degradation in tissue engineering applications. Small angle neutron scattering studies were carried out to estimate the stability of polystyrene as a model-polymer, its chain conformation in as-spun and thermally annealed electrospun fibers. Notable anisotropy of polymeric chains within the fibers was observed. The terminal relaxation time of the polystyrene was estimated and compared to the theoretical value.
267

Avaliação experimental de sistemas de rastreamento ocular do ponto de vista de ações de apontamento e seleção: um estudo de caso.

SARMENTO, Camila Freitas. 18 May 2018 (has links)
Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-05-18T14:39:46Z No. of bitstreams: 1 CAMILA FREITAS SARMENTO - DISSERTAÇÃO (PPGCC) 2016.pdf: 4961377 bytes, checksum: d5055e8a66475194dc09f3c2b5e8009b (MD5) / Made available in DSpace on 2018-05-18T14:39:46Z (GMT). No. of bitstreams: 1 CAMILA FREITAS SARMENTO - DISSERTAÇÃO (PPGCC) 2016.pdf: 4961377 bytes, checksum: d5055e8a66475194dc09f3c2b5e8009b (MD5) Previous issue date: 2016 / O objetivo geral desta dissertação é comparar a usabilidade de dois rastreadores oculares de domínio público (os quais utilizam apenas a imagem capturada por uma webcam convencional) e um rastreador comercial de baixo custo, o Tobii EyeX Controller, dotado de múltiplas câmeras dedicadas, durante a realização de tarefas de apontamento e seleção em um computador desktop. Esta pesquisa tem os seguintes objetivos específicos: (1) adaptar parcialmente a abordagem de avaliação proposta por Queiroz (2001) ao contexto de tarefas de apontamento e seleção via rastreamento ocular; (2) confrontar a natureza das falhas identificadas a partir de indicadores da usabilidade de rastreadores oculares; e (3) verificar quais dos identificadores de desempenho dos rastreadores oculares confrontados influenciam positivamente a satisfação subjetiva do usuário. Concluiu-se que os indicadores de eficiência apresentaram resultados satisfatórios para os rastreadores de domínio público. Concluiu-se também que o indicador da satisfação subjetiva do usuário exibiu os melhores escores para os rastreadores de domínio público. / The main objective of this dissertation is to compare the usability of two eyetrackers of the public domain (which use only the image captured by a conventional webcam), and a low-cost commercial eye tracker, the Tobii EyeX Controller, equipped with multiple dedicated cameras, during pick-and-click tasks on a desktop computer. This research has the following specific objectives: (1) to adjust partially the evaluation approach proposed by Queiroz (2001) to the context of pointing and selection tasks via eye-tracking; (2) to compare the nature of the problems identified from usability indicators of eye trackers; and (3) to determine which performance indicators of the confronted eye trackers positively impact on the subjective user satisfaction. It was concluded that the chosen efficiency indicators have shown satisfactory results for public domain eye tracker solutions. It was also concluded that the subjective user satisfaction indicator has shown best scores for public domain eye tracker solutions.
268

Um estudo da configuração de campanhas de publicidade digital : variáveis que afetam a taxa de cliques

Faria, Fellipe Gomes Marques de January 2017 (has links)
Esta dissertação visa identificar as variáveis que possuem maior influência sobre os resultados de campanhas de publicidade digital. Para levantar possíveis variáveis que interferem na taxa de cliques (click-through rate) nos anúncios online, inicialmente foi realizada uma revisão da literatura disponível sobre o tema. Para tanto, utilizou-se como estrutura conceitual o modelo da Teoria da Informação para categorização dos fatores encontrados. A partir dessa categorização, foram selecionados fatores para um projeto de experimento fatorial utilizando análise de variância (ANOVA). Os fatores escolhidos foram a segmentação do público-alvo por gênero, o segmento econômico do anunciante e características do anúncio: cor, presença de animação e frase de chamada para ação (call to action). O experimento concluiu que a ausência de frase de chamada para ação (call to action), imagens estáticas sem animação e a aderência do público-alvo a ser atingido pela campanha ao publico do produto anunciante são as características que apresentam uma performance significativa para taxas de cliques. As conclusões do estudo apontam direcionamentos úteis para as empresas que investem em mídia digital e elaboram campanhas online de publicidade. Do ponto de vista acadêmico, a revisão da literatura e o projeto de experimento deste estudo fornecem evidências para o entendimento das principais variáveis de influência sobre este tipo de projeto. / This master thesis aims to identify factors that influence on the results of digital advertising campaigns. To understand what can increase the digital click-through rate in these campaings, the first part of this research addressed a literature review about academic and professional studies about the influencing factors of these campaigns. The identified factors were organized in three main categories from the information-processing theory: source, message and recipient dimensions. These factors were then analyzed by means of a factorial experiment project using analysis of variance (ANOVA). The factors chosen were target gender, the advertiser’s economic segment and the advertisment characteristics: color and presence of animation and call to action. The experiment concluded that some factors were meaningful for the increase of the click-through rate. The fit between advertising campaign and the advertiser’s product target, absence of call to action phrase and non-animated banners presented meaningful increases in the performances of the banners click-through rates. The conclusions of this study point useful directions for digital media advertisers. From academic point of view, the literature revision and the analysis of variance in this research provide evidences for the understanding the main influence factors in this kind of projects.
269

Isolamento de cumarinas de espécies de Pterocaulon (Asteraceae) e síntese de 4-metilcumarinas / Isolation of coumarins from Pterocaulon balansae and synthesis of 4-methylcoumarins

