<p>Jedno od specijalnih jestivih ulja koje se proizvodi isključivo mehaničkim postupkom i koje se može uvrstiti u grupu funkcionalnih prehrambenih proizvoda je ulje semena tikve. Ovo ulje je veoma atraktivno za potro&scaron;ace, pre svega zbog svoje karakteristične arome, visoke nutritivne vrednosti i dokazanog blagotvornog delovanja na zdravlje. Cilj istraživanja u okviru ove teze je bio da se izvr&scaron;i karakterizacija senzorsko nutritivnog kvaliteta i oksidativne stabilnosti hladno presovanih i devičanskih ulja tikve sa trži&scaron;ta, ispita uticaj termičke obrade semena na kvalitet, nutritivnu vrednost i održivost devičanskog tikvinog ulja i da se defini&scaron;u senzorska svojstva i održivost hladno presovanog ulja semena tikve. U cilju karakterizacije ulja ispitivanja su sprovedena na većem broju uzoraka hladno presovanih i devičanskih ulja semena<br />tikve nabavljenih neposredno, slučajnim izborom sa domaćeg i inostranog trži&scaron;ta. Definisana su osnovna svojstva i najbitnije kvalitativne razlike između ove dve kategorije ulja proizvedenih različitom tehnologijom. Iako se proizvode iz iste sirovine tikvina ulja se međusobno bitno razlikuju po brojnim kvalitativnim, a naročito senzorskim svojstvima (ukus, miris, aroma i boja) &scaron;to može da stvori zabune kod<br />potro&scaron;aca. Ispitivanjima uticaja različite termičke obrade semena utvrđeno je da proces pečenja mlevenog materijala neposredno pre presovanja bitno utiče na kvalitativna svojstva i održivost devičanskog ulja. Termička obrada mlevenog semena pri temperaturi u interval od 90 do 130 ^oC i vremenu od 30 do 70 min pokazala je različit uticaj na senzorski kvalitet, sadržaj bioaktivnih komponenata i oksidativnu stabilnost ulja ispoljavajući kako negativan, tako i pozitivan efekat. U delu istraživanja vezanih za definisanje senzorskih svojstava i određivanje održivosti ulja izdvojenog postupkom hladnog presovanja osu&scaron;enog semena tikve na pužnoj presi, ustanovljeno je da se najkvalitetnije ulje dobije pri prvom presovanju, buduci da je aroma ulja najbolja, pri tom su kiselinski i peroksidni broj najmanji, a indukcioni period najduži. Ovo se potvrdilo, kako pri presovanju samo semena golice, tako i pri presovanju golice sa dodatkom semena sa ljuskom. Promene najbitnijih pokazatelja u cilju odredivanja održivosti ulja praćene su periodično u trajanju od 2 godine. U<br />tom periodu do&scaron;lo je do izvesnog pogor&scaron;anja senzorskog kvaliteta ulja, određenog porasta kiselinskog i peroksidnog broja, kao i do smanjenja indukcionog perioda. Medutim, bez obzira na intenzitet nastalih promena, ulja su odgovarala svim zakonskim normama kvaliteta i nakon dve godine čuvanja. Ipak, radi obezbeđenja vrhunskog kvaliteta za rok trajanja hladno presovanih ulja semena tikve golice može se preporuciti period najvi&scaron;e do godinu dana.</p> / <p> Pumpkin seed oil is one of the specialty oils produced only by mechanical procedure and can be classified in the group of functional food products. This oil is very attractive (interesting) for the consumers first of all for its characteristic flavour, high nutritive value and proved beneficial effect on health. The aim of the investigations in the scope of this thesis was to characterize the sensoric-nutritive quality and oxidative<br /> stability of cold pressed and virgin pumpkin seed oils from the market, to investigate the effect (influence) of heat treatment of seed on quality, nutritive value and stability of virgin pumpkin seed oil and to define the sensory characteristics and stability of cold pressed pumpkin seed oil. Aiming to characterize the oil, a number of cold pressed and virgin pumpkin seed oil samples, randomly taken from the domestic and foreign market, were investigated (analyzed). The basic characteristics and most important qualitative differences between these two categories of oils produced applying different technologies were defined. Both types of pumpkin seed oils are produced from the same raw material, however, they differ significantly regarding a number of<br /> quality, and expecially sensory proterties (taste, odour, flavour and colour), so the consumers may become embarrassed. Investigating the influence of different heat treatment of seed, it was found that the roasting of ground material before the pressing affects significantly the quality characteristics and stability of virgin oil. The heat treatment of ground seed at temperatures 90 to 130 &deg;C, for 30 to 70 min, showed different influence on sensory quality, content of bioactive components and oxidative stability of oil, exhibiting both negative and positive effect. In the part dealing with the defining of