No description available.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1963. / Vita. Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 151-153).

Submitted by Marlene Santos (marlene.bc.ufg@gmail.com) on 2016-08-17T17:39:28Z No. of bitstreams: 2 Tese - Celice Souza Novais - 2016.pdf: 6944336 bytes, checksum: 396bd8b19fe6b108a627ec89fed1736d (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-08-18T14:38:30Z (GMT) No. of bitstreams: 2 Tese - Celice Souza Novais - 2016.pdf: 6944336 bytes, checksum: 396bd8b19fe6b108a627ec89fed1736d (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-08-18T14:38:30Z (GMT). No. of bitstreams: 2 Tese - Celice Souza Novais - 2016.pdf: 6944336 bytes, checksum: 396bd8b19fe6b108a627ec89fed1736d (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The investigation of the chemical composition of the fruits and floral resin extract of Clusia rosea acclimatized in the Brazilian Savana (Cerrado) by classical chromatographic techniques led to identification of 14 compounds, such as the known hyperibona, nemorosona, plukenetionas and five new compounds. The composition of the volatiles oil of flower bud is significantly different from that observed in essence Clusia rosea grown on Atlantic Rainforest. The evaluation of the cytotoxic activity of the extract of the fruit and floral resin of Clusia rosea showed that these materials are significantly active against the lineage leukemic HL-60 and the floral resin extract was more active than the fruit extract. The selectivity is significant in Lucena resistant strain and the IC50 values are about 20 times larger than the HL-60 in the incubation time 24 hours. In the floral resin extract of Clusia gardnerii was found triterpenoids and benzophenones and no significant differences were observed the majority composition of male and female floral resin extracts. The fruits extract of this species have a large amount of eufol triterpeno. This study also includes the first report of the crystallography structure of propolona A roseafenona A and 1,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl)ethane. / A investigação da composição química do extrato dos frutos e da resina floral de Clusia rosea aclimatada no cerrado por técnicas cromatográficas clássicas levou a identificação 14 compostos, como a hyperibona, a nemorosona, as plukenetionas, sendo cinco estruturas inéditas. A composição do óleo essencial dos botões é significativamente diferente da essência observada na Clusia rosea cultivada em mata atlântica. A avaliação da atividade citotóxica do extrato dos frutos e da resina floral de Clusia rosea aclimatada no cerrado mostrou que estes materiais são 2 significativamente ativos frente à linhagem leucêmica HL-60, sendo o extrato da resina floral mais ativo que o do fruto. A seletividade é significativa na linhagem resistente Lucena cujos valores de IC50 são cerca de 20 vezes maiores que os da HL-60 no tempo de incubação de 24horas.No extrato da resina floral da Clusia gardnerii foram encontrados triterpenos e benzofenonas e não foram observadas diferenças significativas na composição majoritária das resinas dos indivíduos masculinos e femininos. O extrato dos frutos desta espécie é rico no triterpeno eufol.Esse estudo também inclui a primeira descrição por cristalografia dos compostos propolona A, roseafenona A e 1,2-bis(3,5-di-terc-butil-4hidroxifenil)etano.

