Thesis (MSc)--University of Stellenbosch, 2002. / ENGLISH ABSTRACT: The production of wine is a complex process, which involves the conversion of sugar in grape must to ethanol, carbon dioxide and other byproducts. The principal organism in winemaking is yeast, of which Saccharomyces cerevisiae is the most important due to its ability to survive winemaking conditions, its GRAS (Generally Regarded As Safe) status and the favourable flavours it imparts during the winemaking process. However, due to the demands of the consumer and the emergence of sophisticated wine markets, a demand is developing for specialised yeast strains with enhanced and new oenological properties. For these reasons, research into the contribution of wine yeast to the aroma bouquet as well the influence of wine or brandy maturation in wood on the aroma bouquet is important for consumer demands to be met. The fruity aroma of wine is associated with esters, which are produced during the alcoholic fermentation by yeast. Important acetate esters in wine and brandy are ethyl acetate, which has a fruity, solvent-like aroma, and isoamyl acetate, which has a banana-like aroma. These esters are produced through the action of acetyltransferases (AATases), which catalyse the reaction between a higher alcohol and acyl Coenzyme A. Esters are mainly a product of alcoholic fermentation. However, their concentration changes during wood maturation and it has been found that the concentration of acetate esters can increase during the maturation period. In this study, the aim was to investigate the influence of AATase I and AATase II, which are encoded by the ATF1 and ATF2 genes respectively, on the aroma bouquet of wine and brandy. Therefore, the first objective of this study was to clone the ATF2 gene from a commercial wine yeast strain and to overexpress this gene in a commercial wine yeast strain and in a wine yeast strain that already has the A TF1 gene overexpressed. Disruption cassettes were also designed in order to disrupt the ATF1 and ATF2 genes in a commercial wine yeast strain. The resultant recombinant wine yeast strains were used for the production of wine and brandy. GC analyses and tasting trials were conducted to determine the effect of the overexpression or disruption of these genes on the aroma bouquet of wine. The results obtained indicated that there are differences in the aroma bouquet of wine and brandy when changes are made in gene expression. The results indicated that the A TF1 gene plays a large role in the production of ethyl and isoamyl acetate. When this gene was overexpressed, the level of ethyl acetate was 5.6-fold more than that of the control and the level of isoamyl acetate was 3.5-fold higher than that of the control. However, no increase in ethyl acetate or isoamyl acetate was observed when the A TF2 gene was overexpressed. An increase in 2-phenylethyl acetate and diethyl succinate was observed in brandy, although there was a decrease in total ester concentration. A decrease in acetic acid was also observed in the brandy produced, which could be an indication of ester production. Similarly, no increase in ethyl acetate or isoamyl acetate was observed in the wine or brandy produced when both the ATF1 and ATF2 genes were overexpressed in a single yeast. Once again, a marked decrease was observed in acetic acid concentration in both the wine and brandy. In conclusion, it is clear that changes in gene expression can change the aroma profile of wine or brandy. However, the role of the ATF2 gene still remains unclear and further studies are needed to clarify its role in yeast. Future studies involving the effect of wood maturation on ester concentration will also be of importance, so that the winemaker or distiller can make a product that suits the ever-changing market. / AFRIKAANSE OPSOMMING: Die produksie van wyn is 'n komplekse proses wat die omskakeling van die suiker in mos tot etanol, koolstofdioksied en ander byprodukte tot gevolg het. Die hooforganisme betrokke in die wynmaakproses is gis, waarvan Saccharomyces cerevisiae as een van die belangrikste geag word as gevolg van die vermoë daarvan om onder die wynfermentasietoestande te kan oorleef, die "GRAS"-status (Generally Regarded As Safe) daarvan en die invloed wat dit op die aroma van die uiteindelike produk het weens die werking daarvan gedurende alkoholiese fermentasie. Die behoefte aan wyn met nuwe, verbeterde eienskappe het die vraag na meer gespesialiseerde gisrasse deur beide die verbruiker en nuwe wynmarkte gedurende die afgelope paar jaar drasties laat toeneem. Dit is om dié redes dat navorsing oor die bydrae van wyngis en houtveroudering tot die aroma van beide wyn en brandewyn so belangrik geag