A análise de fluxos metabólicos para a produção de PHAMCL por Pseudomonas sp. LFM046 revelou que a baixa eficiência de conversão de carboidratos em PHA (60-70% do valor máximo teórico) deve estar associada à utilização principal da via das pentoses (VP) para o metabolismo de carboidratos. Eficiências significativamente maiores poderiam ser obtidas se uma parcela maior da glicose fosse metabolizada pela via Entner-Doudoroff (ED). Assim, neste trabalho foi realizada a análise de fluxos metabólicos utilizando glicose marcada (C13) e o melhoramento genético de Pseudomonas sp. LFM046 utilizando estratégia de engenharia metabólica. Experimentos com glicose marcada confirmaram um maior fluxo de carboidratos pela VP em relação a ED. A superexpressão de genes específicos de ED em Pseudomonas sp. LFM046 demonstrou apenas pequenos aumentos na eficiência de conversão de carboidratos em PHA pelas linhagens recombinantes. / The metabolic flux analysis for PHAMCL production by Pseudomonas sp. LFM046 revealed that the low efficiency of carbohydrates conversion into PHA (60-70% of the maximum theoretical value) should be associated with the main use of pentose phosphate pathway (PP) for the carbohydrate metabolism. Significantly higher efficiencies could be obtained if a larger portion of the glucose was metabolized via the Entner-Doudoroff (ED). Therefore, the metabolic fluxes analysis was performed in this work using labeled glucose (13C) and the genetic improvement of Pseudomonas sp. LFM046 by using metabolic engineering approach. Experiments with labeled glucose confirmed an increased flow of carbohydrates by PP compared to ED. The overexpression of specific genes from ED in Pseudomonas sp. LFM046 showed only small increases in the efficiency of carbohydrates conversion into PHA by recombinant strains.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-06-02T18:27:27Z No. of bitstreams: 1 fabiodesouzafernandes.pdf: 7715864 bytes, checksum: acdec01f503078f8065c0a21a2cabf58 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-07-02T13:17:43Z (GMT) No. of bitstreams: 1 fabiodesouzafernandes.pdf: 7715864 bytes, checksum: acdec01f503078f8065c0a21a2cabf58 (MD5) / Made available in DSpace on 2016-07-02T13:17:43Z (GMT). No. of bitstreams: 1 fabiodesouzafernandes.pdf: 7715864 bytes, checksum: acdec01f503078f8065c0a21a2cabf58 (MD5) Previous issue date: 2012-02-27 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / As aminas e aminoalcoóis são uma importante classe química que se encontra presente em um vasto grupo de substâncias de ocorrência natural e sintética. O aminoálcool S,S-etambutol é um agente quimioterapêutico antitubercular seguro de primeira escolha. Aminas e aminoalcoóis glicosilados são conhecidos pelas suas atividades antibacterianas. Este trabalho trata da síntese de derivados de aminoalcoóis acoplados a série D-arabinose e D-galactose, que resultou na obtenção de quatorze compostos inéditos. Em um primeiro momento foram preparados seis diaminas e sete aminoálcoois N-alquilados com cadeias carbônicas de diferentes tamanhos. As diaminas e aminoalcoóis obtidos foram acoplados ao intermediário 6-O-(2’,3’- epoxipropil)-1,2:3,4-di-isopropilideno- -D-galactopiranosídeo que foi preparado por meio de reações clássicas da química de carboidratos. Foram obtidos treze compostos inéditos estando todos na forma de mistura de diasteroisômeros. Obteve-se também um aminoálcool derivado da série D-arabinose. Este foi preparado pela reação de abertura do epóxido do derivado 2,3-anidro-5-Obenzil- -D-lixofuranosídeo de metila pelo aminoálcool comercial monoetanolamina. Vários aminoálcoois da série D-galactose, foram submetidos à avaliação de suas atividades antibacterianas e antituberculose e apresentaram resultados promissores. / A amines and aminoalcohols are important chemical classes that are present in a large group of synthetic and naturally occurring substances. The presence of alcohol and amine functional groups allow these substances aminoalcohol S,S-ethambutol is a reliable first-line antitubercular chemotherapeutic agent. Glycosylated amines and aminoalcohols are known for their antibacterial activities. This work describes the synthesis of aminoalcohols derived from Darabinose and D-galactose