Anthraquinone-xanthone heterodimeric natural products are a diverse family of polyketides highlighted by a unique bicyclo [3.2.2] ring system which links both anthraquinone and xanthone moieties. Both the connectivity of the unique bicyclic ring system and the oxidation state of the two heterocycles vary among the members of this family of natural products. These molecules have been generally isolated as fungal metabolites but also have shown anticoccidial (xanthoquinodin A:0.02 μg/mL), antibiotic (acremonidins A and C; 32 μM and acremoxanthone, MIC; 12.5 μg/mL), and cytotoxicity against various human cancer cell lines. Both anthraquinone and xanthone heterocycles are derived from the anthraquinone chrysophanol, a common biosynthetic intermediate for polyketide synthesis. To date, there have been no reported synthetic efforts or total syntheses of the anthraquinone-xanthone heterodimeric natural products. Related synthetic examples include complex anthraquinone-xanthone biaryls, anthraquinone dimers, and monomeric xanthone and benzophenone-derived natural products. We describe an initial proposed synthesis wherein we aimed to prepare the unique bicyclo [3.2.2] ring system in a late stage operation of functionalized anthraquinone and xanthone units through a photo-mediated cycloaddition. We achieved synthesis of both an anthraquinone-derived oxanthrone ester fragment and the synthesis of several xanthone related natural products, namely graphisin A, sydowinin B, acremonidin E, and pinselin. Key steps involve aryl anion addition to substituted benzaldehyde derivatives, subsequent methyl ester installation, and dehydrative cyclization. Although we have not yet achieved the desired cycloaddition, we contributed to this area by developing efficient, reliable syntheses of various benzophenone and xanthone natural products. We will also describe an alternative strategy to access the bicyclo [3.2.2] core of these natural products via various proposed rearrangements of an anthraquinone-xanthone biaryl intermediate. Cross-coupling of substituted xanthone and naphthalene fragments established the desired biaryl linkage which was further elaborated to afford anthraquinone-xanthone biaryl structures. Attempts to rearrange these biaryls are ongoing to produce the unique core structure of the parent natural products. Initially discovered as a byproduct of the aforementioned cross-coupling reaction, we have achieved homo-coupling of substituted naphthalene fragments. The resulting naphthalene dimers could be further advanced to a series of novel 2,2'-linked anthraquinone dimers including the natural product chrysotalunin.

This thesis reports an electron spin resonance absorption study of the hyperfine interaction between nuclei and a single "nearly-free" electron in dilute solutions of the benzophenone phenylhydrazone free radical in tetrahydrofuran.

No description available.

This dissertation aims to both deepen and broaden our understanding of copolymers with pendent benzophenone (BP) in relation to both established applications and novel directions in materials science. Photo-reaction of these BP copolymers is explored in attempts to achieve three distinct goals: (1) robust and efficiently photo-crosslinkable solid polymer films, (2) photo-reacted polymer blends with disordered bicontinuous nanostructures, and (3) photo-patterned hydrogel materials with environmental UV stability. We begin by investigating the fundamental gelation behavior of solid polymer films, finding BP copolymers to be particularly effective crosslinkable materials. Gelation efficiency can be tuned according to comonomer chemistry, as BP hydrogen abstraction on the main polymer chain increases chain scission, reducing crosslinking efficiency. This knowledge is then applied in Chapter 3, wherein we discuss two potential methods for preparing nanostructured polymer blends from these copolymers, namely spinodal decomposition of a photo-crosslinked polymer blend and solution-state photografting to create interfacially active species. While each technique shows promise, the ultimate goal of a disordered bicontinuous morphology will require further tuning of materials systems and protocols. Finally, chemical deactivation of BP photo-crosslinker in copolymers for use as photo-patternable and environmentally stable hydrogel materials is investigated. Reduction of BP by sodium borohydride proves a feasible route toward deactivating residual photo-crosslinker in patterned hydrogel films. These results confirm the utility of copolymers with pendent benzophenone photo-crosslinkers as useful tools for complex material systems.

No description available.