word. Die vrugtige aroma van wyn word geassosieer met die esters wat gedurende die alkoholiese fermentasie deur gis gevorm word. Die belangrikste asetaatesters in wyn en brandewyn is etielasetaat, wat vir 'n oplosmiddelagtige, vrugtige aroma bekend is, en isoamielasetaat, wat 'n piesangaroma veroorsaak. Die esters word geproduseer deur die werking van asetieltransferases (AATases), wat as katalis in die reaksie tussen 'n hoër alkohol en asetiel-Ko-ensiem A optree. Alhoewel esters hoofsaaklik 'n produk van alkoholiese fermentasie is, wissel die konsentrasie daarvan gedurende houtveroudering. Daar is gevind dat die konsentrasie van die asetaatesters gedurende die verouderingsproses kan verhoog. Die studie het ten doelom die invloed van AATase I en AATase II, wat onderskeidelik deur die ATF1- en ATF2-gene geënkodeer word, op die aroma van wyn en brandewyn te ondersoek. Die eerste doelwit van die studie was vervolgens om die ATF2-geen vanaf 'n kommersiële wyngisras te kloneer en dit daarna te ooruitdruk in 'n kommersiële wyngisras, asook die geen te ooruitdruk in 'n kommersiële wyngisras wat reeds die ATF1-geen ooruitdruk. Disrupsiekassette is ook vir die disrupsie van die ATF1- en ATF2-gene in 'n kommersiële wyngisras ontwerp. Die rekombinante wyngisrasse wat gedurnde die studie gemaak is, is vir die produksie van wyn en brandewyn gebruik. Gas chromatografise-ontledings en sensoriese evaluerings is ook op die wyn en brandewyn uitgevoer. Die resultate van die studie het bewys dat daar wel veranderings plaasvind wanneer 'n verandering in geenuitdrukking gemaak is. Die resultate het weereens bevestig dat die ATF1-geen 'n belangrike rol in die produksie van etiel- en isoamielasetaat speel. Wanneer die ATF1-geen ooruitgedruk is, is die etielasetaatproduksie 5.6 keer meer en die isoamielasetaatproduksie 3.5 keer meer as in die kontrole. Die ooruitdrukking van die ATF2-geen het geen verhoging in etielasetaat of isoamielasetaat of in totale esters in die wyn getoon nie, alhoewel die ras 2.7 keer meer diëtielsuksinaat geproduseer het. In die brandewyn wat geproduseer is met die gisras waarin ATF2 ooruitgedruk is, was daar wel 'n verlaging in die asynsuur, wat 'n aanduiding van estervorming kan wees, alhoewel die totale esters wat geproduseer is minder was as in die kontrole. 'n Verhoging in diëtielsuksinaat en 2-fenielasetaat is ook gevind. Daar is geen verhoging in etiel- of isoamielasetaat getoon wanneer die ATF1- en ATF2-geen saam ooruitgedruk is nie. Die ras het minder totale sure in wyn en brandewyn geproduseer en ook geen verhoging in totale esters getoon nie. Uit die resultate is dit duidelik dat veranderings in geenuitdrukking 'n verandering in die aromaprofiel van wyn en brandewyn kan veroorsaak. Die rol van dié A TF2-geen is nog steeds onduidelik en verdere studies sal moet plaasvind om die rol van die geen te verduidelik. Studies wat konsentreer op die invloed van houtveroudering op esterkonsentrasie is ook belangrik vir die toekoms, want dit sal die wyn- of brandewynmaker meer beheer oor die uiteindelike produk gee en daardeur die wyn- of brandewynmaker help om 'n produk te vervaardig wat sy mark bevredig.

Objetivos: Avaliar a farmacocinética do éster etílico de indometacina (IndOEt) em ratos Wistar, após sua administração oral (p.o) e intravenosa (i.v.) nas formas livre ou nanoencapsulada, e monitorar a formação de indometacina (IndOH) in vivo. Metodologia: Os protocolos experimentais foram aprovados pelo Comitê de Ética em Pesquisa da UFRGS (2005478). Nanocápsulas (NC) contendo IndOEt (IndOEt- NC) foram administradas p.o. (10 mg/kg) e i.v. bolus (5 mg/kg) a ratos machos Wistar (n = 5 a 7/grupo) e as concentrações plasmáticas de IndOEt e IndOH resultantes foram determinadas por CLAE com detecção por UV, empregando-se metodologia validada. Os grupos controle foram tratados com suspensão aquosa de IndOEt (10 mg/kg), com ou sem polissorbato 80, ou com IndOH pelas vias i.v. ou p.o. (10 mg/kg) (n = 7 a 11/grupo). Os perfis plasmáticos individuais foram avaliados por abordagem não-compartimental e compartimental utilizando os softwares Excel® 2003 e Scientist® 2.01, respectivamente, para a determinação dos parâmetros farmacocinéticos, que foram comparados estatisticamente utilizando-se teste “t” de Student ou ANOVA (α = 0,05). A avaliação do local de absorção p.o. de IndOEt-NC foi realizada pela quantificação de IndOEt e IndOH no plasma periférico e da veia porta, homogeneizado de fígado e de parede, bem como conteúdo, de porções do intestino delgado (n= 4/tempo) após a administração oral da formulação. Resultados e Discussão: Após a administração de IndOEt-NC por ambas as vias, apenas a IndOH foi detectada, indicando uma rápida hidrólise do éster. Em todos os