which resulted in the synthesis of fourteen novel compounds. Initially we reported the preparation of six diamines and seven Nalkylated amines with carbon chains of different lengths. The diamines and aminoalcohols thus obtained were coupled to the intermediate 6-O-(2’,3’- epoxypropyl)-1,2:3,4-di-isopropylidene- -D-galactopyranoside that was prepared by classical carbohydrate chemical reactions. Thirteen new compounds were obtained, all in the form of diastereoisomeric mixture. We also obtained an aminoalcohol derived from D-arabinose series. This was prepared by the epóxido opening reaction of methyl 2,3-anydro-5-Obenzyl- -D-lyxofuranoside from the commercial aminoalcohol monoethanolamine. Several aminoalcohols of the D-galactose series were submitted for biological assays in order to evaluate their antibacterial and antitubercular activities and showed promising results.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-06-28T19:17:55Z No. of bitstreams: 1 fabiodesouzafernandes.pdf: 7715864 bytes, checksum: acdec01f503078f8065c0a21a2cabf58 (MD5) / Approved for entry into archive by Diamantino Mayra (mayra.diamantino@ufjf.edu.br) on 2016-07-05T14:33:16Z (GMT) No. of bitstreams: 1 fabiodesouzafernandes.pdf: 7715864 bytes, checksum: acdec01f503078f8065c0a21a2cabf58 (MD5) / Made available in DSpace on 2016-07-05T14:33:16Z (GMT). No. of bitstreams: 1 fabiodesouzafernandes.pdf: 7715864 bytes, checksum: acdec01f503078f8065c0a21a2cabf58 (MD5) Previous issue date: 2012-02-27 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / As aminas e aminoalcoóis são uma importante classe química que se encontra presente em um vasto grupo de substâncias de ocorrência natural e sintética. O aminoálcool S,S-etambutol é um agente quimioterapêutico antitubercular seguro de primeira escolha. Aminas e aminoalcoóis glicosilados são conhecidos pelas suas atividades antibacterianas. Este trabalho trata da síntese de derivados de aminoalcoóis acoplados a série D-arabinose e D-galactose, que resultou na obtenção de quatorze compostos inéditos. Em um primeiro momento foram preparados seis diaminas e sete aminoálcoois N-alquilados com cadeias carbônicas de diferentes tamanhos. As diaminas e aminoalcoóis obtidos foram acoplados ao intermediário 6-O-(2’,3’- epoxipropil)-1,2:3,4-di-isopropilideno- -D-galactopiranosídeo que foi preparado por meio de reações clássicas da química de carboidratos. Foram obtidos treze compostos inéditos estando todos na forma de mistura de diasteroisômeros. Obteve-se também um aminoálcool derivado da série D-arabinose. Este foi preparado pela reação de abertura do epóxido do derivado 2,3-anidro-5-Obenzil- -D-lixofuranosídeo de metila pelo aminoálcool comercial monoetanolamina. Vários aminoálcoois da série D-galactose, foram submetidos à avaliação de suas atividades antibacterianas e antituberculose e apresentaram resultados promissores. / A amines and aminoalcohols are important chemical classes that are present in a large group of synthetic and naturally occurring substances. The presence of alcohol and amine functional groups allow these substances aminoalcohol S,S-ethambutol is a reliable first-line antitubercular chemotherapeutic agent. Glycosylated amines and aminoalcohols are known for their antibacterial activities. This work describes the synthesis of aminoalcohols derived from Darabinose and D-galactose which resulted in the synthesis of fourteen novel compounds. Initially we reported the preparation of six diamines and seven Nalkylated amines with carbon chains of different lengths. The diamines and aminoalcohols thus obtained were coupled to the intermediate 6-O-(2’,3’- epoxypropyl)-1,2:3,4-di-isopropylidene- -D-galactopyranoside that was prepared by classical carbohydrate chemical reactions. Thirteen new compounds were obtained, all in the form of diastereoisomeric mixture. We also obtained an aminoalcohol derived from D-arabinose series. This was prepared by the epóxido opening reaction of methyl 2,3-anydro-5-Obenzyl- -D-lyxofuranoside from the commercial aminoalcohol monoethanolamine. Several aminoalcohols of the D-galactose series were submitted for biological assays in order to evaluate their antibacterial and antitubercular activities and showed promising results.