Atualmente, muitas pesquisas são realizadas com o objetivo de desenvolver novas formulações, sejam elas cosméticas ou farmacêuticas baseadas em nanocarreadores. Devido às suas características favoráveis, nanopartículas poliméricas são propostas como veículos tópicos, principalmente para fotoprotetores, com o intuito de prolongar o tempo de resistência dos filtros na pele, evitando assim o processo de fotodegradação. Filtros solares, de uma maneira geral, são formas cosméticas emulsionadas as quais são termodinamicamente instáveis. Para evitar este processo é necessário um componente capaz de manter esta estabilidade, isto é, um tensoativo. Em alguns sistemas, polissacarídeos ou proteínas atuam como tensoativos/estabilizantes em emulsões óleo/água (O/A). Neste contexto, a proposta deste trabalho é introduzir amidos modificados (catiônicos e aniônicos) e hidrolisados como tensoativo em uma formulação para a encapsulação da benzofenona-3 com uma matriz polimérica de poli(?-caprolactona) (PCL), avaliando a influência deste estabilizante nas características físico-químicas das nanopartículas. As nanopartículas foram preparadas mediante a técnica de deposição interfacial do polímero pré-formado, empregando-se um planejamento de experimentos de mistura. Previamente, foram avaliadas as condições da hidrólise enzimática, via planejamento de experimentos, para verificar quais parâmetros (tempo e concentração da enzima) maximizariam este processo reduzindo de maneira satisfatória a massa molar do amido para posterior aplicação como estabilizante. Foram realizados testes de tensão para avaliar a capacidade tensoativa das soluções aquosas dos amidos hidrolisados, para posterior aplicação na formulação de nanopartículas. Os resultados indicaram que dois lotes de amido, de quatro avaliados, podem ser empregados como tensoativos na formulação de nanopartículas, sem alterar significativamente propriedades, como diâmetro, polidispersão e teor de encapsulação. / Currently, many researches are conducted with the aim of developing new formulations, whether cosmetic or pharmaceutical-based nanocarriers. Due to its favorable characteristics, polymeric nanoparticles are proposed as topics vehicles, mainly for sunscreens, in order to prolong the resistance of the filters on the skin, thus preventing the photodegradation process. Sunscreens, in general, are emulsified cosmetic forms which are thermodynamically unstable. To avoid this process requires a component capable of maintaining this stability, i.e., a surfactant. In some systems, polysaccharides or proteins act as surfactants/stabilizers in oil-water emulsions (O/W). In this context, the purpose of this work is to introduce modified starches (cationic and anionic) and hydrolyzed as surfactant in a formulation for the encapsulation of benzophenone-3 with a polymer matrix of poly(?-caprolactone) (PCL), evaluating the influence of this stabilizer the physical-chemical characteristics of nanoparticles. The nanoparticles were prepared by interfacial deposition pre-formed polymer technique, using a design of experiments like mixture. Previously evaluated the conditions of enzymatic hydrolysis, by design of experiments to determine which parameters (time and enzyme concentration) to maximize this process satisfactorily reducing the molecular weight of the starch for subsequent use as a stabilizer. Tension tests were conducted to assess the ability of surfactant aqueous solutions of hydrolyzed starch for application in the formulation of nanoparticles. The results indicated that two batches of starch, four-valued, can be employed as a surfactant in the suspension of nanoparticles, without significantly altering properties such as diameter, polydispersity and the content of encapsulation.