casos, o IndOEt não alterou os parâmetros farmacocinéticos da IndOH, exceto a biodisponibilidade. Os perfis plasmáticos de IndOH i.v. foram descritos pelo modelo de 2 compartimentos, e os orais, pelo de 1 compartimento com absorção de primeira ordem. A avaliação da absorção oral de IndOEt-NC evidenciou que o IndOEt é, provavelmente, liberado e hidrolisado ainda na luz do trato gastrintestinal, sendo a IndOH formada in vivo e absorvida. Conclusões: O IndOEt nanoencapsulado ou não, quando administrado pelas vias oral e i.v., é rapidamente convertido a IndOH. A IndOH é, portanto, responsável pela atividade antiedematogênica relatada para o IndOEt-NC. / Objective: To evaluate the pharmacokinetics of either nanoencapsulated (NC) or free indomethacin ethyl ester (IndOEt) after intravenous (i.v.) and oral (p.o.) administration to Wistar rats and to determine the pharmacokinetics of indomethacin (IndOH) formation. Methodology: Animal experiments were approved by UFRGS Ethics in Research Committee (# 2005478). The pharmacokinetics was investigated in male Wistar rats after oral and i.v. administration of IndOEt-NC (10 mg/kg and 5 mg/kg, respectively) (n = 5-7/group) and IndOEt and IndOH plasma concentrations were determined by a validated HPLC with UV detection method. The control groups were treated with IndOEt aqueous suspension (10 mg/kg p.o.) or with IndOH aqueous suspension by the p.o. or i.v. routes (10 mg/kg) (n = 7 -11/group). Noncompartmental and compartmental approaches were used for individual profiles analysis using Excel® 2003 or Scientist® 2.01 softwares, respectively. The site of IndOEt-NC oral absorption was investigated in peripheral and portal vein plasma, hepatic tissue, intestine epithelia, and lumen content (n = 4/time). Results and Discussion: After IndOEt administration by both routes, only IndOH was detected in plasma, suggesting a fast hydrolysis of the ester. The IndOH parameters after administration of IndOEt and IndOH were similar, except for the bioavailability. The pharmacokinetic parameters of IndOH were modeled by two compartment open model after i.v. dosing and by one compartment with first order absorption after oral administration. After oral administration, IndOEt-NC was converted in IndOH in the gastrointestinal tract and then absorbed as such. Conclusions: After i.v. and oral administration, either IndOEt-NC or the free drug is quickly converted in IndOH. After oral administration, IndOEt-NC is released and hydrolyzed to IndOH following its absorption at the gastrointestinal tract. Therefore, the IndOH is responsible for antiendematogenic activity reported for IndOEt-NC.

My thesis is devoted to the resistance of pollen beetle (Meligethes aeneus, son. Brassicogethes aeneus Fabricius, 1775) to pesticides in selected localities in southern Moravia. Collecting adults was performed in the spring of 2013 by tapped into polyethylene bags. Adults are collected from the stands of oilseed rape, mustard and poppy. Tests were performed on the basis of the methodology of Insecticide Resistance Action Committee number 011, 021, 025. In total, we tested the pollen population from 18 locations. For testing, we used the following chemical substances: Biscaya 240 OD, cypermethrin, lambda-cyhalothrin, tau-fluvalinate, etofenprox, chlorpyrifos(ethyl). We evaluated 100% of the registered dose of pesticides after 24 hours. From the results of the individual populations, we found large differences in resistance to chemicals.

This thesis deals with use of growth regulators to reduce lodging of spring barley (Hordeum vulgare L.). The field trial was conducted in corn production area on a clay-loamy glue fluvisol since 2012 to 2014. An effect of growth regulators was monitored on spring barley of the variety Bojos. Preparations Retacel extra R 68 (chlormequat chloride), Moddus (trinexapac-ethyl) and Cerone 480 SL (etephon) were chosen to crop regulation. The aim of the thesis was to carry intensive crop barley focused on correct application of growth regulators according to the cultivation methodologies. Growth regulators were used in various combinations with one another in three dose and dosage times. From this reason cob length, number of seeds per spike, grain yield and selected parameters of malting barley quality were monitored and evaluated. There was no negative effect of different combinations and does of growth regulators on production and quality of spring barley while the aim of crop shortening was achieved. In 2014 up to 20% of the effect of stalk length shortage was achieved. The greatest shortening was achieved on the stalks with higher dose of Cerone. In 2013 the yield increased of 1,95 t.ha-1 in variants with growth regulators.