Torres, Fernando Cidade January 2014 (has links)
As cumarinas são estruturas interessantes aos olhos da química medicinal, apresentando diversas atividades biológicas sobre os mais variados alvos. Neste trabalho, em um primeiro momento, realizamos a extração com CO2 em meio supercrítico das cumarinas de Pterocaulon balansae, planta nativa do Rio Grande do Sul que apresenta em sua composição grandes quantidades destes compostos. A extração com CO2 supercrítico apresentou rendimentos satisfatórios em massa de sete cumarinas previamente descritas para estas espécies. Dentre estes se destacam os compostos majoritários 7-(2,3-epoxi-3-metil-3-butiloxi)-6-metoxicumarina e 5,6-dimetoxi-7-(2’,3’-epoxi-3-metilbutiloxi) cumarina. Realizamos também a síntese de 4-metilcumarinas através de reação de Pechmann, obtendo o composto LaSOM 77 (7-hidroxi-4-matilcumarina) com excelentes rendimentos, onde realizamos uma diversificação estrutural através da adição de um linker e posteriormente a síntese de triazóis através de “Click Chemistry”. Para tanto, utilizamos uma biblioteca de 35 alcinos disponíveis comercialmente e outros 3 sintetizados em nosso laboratório. Sendo assim, obtivemos uma biblioteca de 38 híbridos cumarina-triazol que apresentaram excelentes rendimentos, em tempos reacionais que variaram entre 20 e 50 minutos de reação sob irradiação de microondas. Os testes biológicos preliminares frente a linhagens cancerígenas indicaram que os compostos sintetizados apresentam potencial utilização como anticancerígenos, sendo ativos frente a linhagens celulares de câncer de pulmão, fígado e mama, apresentando baixa toxicidade em células sadias. A partir das investigações teóricas e experimentais relacionadas à este trabalho foi produzido um artigo de revisão, intitulado “New insights into the chemistry and antioxidante activity of coumarins” está aceito pelo periódico Current Topics in Medicinal Chemistry. / Coumarins are interesting structures for the medicinal chemistry, because present several biological activities. At first, we performed the supercritical CO2 extraction from Pterocaulon balansae, a plant native from Rio Grande do Sul, which has in its composition large amounts of these compounds. The extraction with supercritical CO2 showed satisfactory yields of seven coumarins previously described for this species. Among these compounds the coumarins 7-(2,3-epoxy-3-methyl-3-butyloxy)-6-methoxycoumarin e 5,6-dimethoxy-7-(2’,3’-epoxy-3-methylbutyloxy) coumarin are the majority compunds. We also performed the synthesis of 4-methylcoumarins using Pechmann reaction, obtaining the compound LaSOM 77 (7-hydroxy-4-methyl-coumarin) in excellent yield and perfomed the structural diversification trougth the addition of a linker and subsequentely synthesis of 1,2,3-triazoles by Click Chemistry. Therefore, was used a colection of 35 commercialy available alkynes and other 3 synthesized in our laboratory to obtain a colection of 38 coumarin-triazole hybrids in excellent yields and time of reaction ranging betwenn 20 and 50 minutes under microwave radiation. Preliminary biological tests against cancerous strains indicated that the synthesized compounds have potential use as anticancer agents against cell lines of lung, liver and breast cancer. From the theorical and experimental data from this work, one review paper was produced: The article is intitled “New insights into the chemistry and antioxidante activity of coumarins” is accepted to the journal "Current Topics in Medicinal Chemistry".
270

Síntese e avaliação antiparasitária de quinolinas conjugadas à 1,2,3-triazóis

Meinel, Raíssa Soares 22 July 2016 (has links)
Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-04T14:25:19Z No. of bitstreams: 1 raissasoaresmeinel.pdf: 3680186 bytes, checksum: ec85e901c8bb646178cf7aa00e18cdd6 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-13T13:49:00Z (GMT) No. of bitstreams: 1 raissasoaresmeinel.pdf: 3680186 bytes, checksum: ec85e901c8bb646178cf7aa00e18cdd6 (MD5) / Made available in DSpace on 2017-05-13T13:49:00Z (GMT). No. of bitstreams: 1 raissasoaresmeinel.pdf: 3680186 bytes, checksum: ec85e901c8bb646178cf7aa00e18cdd6 (MD5) Previous issue date: 2016-07-22 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A presente dissertação, intitulada "Síntese e Avaliação Antiparasitária de Quinolinas Conjugadas à 1,2,3-Triazóis” trata da preparação, caracterização e avaliação biológica de compostos orgânicos contendo uma porção quinolínica associada a um anel triazólico 1,4-dissubstituído. Explorando a ferramenta de hibridação molecular, encontra-se descrita também neste trabalho a preparação de Bases de Schiff a partir das quinolinas conjugadas. Os compostos foram preparados através da formação de triazóis utilizando a reação do tipo “click” chemistry. As estruturas químicas dos produtos obtidos foram confirmadas por espectroscopia no infravermelho, ressonância magnética nuclear de 1H e de 13C e faixa de fusão. Os compostos sintetizados foram avaliados em crescimentos de parasitos in vitro e in vivo (P. berghei e leishmania). / The dissertation entitled “Synthesis and antiparasitic evaluation of Quinolines conjugated 1,2,3- Triazoles” deals with the preparation, characterization and evaluation of the biological potential of organic compounds containing a quinoline portion associated with 1,2,3-Triazole 1,4-dissubstituted. Further exploring the molecular hybridization tool is also described the preparation of Schiff bases from these conjugated quinolines. The compounds were prepared by using the triazole forming reaction such as "click " chemistry . The chemical structures of the products obtained were confirmed by infrared spectroscopy , nuclear magnetic resonance 1H and 13C and melting point . The synthesized compounds were evaluated in growth of parasites in vitro and in vivo (P. berghei and leishmania).

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