Bisfenóis, filtros UV de benzofenona, parabenos e antimicrobianos como triclocarban são amplamente utilizados em produtos alimentares, farmacêuticos, cosméticos e de cuidados pessoais e também são encontrados como contaminantes. A maioria destes compostos apresentam possíveis efeitos adversos à saúde, principalmente devido ao fato de sua potencial atividade desreguladora endócrina. Neste sentido, é crescente o interesse pelo desenvolvimento de métodos analíticos que sejam mais simples e que possam ter a capacidade de detecção do maior número de analitos possíveis simultaneamente para uso em estudos de biomonitoramento humano. O objetivo deste projeto foi desenvolver um novo método de preparo de amostras em microextração em sorvente empacotado (MEPS, do inglês \"microextraction by packed sorbent\") para a extração simultânea de substâncias potencialmente desreguladoras endócrinas (parabenos, bisfenóis, benzofenonas e triclocarban). Em 250 ?L de urina sintética (pH 5,3) foram adicionados os analitos a uma concentração de 20 ng/mL e diluídos com 250 ?L de água. Após este procedimento, os compostos foram extraídos manualmente da amostra de urina usando MEPS C18 com 5 ciclos de aspirar-dispensar de 100 ?L. A eluição dos analitos foi realizada utilizando 100 ?L (metanol/água 80:20), seguido de análise em LC-MS/MS. O cartucho MEPS, após a limpeza, foi reutilizado para extrações múltiplas sem a presença de efeito de memória. As separações cromatográficas foram conduzidas em uma coluna C18 a 40 °C. A fase móvel foi composta por um gradiente de metanol e água a uma vazão de 500 ?L/min. Os dados foram adquiridos no modo MRM com íons negativos como precursores. O método MEPS-LC-MS/MS proposto apresentou curva de calibração linear para todos os analitos com coeficiente de correlação (r) maior que 0,99 no intervalo do limite inferior de quantificação (LIQ) a 20,0 ng/mL. Os LODs variaram de 0,005-0,1 ng/mL e os LIQ variaram de 0,5-2,5 ng/mL. Além disso, a precisão foi expressa como o coeficiente de variação, onde os valores obtidos foram menores que 20% (n=3) nos LIQ e menores que 15% (n=3) nas concentrações de 10,0 e 20,0 ng/mL. A exatidão foi expressa na forma de erro padrão relativo, onde os valores obtidos não foram superiores a ±20% (n=3) para os LIQ e ±15% (n=3) nas concentrações 10,0 e 20,0 ng/mL. O procedimento MEPS proposto apresentou vantagens que incluem a possibilidade de extração e determinação simultânea de 16 analitos em urina, com redução dos volumes de amostra e solvente utilizados, além de vantagens como tempo reduzido de preparo de amostra, clean up da matriz e dispensa etapa prévia ao preparo de amostra / Bisphenol, benzophenone UV filters, parabens and antimicrobials as triclocarban are widely used in food, pharmaceuticals products, cosmetic and personal care products or they are fond as contaminants. Most of these compounds show possible health adverse effects, mainly due to the fact of its potential endocrine disrupting activity. Thus, there is an increasing interesting in new analytical method development that will be simple and able to detect largest number of analytes possible simultaneously to be used in human biomonitoring studies. The project goal was developed a new sample preparation methody in Microextraction in packed sorbent (MEPS) to simultaneous extraction followed by liquid chromatography coupled to mass spectrometry in tandem analysis (LC-MS/MS) of 16 substances potentially endocrine disrupting (parabens, bisphenols, benzophenones and triclocarban). In 250 ?L of synthetic urine (pH 5.3) were spiked with compounds at a concentration of 20 ng/mL and diluted with 250 ?L of water. After this procedure, the compounds were extracted manually from urine sample using MEPS C18 with 5 draw-eject 100 ?L cycles. The elution was performed using 100 ?L (methanol/water 80:20) followed by LC-MS/MS analysis. The MEPS cartridge, after cleaned, was used for multiple extractions without any carry-over effect. Chromatographic separations were carried out on a C18 column at 40 oC. The Mobile phase was composed by a gradient methanol and water at a flow rate of 500 ?L/min. Data were acquired the MRM mode with negative ions as precursors. The proposed MEPS-LC-MS/MS method showed calibration curve linear to all analytes with correlation coefficient higher than 0,99 in the range from low limit of quantification (LIQ) to 20,0 ng/mL. The LODs range from 0,005-0,1 ng/mL and LIQ range from 0,5 to 2,5 ng/mL. Moreover, the precision was reported as variation coefficient, where the values were less than 20% (n=3) to the LIQ and less than 15% (n=3) to 10,0 and 20,0 ng/mL concentrations. The accuracy was reported as relative standard error, where the values were less than ±20% to the LIQ and less than ±15% (n=3) to 10,0 and 20,0 ng/mL concentrations. The MEPS procedure proposed showed advantages including possibility to extraction and simultaneous determination of 16 analytes in urine, with sample and solvents volume reduction besides it shows advantages as time reducing in sample preparation, matrix clean up and dispense previous sample preparation step.