SAMPAIO NETA, Nair do Amaral. Estudo da reação de produção de ésteres de ácidos graxos por via enzimática objetivando aplicações alimentícias. 2007. 99 f. : Dissertação (mestrado) - Universidade Federal do Ceará, Centro de Ciências Agrárias, Departamento de Tecnologia de Alimentos, Fortaleza-CE, 2007 / Submitted by Nádja Goes (nmoraissoares@gmail.com) on 2016-07-05T15:42:42Z No. of bitstreams: 1 2007_dis_nasampaioneta.pdf: 429587 bytes, checksum: e95171ae3ed4bc0f19b43d878deb4444 (MD5) / Approved for entry into archive by Nádja Goes (nmoraissoares@gmail.com) on 2016-07-05T15:43:09Z (GMT) No. of bitstreams: 1 2007_dis_nasampaioneta.pdf: 429587 bytes, checksum: e95171ae3ed4bc0f19b43d878deb4444 (MD5) / Made available in DSpace on 2016-07-05T15:43:09Z (GMT). No. of bitstreams: 1 2007_dis_nasampaioneta.pdf: 429587 bytes, checksum: e95171ae3ed4bc0f19b43d878deb4444 (MD5) Previous issue date: 2007 / Several experiments were done aiming at the study on the enzymatic esterification of the oleic acid with fructose in ethanolic medium, focusing the synthesis of biodegradable biosurfactants. For that purpose, it was utilized the enzyme, Candida antartica B., at temperature of 55 ºC, in reacting time of 48, 72, 96 e 120 hours. Accordingly to the obtained results it was verified that the related enzyme catalyzed primarily the ethanol present in the reactional medium to form the ester: ethyl oleate. This fact was confirmed through magnetic nuclear resonance spectra (1H and 13C) as well as, through infrared spectrum, by the presence of absorption peak at 1738, 4 cm- 1, characteristic of that ester. The results of the reaction of ethyl oleate production indicate that the highest yield was observed in about 96 hours time, and for the 120 hours time it was observed also an inferior yield. The experiments accomplished for the obtention of fructose esters from oleic acids in ethanolic medium were not successful like in other solvents not recommended for food use. The ethyl oleate shows a lipophilic character and in the food industry it finds application in the osmotic dehydration of tomatoes and peppers “dedo de moça”, improving water release, sugar yield and solar brightness. The use of ethyl oleate in the dehydration process decreases the drying time increases its efficiency without leaving any traces pf chemical residues / Diversos experimentos foram realizados com o objetivo de estudar a reação de esterificação enzimática do ácido oléico com a frutose em meio etanólico, visando a síntese de biosurfactantes biodegradáveis. Para tanto, foi utizada a enzima Cândida Antartica B na temperatura de 55 °C e em tempos de reação variando entre 48, 72, 96 e 120 horas. De acordo com os resultados obtidos, constatou-se que a citada enzima catalisou preferencialmente o etanol presente no meio reacional para a formação do éster oleato de etila. Este fato foi confirmado através do espectro de ressonância magnética nuclear (1H e 13C), bem como do espectro de infravermelho pela presença de um pico de absorção em 1738,4 cm-1, característico deste éster. Os resultados da reação de formação do oleato de etila indicam que o maior rendimento da reação foi observado no tempo de 96 horas e que o tempo de 120 horas o rendimento foi inferior. Os experimentos realizados com o objetivo de se obter ésteres de frutose a partir do ácido oléico em meio etanólico não lograram êxito, apesar da literatura indicar a possibilidade de se realizar esta reação em outros meios que utilizam solventes não recomendados para o uso alimentício. O oleato de etila apresenta caráter lipofílico e na indústria de alimentos encontra aplicação na desidratação osmótica de tomates e pimentas do tipo “dedo de moça”, facilitando a perda de água, ganho de açúcar e cor mais luminosa. O uso do oleato de etila no processo de desidratação diminui o tempo de secagem, aumenta sua eficiência sem deixar nenhum tipo de resíduo químico.

Submitted by JULIANA ROBERTA GOBI QUEIROZ null (julianaque@gmail.com) on 2016-03-28T21:06:31Z No. of bitstreams: 1 Juliana Regina Gobi Queiroz tese final.pdf: 1884473 bytes, checksum: 87837c22f3ac5eb237d7d319e1daa775 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-03-29T18:07:42Z (GMT) No. of bitstreams: 1 queiroz_jrg_dr_bot.pdf: 1884473 bytes, checksum: 87837c22f3ac5eb237d7d319e1daa775 (MD5) / Made available in DSpace on 2016-03-29T18:07:42Z (GMT). No. of bitstreams: 1 queiroz_jrg_dr_bot.pdf: 1884473 bytes, checksum: 87837c22f3ac5eb237d7d319e1daa775 (MD5) Previous issue date: 2016-02-04 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Os gramados podem ser utilizados em diversos ambientes com diferentes propósitos, e possuem características intrínsecas como a espécie de grama utilizada, o nível de manutenção e as técnicas adotadas. O uso de reguladores de crescimento, dentro de um manejo adequado, possibilita uma maior eficiência seja na manutenção ou produção de tapetes de qualidade. Dessa forma, o presente trabalho teve por objetivo avaliar os efeitos de trinexapac-ethyl, piraclostrobina associado ou não ao epoxiconazol e prohexadionecálcio como reguladores vegetais, sobre o crescimento e a qualidade dos tapetes de gramas das espécies Esmeralda (Zoysia japonica Steud.), São Carlos (Axonopus compressus (Sw.) Beauv.) e Bermuda (Cynodon dactylon (L.)). No primeiro estudo, os tratamentos e doses (g i.a. ha-1) testados, com e sem reaplicação foram: trinexapac-ethyl de 113,0 a 226,0, piraclostrobina + epoxiconazol de (66,5+25,0) a (113,0+50), piraclostrobina de 100,0 a 200,0, além de uma testemunha para cada espécie avaliada. No segundo estudo, os tratamentos e doses (g i.a. ha-1) testados, com duas e três reaplicações foram: prohexadione-cálcio de 27,5 a 165,0, além de uma testemunha sem aplicação do regulador de crescimento. Em ambos os estudos, foram realizadas