Orientadores: Márcia Regina Braga, Fábio Sérgio Barbosa da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-26T06:23:41Z (GMT). No. of bitstreams: 1 Coelho_LeilyaneConceicaodeSouza_D.pdf: 6987430 bytes, checksum: fca51edac0c11a47ee297e2afe9a5a4c (MD5) Previous issue date: 2014 / Resumo: Sesbania virgata (Cav.) Pers. é uma Fabaceae com potencial para revegetação de áreas degradadas e que forma simbiose com fungos micorrízicos arbusculares (FMA). Suas sementes possuem aleloquímicos que são exsudados no início do processo de embebição e encontrados no ambiente que circunda a semente germinante. Ao analisar a co-germinação de S. virgata com sementes de tomate (Solanum lycopersicum L.), foi observada inibição da germinação e redução no índice de velocidade de germinação (IVG) de sementes de tomate, afetando severamente o crescimento inicial da plântula. Para arroz (Oryza sativa L.), os únicos parâmetros sensíveis à co-germinação com S. virgata foram o comprimento radicular e da parte aérea. A avaliação dos efeitos alelopáticos de extratos aquosos de exsudatos de sementes de S. virgata sobre essas espécies agronômicas mostrou que a germinação e o crescimento das plântulas foram afetados já com a menor concentração utilizada (1 mg mL-1). Além disso, em presença do exsudato, as sementes de tomate e arroz mostraram redução na mobilização dos carboidratos de reserva, fato não observado quando (+)-catequina comercial foi utilizada, sugerindo que existem outros compostos alelopáticos em sementes de S. virgata, além da (+)-catequina, que podem interferir no desenvolvimento das espécies estudadas. Os exsudatos de sementes de S. virgata reduziram a atividade da endo-?-mananase e aumentaram a da invertase ácida vacuolar em tomate, enquanto que a (+)-catequina comercial promoveu a atividade da endo-?-mananase e inibiu a da invertase ácida de parede celular. Ao examinar os efeitos de exsudatos brutos de sementes e de raízes de S. virgata em relação à fase assimbiótica de FMA, avaliando-se a germinação e o crescimento micelial in vitro de esporos de Gigaspora albida Becker & Hall, foi observado estímulo a G. albida somente na presença dos exsudatos de sementes. Pode-se concluir que as sementes de S. virgata apresentam efeito alelopático sobre as espécies agronômicas avaliadas, inibindo o seu crescimento e interferindo com a mobilização de reservas, e que seus exsudatos exercem efeitos positivos sobre a fase assimbiótica de G. albida / Abstract: Sesbania virgata (Cav.) Pers. is a legume species with potential for restoration of degraded areas and that forms symbiosis with arbuscular mycorrhizal fungi (AMF). Their seeds have allelochemicals that are exudated at the beginning of the imbibition process and found in the environment that surrounds the germinating seed. Co-germination of S. virgata with seeds of tomato (Solanum lycopersicum L.) caused reduction in the germination percentage and germination speed index (IVG) of tomato, severely affecting seedling initial growth. Co-germination of rice (Oryza sativa L.) with S. virgata reduced root length and the growth of the aerial part of rice seedlings. The allelopathic effects of the S. virgata seed exudates on germination and seedling growth of these agronomic species were seen at the lowest assayed concentration (1 mg mL-1). In addition, in the presence of the exudates, reduction in mobilization of storage carbohydrates was observed in seeds of tomato and rice, an effect that was not seen when commercial (+)-catechin was used. These results suggest that, besides (+)-catechin, there are other allelopathic compounds in seeds of S. virgata that can interfere with the development of the agronomic species. In tomato, seed exudates of S. virgata reduced the activity of endo-?-mannanase and increased vacuolar acid invertase, whereas commercial (+)-catechin promoted the activity of endo-?-mannanase and inhibited cell wall acid invertase. When seed or root exudates of S. virgata were assayed on the assymbiotic phase of the AMF, spore germination and mycelial growth of Gigaspora albida Becker & Hall were stimulated in vitro only in the presence of the seed exudates. We concluded that seeds of S. virgata have allelopathic effect on agronomic species, inhibiting their growth and interfering with the mobilization of reserves and that their exudates exert positive effects on the assymbiotic phase of G. albida / Doutorado / Biologia Celular / Doutora em Biologia Celular e Estrutural

No description available.