avaliações visuais de fitotoxicidade através de uma escala de notas, na qual, “0” correspondeu a nenhuma injúria demonstrada pelas plantas e “100” a morte das plantas. Também foram avaliados: altura das plantas, número de inflorescências, além da coleta das aparas para determinação da massa seca. Ao final do estudo, os vasos foram desmontados sobre uma peneira e os tapetes foram lavados, bem como o sistema radicular. Em seguida avaliou-se a espessura total do tapete com e sem aparas, comprimento de raiz e posteriormente determinou-se da massa seca deste material. Todos os experimentos foram instalados no delineamento experimental inteiramente casualizado, com quatro repetições. Os resultados foram submetidos à análise de variância pelo Teste F, e as médias dos tratamentos foram comparadas pelo teste de “t” a 5% de probabilidade, com auxílio do programa estatístico Sisvar. Todos os reguladores vegetais foram visualmente seletivos às espécies de grama. Os tratamentos com trinexapac-ethyl e prohexadione-cálcio reduziram o crescimento das três espécies de grama dependendo da dose e da época testada. Os tratamentos com piraclostrobina aplicada isolada ou em mistura dependendo da época, da dose e da espécie podem proporcionar uma melhor qualidade do tapete de grama. / The turfgrasses can be used in different environments for different purposes, and possess intrinsic properties such as species of grass used, the level of maintenance and the techniques adopted. The use of plant growth regulators within a proper handling, enables a higher efficiency is the maintenance or production grass sod quality. Thus, this study aimed to evaluate the effects of trinexapac-ethyl, pyraclostrobin associated or not with epoxiconazole and prohexadione-calcium as plant regulators on the growth and quality of species grasses Esmeralda (Zoysia japonica Steud.), São Carlos (Axonopus compressus (SW.) Beauv.) and Bermuda (Cynodon dactylon (L.)). In the first study, the doses and treatments (g a.i. ha-1 ) tested, both with and without reapplication were: trinexapac-ethyl of 113.0 to 226.0, pyraclostrobin + epoxiconazol of (66.5+25.0) to (113.0+50.0), pyraclostrobin of 100.0 to 200.0, in addition to a control for each species evaluated. In the second study, the doses and treatments (g a.i. ha-1 ) tested with two and three reapplication were prohexadione-calcium of 27.5 to 165.0, plus a control without application of growth regulator. In both studies, were performed visual injury evaluations using a scale of notes, in which "0" corresponded to any injury, demonstrated by plants and "100" the death of plants. Were also assessed: plant height, number of inflorescences, in addition to the collection of scrap to determine the dry mass. At the end of the period of conducting the study, the vessels were dismantled on a sieve and rugs were washed away, as well as the root system. Then the total thickness of the mat with and without chips, root length and subsequently was dry mass of this material. All experiments were installed in completely randomized experimental design with four replications. The results were submitted to analysis of variance F-test, and the averages of the treatments were compared by t test at 5% probability, with the aid of statistical program Sisvar. All plant growth regulators were visually selective to the grass species. The treatment with trinexapac-ethyl and prohexadione-calcium reduced the growth of three species of grass depending on dose and season tested. Treatments with pyraclostrobin applied alone or in combination depending on the season, the dose and the species can provide a better quality of the grass sod. / CNPq: 141423/2012-9

Submitted by ADONIS COELHO null (adonis.don@hotmail.com) on 2016-04-05T19:14:23Z No. of bitstreams: 1 DISSERTAÇÃO FINAL - Adônis Coelho.pdf: 3593393 bytes, checksum: d9939c50e525b3eae4cc80b3170b6281 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-04-07T12:23:06Z (GMT) No. of bitstreams: 1 coelho_a_me_sjrp.pdf: 3593393 bytes, checksum: d9939c50e525b3eae4cc80b3170b6281 (MD5) / Made available in DSpace on 2016-04-07T12:23:06Z (GMT). No. of bitstreams: 1 coelho_a_me_sjrp.pdf: 3593393 bytes, checksum: d9939c50e525b3eae4cc80b3170b6281 (MD5) Previous issue date: 2016-02-24 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A produção e o consumo de biodiesel no Brasil e no mundo vem aumentando a cada ano em decorrência da busca por combustíveis menos poluentes e processos de produção mais baratos. Este biocombustível é produzido pela esterificação ou transesterificação de óleos ou gorduras com álcoois de cadeia curta. A catálise homogênea alcalina é a mais empregada na transesterificação gerando grandes quantidades de resíduos ao final do processo, já os catalisadores heterogêneos, menos usados em razão do custo e eficiência, são facilmente separados do produto final e ainda melhoram a qualidade do glicerol residual. O uso do etanol na produção do biodiesel fortalece a agroindústria brasileira, porém possui como principal desvantagem a sua higroscopicidade, o que pode favorecer a reação de saponificação afetando a qualidade do biodiesel e dificultando seu processo de produção. Neste trabalho, hidróxidos duplos lamelares tipo hidrotalcitas e piroauritas com substituição parcial de Mg e Al por Ba, Cu, Zn e Fe foram estudados como precursores de óxidos metálicos com atividade catalítica transesterificante na produção de biodiesel etílico de óleo de soja e caracterizados por TGA, DSC, FTIR-ATR, BET, XRD e SEM. Cromatografia em fase gasosa (GC-FID) foi empregada na quantificação dos produtos. Foram testadas 40 variações dos catalisadores, sendo 20 em cada temperatura de calcinação (450 e 600ºC). Dentre os materiais estudados, aqueles contendo Ba houve formação de fase secundária e os materiais com zinco e cobre obtiveram alta cristalinidade, maior perda de massa quando calcinados e altas áreas superficiais. Nos testes catalíticos em recipientes fechados com pressão autogerada a 120ºC por 12 horas utilizando razão 1:20 (massa óleo/massa etanol) e com 20% (massa catalisador/massa óleo). Os materiais de referência (hidrotalcita e piroaurita sem modificações calcinadas a 450ºC) proporcionaram conversões em biodiesel de 42 e 26%, respectivamente. Em geral, os materiais tipo piroaurita obtiveram rendimentos menores que os materiais tipo hidrotalcita, com destaque para o material com substituição de 10% de magnésio por zinco e 10% de alumínio por ferro calcinado a 450ºC que atingiu 61% de conversão em biodiesel nas condições testadas, e o pior resultado foi conseguido com o material tipo piroaurita preparado com 10% de cobre em substituição ao magnésio calcinado a 450ºC, que atingiu 15% de conversão. / Both the production and consumption of biodiesel have constantly increased worldwide and in Brazil due to a search for fuels which pollute less and production processes which cost less as well. Such biofuel is produced by means of esterification and transesterification of oils or fat with short-chain alcohols. Alkaline homogeneous catalysis is still widely used in transesterification, even though it generates a massive amount of residues at the end of the process; however, heterogeneous catalysts are not employed so frequently because they are more costly and less efficient. Nevertheless, they can be easily separated from the final product and improve the quality of residual glycerol. Although the use of ethanol in the production of biodiesel strengthens the Brazilian agro-industry, it poses a disadvantage: its hygroscopicity, which can generate a saponification reaction and, thus, affect the quality of the biodiesel and make its production process more difficult. In this study, we analyzed lamellar double hydroxides from hydrotalcite and pyroaurite types, with a partial substitution of Mg and Al for Ba, Cu, Zn, and Fe. We studied as metal oxide precursors with a transesterification catalytic activity on production of ethyl biodiesel from soybean oil and characterized them through TGA, DSC, FTIR-ATR, BET, XRD, and SEM. Gas chromatography (GC-FID) was used for products quantification. We conducted tests with 40 variations of catalysts, 20 for each calcination temperature (450 and 600ºC). Among the studied materials, those with Ba presented a secondary phase formation and materials with zinc and copper showed high crystallinity, high mass loss when calcined and high surface areas. In closed containers with auto-generated pressure at 120ºC for 12h using the ratio 1:20 (oil mass/ ethanol mass) and 20% (catalyst mass/ oil mass), the reference materials (hydrotalcite and pyroaurite, without modifications, calcined at 450ºC) yielded biodiesel conversions between 42 and 26%, respectively. Among all materials, pyroaurite obtained smaller yields compared to those from hydrotalcite materials, especially the material with a 10% substitution of magnesium for zinc and 10% of aluminum for iron calcined at 450ºC, which reached 61% conversion into biodiesel on tested conditions. Pyroaurite material prepared with 10% copper substituting calcined magnesium at 450ºC and reaching 15% conversion showed the worst result. / CNPq: 380625/2014-8

Made available in DSpace on 2014-06-11T19:32:27Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-11-07Bitstream added on 2014-06-13T20:04:01Z : No. of bitstreams: 1 mouco_mac_dr_botfca.pdf: 976151 bytes, checksum: 028a98e349191bffef5f2b0e8c7d42fa (MD5) / Outra / A mangicultura na região semi-árida destaca-se no cenário nacional não só pela expansão da área cultivada, volume de produção, altos rendimentos e qualidade do fruto produzido, mas também pela possibilidade de produção durante todo o ano devido às condições climáticas e às tecnologias para o manejo do crescimento vegetativo e da floração, com uso da irrigação, podas e utilização de reguladores vegetais. O paclobutrazol aplicado ao solo é utilizado no manejo da produção da mangueira na maioria dos pomares. Entretanto, há a necessidade de identificar outros reguladores vegetais que ofereçam a eficiência no manejo de produção das diferentes cultivares e que possam ser aplicados via foliar, de forma a minimizar os riscos de resíduo no solo e da aplicação de quantidades inadequadas ao longo dos anos. Assim, este trabalho teve como objetivo avaliar o efeito de reguladores vegetais aplicados via foliar quanto à eficiência no manejo da floração das cultivares Tommy Atkins e Kent, com maior precisão na recomendação da dose e menores riscos de contaminação da planta e do solo, permitindo o escalonamento da produção da mangueira. Os experimentos foram conduzidos na região do Vale do Rio São Francisco, em casa de vegetação, na Embrapa SemiÁrido e em condições de campo, nas Fazendas Frutavi e Andorinhas, localizadas no município de Petrolina, PE, entre outubro de 2005 e julho de 2008. Foram avaliados três reguladores vegetais aplicados via foliar: prohexadione-Ca, etil-trinexapac e cloreto de chlormequat, em duas doses, sendo estes comparados ao paclobutrazol aplicado ao solo, em delineamento de blocos ao acaso, com quatro repetições e duas plantas por parcela. Para a comparação do efeito dos tratamentos, registraram-se dados relativos à brotação vegetativa (percentagem e comprimento dos ramos), emissão de panículas (percentagem e comprimento),... / The mango crop within the semi-arid region stands out in the national scenario due to the expansion of the planted area, the production quantity, high yields and quality of the fruit produced, as well as to the possibility of all-year production due to climatic conditions and technologies that allow the management of plant growth