M.Sc. / The main objective of this project was to synthesize carbohydrates that contain a thiol functional group, commonly known as thiocarbohydrates and subsequently employ them as stabilizing agents in the synthesis of gold nanoparticles and as ligands in the synthesis of phosphine thiocarbohydrate gold(I) complexes. In achieving our objective, thiocarbohydrate compounds 62, 64, 69 and 71 were successfully synthesized from acetylated 60 or benzylated glucal 66 using a Ferrier rearrangement reaction. NaHSO4-SiO2 was used as a catalyst for Ferrier rearrangement reaction in the presence of dithiol type nucleophiles (i.e. 1,2-dithiol ethane or 1,5-dithiol pentane) to afford the desired thiocarbohydrate compounds. The S-acetate derivatives 63, 65, 70 and 72 of the corresponding thiocarbohydrates were prepared as a confirmatory test for the presence of the terminal thiol (SH) in the thiocarbohydrate compounds. C-2 modified thiocarbohydrate compounds 78 and 80 were synthesized from C-2 iodomethyl glycoside 77 following a literature reported procedure in the presence of 1,2-dithiol ethane or 1,5-dithiol pentane as nucleophiles. S-acetate derivatives 79 and 81 of the corresponding thiocarbohydrate compounds were synthesized again to confirm the presence of the terminal thiol (SH). All the thiocarbohydrate compounds and their corresponding S-acetate derivatives were characterized with NMR spectroscopy and HRMS. Ethyl thiocarbohydrate compounds 62, 69 and 78 were successfully employed as stabilizing agents in the preparation of gold nanoparticles GNP1-GNP9 following a Brust-Schiffrin procedure. UV-Vis spectroscopy and transmission electron microscopy (TEM) were used to characterize these gold nanoparticles. Phosphine thiocarbohydrate gold(I) complexes 84-94 were synthesized from selected thiocarbohydrate compounds. NMR spectroscopy and HRMS were used to characterize these gold(I) complexes. Having synthesized the target thiocarbohydrate compounds, gold nanoparticles and gold(I) complexes, our aim was to investigate their biological activity against cancer and HIV. However, the biological testing process took considerably longer and as a result this dissertation was submitted without the biological tests results.

8 pp. / With the growing popularity of the gluten-free diet, there are many misconceptions surrounding gluten, carbohydrates, celiac disease, and gluten-sensitivity. This article explains the definitions of and differences between celiac disease, gluten-sensitivity, and other gluten-related conditions. The article also addresses the risks of adopting a gluten-free diet without a medical necessity to do so. Lastly, the article provides a healthy gluten-free recipe.

No description available.

Inhibiting the formation of ice is an essential process commercially, industrially, and medically. Compounds that work to stop the formation of ice have historically possessed drawbacks such as toxicity or prohibitively high active concentrations. One class of molecules, ice recrystallization inhibitors, work to reduce the damage caused by the combination of small ice crystals into larger ones. Recent advances made by the Ben lab have identified small molecule carbohydrate analogues that are highly active in the field of ice recrystallization and have potential in the cryopreservation of living tissue. A similar class of molecules, kinetic hydrate inhibitors, work to prevent the formation of another type of ice – gas hydrate. Gas hydrates are formed by the encapsulation of a molecule of a hydrocarbon inside a growing ice crystal. These compounds become problematic in high pressure and low temperature areas where methane is present - such as an oil pipeline. A recent study has highlighted the effects of antifreeze glycoprotein, a biological ice recrystallization inhibitor, in the inhibition of methane clathrates. Connecting these two fields through the synthesis and testing of small molecule ice recrystallization inhibitors in the inhibition of methane hydrates is unprecedented and may lead to a novel class of compounds.