and blossom, through irrigation, pruning and use of plant growth regulators. Paclobutrazol applied to the soil is used for the production management of mango in most of the orchards. However, it is necessary to identify other vegetal regulators that might be efficient for the production management of different cultivars and might be applied to the leaves, so as to minimize the risk of residues in the soil and inadequate application quantities over several years. Therefore, the present paper has the purpose to evaluate the effect of plant growth regulators that can be applied to the leaves, regarding their efficiency for the blossom management of the cultivars Tommy Atkins and Kent, allowing off season mango production with higher precision in dosage recommendation and lesser contamination risk for the plant and the soil. The experiments were carried out in the area of the São Francisco river valley, under green-house conditions at Embrapa Semi-Àrido, and under field conditions on the farms Frutavi and Andorinhas, both located in the municipality of Petrolina, Pernambuco state, from October 2005 to July 2008. Three plant growth regulators, sprayed to the leaves, were evaluated: prohexadione-Ca, trinexapac-ethyl and chlomequat cloride, applied in two dosages, and compared to paclobutrazol applied to the soil, using a randomized blocks design, with four replications and two plants per plot. In order to compare the effects of the treatment, data were recorded related to vegetative growth (percentage and length of the shoots), ...(Complete abstract, click electronic access below)

Objetivos: Avaliar a farmacocinética do éster etílico de indometacina (IndOEt) em ratos Wistar, após sua administração oral (p.o) e intravenosa (i.v.) nas formas livre ou nanoencapsulada, e monitorar a formação de indometacina (IndOH) in vivo. Metodologia: Os protocolos experimentais foram aprovados pelo Comitê de Ética em Pesquisa da UFRGS (2005478). Nanocápsulas (NC) contendo IndOEt (IndOEt- NC) foram administradas p.o. (10 mg/kg) e i.v. bolus (5 mg/kg) a ratos machos Wistar (n = 5 a 7/grupo) e as concentrações plasmáticas de IndOEt e IndOH resultantes foram determinadas por CLAE com detecção por UV, empregando-se metodologia validada. Os grupos controle foram tratados com suspensão aquosa de IndOEt (10 mg/kg), com ou sem polissorbato 80, ou com IndOH pelas vias i.v. ou p.o. (10 mg/kg) (n = 7 a 11/grupo). Os perfis plasmáticos individuais foram avaliados por abordagem não-compartimental e compartimental utilizando os softwares Excel® 2003 e Scientist® 2.01, respectivamente, para a determinação dos parâmetros farmacocinéticos, que foram comparados estatisticamente utilizando-se teste “t” de Student ou ANOVA (α = 0,05). A avaliação do local de absorção p.o. de IndOEt-NC foi realizada pela quantificação de IndOEt e IndOH no plasma periférico e da veia porta, homogeneizado de fígado e de parede, bem como conteúdo, de porções do intestino delgado (n= 4/tempo) após a administração oral da formulação. Resultados e Discussão: Após a administração de IndOEt-NC por ambas as vias, apenas a IndOH foi detectada, indicando uma rápida hidrólise do éster. Em todos os casos, o IndOEt não alterou os parâmetros farmacocinéticos da IndOH, exceto a biodisponibilidade. Os perfis plasmáticos de IndOH i.v. foram descritos pelo modelo de 2 compartimentos, e os orais, pelo de 1 compartimento com absorção de primeira ordem. A avaliação da absorção oral de IndOEt-NC evidenciou que o IndOEt é, provavelmente, liberado e hidrolisado ainda na luz do trato gastrintestinal, sendo a IndOH formada in vivo e absorvida. Conclusões: O IndOEt nanoencapsulado ou não, quando administrado pelas vias oral e i.v., é rapidamente convertido a IndOH. A IndOH é, portanto, responsável pela atividade antiedematogênica relatada para o IndOEt-NC. / Objective: To evaluate the pharmacokinetics of either nanoencapsulated (NC) or free indomethacin ethyl ester (IndOEt) after intravenous (i.v.) and oral (p.o.) administration to Wistar rats and to determine the pharmacokinetics of indomethacin (IndOH) formation. Methodology: Animal experiments were approved by UFRGS Ethics in Research Committee (# 2005478). The pharmacokinetics was investigated in male Wistar rats after oral and i.v. administration of IndOEt-NC (10 mg/kg and 5 mg/kg, respectively) (n = 5-7/group) and IndOEt and IndOH plasma concentrations were determined by a validated HPLC with UV detection method. The control groups were treated with IndOEt aqueous suspension (10 mg/kg p.o.) or with IndOH aqueous suspension by the p.o. or i.v. routes (10 mg/kg) (n = 7 -11/group). Noncompartmental and compartmental approaches were used for individual profiles analysis using Excel® 2003 or Scientist® 2.01 softwares, respectively. The site of IndOEt-NC oral absorption was investigated in peripheral and portal vein plasma, hepatic tissue, intestine epithelia, and lumen content (n = 4/time). Results and Discussion: After IndOEt administration by both routes, only IndOH was detected in plasma, suggesting a fast hydrolysis of the ester. The IndOH parameters after administration of IndOEt and IndOH were similar, except for the bioavailability. The pharmacokinetic parameters of IndOH were modeled by two compartment open model after i.v. dosing and by one compartment with first order absorption after oral administration. After oral administration, IndOEt-NC was converted in IndOH in the gastrointestinal tract and then absorbed as such. Conclusions: After i.v. and oral administration, either IndOEt-NC or the free drug is quickly converted in IndOH. After oral administration, IndOEt-NC is released and hydrolyzed to IndOH following its absorption at the gastrointestinal tract. Therefore, the IndOH is responsible for antiendematogenic activity reported for IndOEt-NC.

Submitted by THAÍS DOS SANTOS DE ALMEIDA null (ms.almeidaunesp@gmail.com) on 2016-06-23T18:30:37Z No. of bitstreams: 1 DISSERTAÇÃO Versão Final 23.06.2016.pdf: 2427944 bytes, checksum: 7d0fd3e8b7622649cec5ade2e7459c4c (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-06-27T18:16:00Z (GMT) No. of bitstreams: 1 almeida_ts_me_guara.pdf: 2427944 bytes, checksum: 7d0fd3e8b7622649cec5ade2e7459c4c (MD5) / Made available in DSpace on 2016-06-27T18:16:01Z (GMT). No. of bitstreams: 1 almeida_ts_me_guara.pdf: 2427944 bytes, checksum: 7d0fd3e8b7622649cec5ade2e7459c4c (MD5) Previous issue date: 2016-05-12 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Dentre os biocombustíveis hoje explorados, o biodiesel vem se destacando como uma alternativa ao óleo diesel derivado do petróleo por ser um combustível renovável, biodegradável e não tóxico. Atualmente, a produção desse biocombustível é quase que 100 % via transesterificação alcalina em fase homogênea de triglicerídeos presentes em óleos vegetais. Entretanto, cerca de 70 % do preço final do biodiesel é resultado do custo dessas matérias-primas. Desse modo, desenvolver tecnologias de usabilidade máxima e compatibilidade ambiental para diversas matérias-primas baratas, como gorduras animais e rejeitos de óleo de cozinha, as quais têm alto teor de ácidos graxos livres e são incompatíveis com catalisadores alcalinos, torna-se cada vez mais importante. As tecnologias de produção disponíveis empregam catalisadores ácidos minerais homogêneos (ácidos Brönsted), os quais são corrosivos, não recicláveis, e resultam em grande geração de resíduos e efluentes nas etapas de neutralização e de separação. Neste trabalho, investigamos a atividade catalítica de três complexos metálicos exibindo caráter ácido de Lewis: dibutil diacetato de estanho, brometo de estanho e cloreto de estanho. Testamos esses complexos catalíticos na alcoólise de óleos de soja e de pinhão-manso, visando à obtenção de uma mistura de ésteres alquílicos de ácidos graxos (biodiesel), empregando metanol e, também, etanol, a fim de valorizar essa matéria-prima nacional. Também avaliamos a atividade catalítica desses complexos comparando com a transesterificação catalítica clássica básica (NaOH) e ácida (H2SO4). Além do tipo de catalisador, estudamos também a concentração do catalisador (0,5, 1,0 e 2,0 %) e a temperatura (50 e 120 ºC), para uma razão molar de óleo:álcool 1:6 e tempo de reação de 6 horas. O infravermelho revelou as principais bandas referentes aos ésteres metílicos e etílicos e as análises de rendimento dos biodieseis produzidos foram realizadas por cromatografia gasosa. / Among biofuels exploited nowadays, biodiesel has emerged as an alternative to diesel fuel derived from petroleum for being a renewable fuel, biodegradable and nontoxic. Currently, the production of this biofuel is almost 100 % via alkaline transesterification in homogeneous phase of triglycerides present in vegetable oils. However, about 70 % of the final price of biodiesel is due to the cost of these raw materials. Thus, developing technologies of maximum usability and environmental compatibility for a variety of cheap raw materials, such as animal fats and cooking oil waste, which have a high content of free fatty acids and are incompatible with alkaline catalysts, it becomes increasingly important. The available production technologies employ homogeneous catalysts mineral acids (Brönsted acids) which are corrosive, not being recyclable and result in great waste generation and effluents in neutralization and separation steps. In this work, we investigated the catalytic activity of three metal complexes exhibiting Lewis acid character: tin dibutyl diacetate, tin bromide and tin chloride. We tested these catalytic complexes in the alcoholysis of soybean oil and jatropha curcas oil, in order to obtain a mixture of alkyl esters of fatty acids (biodiesel) using methanol and also ethanol, in order to enhance this national raw material. We also evaluated the catalytic activity of these complexes compared to the basic classical catalytic transesterification (NaOH) and acid (H2SO4). Besides the catalyst type, we also studied the catalyst concentration (0.5, 1.0 and 2.0 %) and temperature (50 and 120 °C) for a molar ratio of oil: ethanol 1:6 and reaction time of 6 hours. The infrared revealed the main bands related to the methyl and ethyl esters and the performance analysis of biodiesels produced were carried out by gas chromatography.