Orientadores: Telma Teixeira Franco, Eduardo Jacob-Lopes / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-24T13:35:37Z (GMT). No. of bitstreams: 1 Francisco_ErikaCristina_D.pdf: 1584353 bytes, checksum: 7fa11e2a9de2d170e12cddabf84ac647 (MD5) Previous issue date: 2014 / Resumo: O objetivo do estudo foi avaliar a produção de biomassa e o acúmulo lipídico da cianobactéria Phormidium sp. a partir do cultivo heterotrófico com diferentes fontes de carbono orgânico, estudar diferentes estratégias de cultivo empregando a manipueira (água residual do processo para obtenção da farinha de mandioca) e avaliar o acúmulo lipídico a partir de diferentes fontes de nitrogênio. Primeiramente avaliou-se a capacidade da cianobactéria Phormidium sp. em se desenvolver a partir de 15 diferentes fontes de carbono orgânico exógeno. Os resultados indicaram o amido de mandioca e a maltodextrina como as fontes com maior potencial de exploração para a produção de biomassa e lipídeos. Em um segundo momento, foi realizada a intensificação do processo de produção de biomassa a partir do amido de mandioca empregando-se um planejamento experimental. Os resultados indicaram que relação C/N de 68 e temperatura de 30ºC são as condições operacionais ideais. A extrapolação do cultivo em Erlenmeyers para as operações em batelada e batelada com alimentação descontínua em biorreatores resultou em produtividades de biomassa de 50,72 mg/L.h e 42,13 mg/L.h, respectivamente. A terceira etapa do projeto contemplou o estudo do cultivo heterotrófico da cianobactéria empregando diferentes modos de cultivo utilizando manipueira como substrato, inicialmente através de diferentes concentrações (v/v) de manipueira em água (5, 10, 20, 40, 60, 80 e 100%). Os resultados demonstraram que a melhor concentração da manipueira foi a de 60% (v/v). Em seguida, iniciou-se cultivos em biorreator, nos modos de batelada (Sistema A) e batelada com alimentação descontínua, empregando-se manipueira como meio de cultivo e diferentes soluções de alimentação. No primeiro sistema alimentado (Sistema B), empregou-se uma solução de amido de mandioca concentrado, e no segundo (Sistema C), o biorreator foi alimentado com manipueira não diluída. As alimentações foram efetuadas assim que a concentração de DQO no biorreator atingisse uma concentração de 6000mg/L. A extrapolação para cultivos em biorreator resultou em maiores produtividades em biomassa (53,12mg/L.h) e lipídica (7,45mg/L.h) sob batelada (sistema A). A última etapa do projeto contemplou o estudo de diferentes fontes de nitrogênio (extrato de levedura, nitrato de sódio, nitrito de sódio, molibidato de amônio e ureia) no cultivo heterotrófico da Phormidium sp. empregando amido de mandioca como fonte de carbono orgânico. A partir dos resultados obtidos selecionou-se o nitrato de sódio sob razão C/N de 60 como a fonte com maior potencial na produção de lipídeos, resultando na quantidade de lipídeos, produtividades lipídica e de biomassa de 20,58%, 7,62mg/L.h e 37,02mg/L.h, respectivamente. O processo de depleção do nitrato de sódio resultou em um aumento na quantidade de lipídeos (25,07%) e na produtividade lipídica (10,47mg/L.h) / Abstract: The aim of the study was to evaluate the production of biomass and lipid accumulation of cyanobacteria Phormidium sp. from heterotrophic cultivation with different sources of organic carbon, study diferente strategies of cultures employing cassava wastewater and analyse the lipid accumulation from different nitrogen sources. First we assessed the ability of the cyanobacterium Phormidium sp. to growth in 15 different exogenous sources of organic carbon. Results indicated that the cassava starch and maltodextrin as those with the highest potential for exploitation for the production of biomass and lipids. In a second step, the increase in biomass production process was made from cassava starch employing an experimental design. The results indicated that the C/N of 68 and temperature of 30ºC are the optimal operating conditions. Extrapolation of cultivation in flasks for batch and batch with fed discontinuous operations in bioreactors resulted in biomass productivity of 50.72 mg/L.h and 42.13mg/L.h, respectively. The third stage of the project involved the study of the heterotrophic system of cyanobacteria using different modes of cultivation using cassava wastewater as substrate, initially through different concentrations (v/v) of wastewater in water (5, 10, 20, 40, 60, 80 and 100%). The results showed that the best concentration of cassava was 60%. Then, in a bioreactor cultivation was started in batch mode (System A), and batch with descontinuous feeds, using the culture medium as wastewater and different feed solutions. In the first feed system (System B) used a concentrated solution of cassava starch, and in second (System C), the bioreactor was fed with undiluted wastewater. The feeds were made so that the concentration of COD in the bioreactor to achieve a concentration of 6000mg/L. The extrapolation to cultivations in bioreactor resulted in productivity of biomass (53.12 mg/L.h) and lipid (7.45 mg/L.h) under simple batch (System A). The last stage of the project involved the study of different nitrogen sources (ammonium molybdate, sodium nitrate, sodium nitrite, urea and yeast extract) in heterotrophic cultures of Phormidium sp. using cassava starch as a source of organic carbon. From the results obtained, we selected sodium nitrate under C/N ratio of 60 as the source with the highest potential in the production of lipids, resulting in the amount of lipids, productivity of lipid and biomass of 20.58%, 7.62 mg/L.h and 37.02 mg/L.h, respectively. The process of depletion of sodium nitrate resulted in an increase in the amount of lipids (25.07%) and the lipid productively (10.47mg/L.h) / Doutorado / Engenharia de Processos / Doutora em Engenharia Quimica