sensory characteristics and stability determination of oil obtained by cold pressure of dried pumpkin seed on screw press, it was found that most quality oil was obtained by the first pressing process, the oil flavur is the best, with lowest acid and peroxide value, and the induction period is the longest. This was confirmed by pressing both hull-less pumpkin and hull-less with the addition<br /> of pumpkin seed with hull. The most important characteristics for oil stability were<br /> followed for two years. In this period a certain deterioration of sensory quality was found, the acid and peroxide value increased, and the induction period decreased. However, disregarding the intensity of changes, the oil samples are in accordance with all legal quality normatives even after two years from the production date. However, in order to maintain the high (first-class) quality of cold pressed oil of hull-less pumpkin seed, the recomended period for the shelf-life of oil is one year.</p>

A nanotecnologia é um fenômeno que se aplica a praticamente todos os etores da ciência, sendo que na área cosmética o elevado investimento neste campo tem reforçado a idéia de que os produtos nanotecnológicos proporcionam vantagens reais aos consumidores. A crescente exigência do consumidor e os avanços no conhecimento sobre a obtenção e estabilidade dos sistemas dispersos viabilizam o desenvolvimento de veículos diferenciados como, por exemplo, nanoemulsões, que além da inerente estabilidade, apresentam aspecto sensorial agradável, alta capacidade de espalhabilidade e hidratação. Existem dois métodos de obtenção das nanoemulsões: empregando baixa ou alta energia de emulsificação. O uso de óleos vegetais em produtos cosméticos tem sido intensamente valorizado, baseando-se no conceito de que são seguros e biocompatíveis. Podem ser utilizados em cosméticos com sua funcionalidade potencializada, sendo estes ricos em ácidos graxos essenciais, Ômega 3, Ômega 6, Ômega 9, fitosteróis, vitamina C e polifenóis (antocianinas). Alguns óleos vegetais têm poder antioxidante comprovado, previnem as oxidações biológicas e reduzem a formação de radicais livres responsáveis pelo dano celular, grande vilão do envelhecimento e das doenças crônico-degenerativas, como o câncer. Atualmente é crescente o interesse da pesquisa sobre a atividade de substâncias capazes de proteger a pele contra a radiação ultravioleta de forma eficaz. O metoxicinamato de octila é um filtro solar químico capaz de proteger a pele e conferir um fator de proteção solar ao produto final. Nesse estudo foram desenvolvidas nanoemulsões à base de óleos de oliva e semente de uva aditivadas de metoxicinamato de octila. Após a análise da estabilidade físico-química e caracterização das formulações, foram avaliados o potencial antioxidante das formulações, o efeito de proteção solar do sistema, liberação e permeação do ativo e uma possível irritação ocular das formulações que se mantiveram estáveis. / Nanotechnology is a phenomenon that is applied to mainly all sectors of science. In the cosmetic area the high investment has strengthened the idea that nanotechnology products offer real advantages to consumers. The growing demand of consumers and the advances in the knowledge about production and stability of dispersed systems enable the development of differentiated vehicles such as nano-emulsions, which besides their inherent stability, they have pleasant sensorial aspect, high spread ability and hydration power. There are two methods of nano-emulsions attainment: low or high energy of emulsifying. The use of vegetable oils in cosmetic products has had enormous and growing value, based in the concept that they are safe and biocompatible. They can be used in cosmetics with their functionality improved, being rich in essential fatty acids, Omega 3, Omega 6, Omega 9, phytosterols, vitamin C and polyphenols (anthocyanins). Some vegetable oils have proved antioxidant power, as well as they avoid biological oxidation and decrease the forming of free radicals responsible for cellular damage, which are the causes of aging and disease such as cancer. Nowadays, the interest of research about the activity of substances that protect the skin against ultraviolet irradiation in an efficacious way is growing. Octylmethoxycinnamate is a chemical sunscreen that can protect skin and offers sun protection factor to final product. In this study nano-emulsions were developed using olive oil and grape seed oil added with octylmethoxycinnamate. After the analysis of the physic-chemical stability and formulation characterization, the antioxidant potential of formulations, the effect of sun protection of the system, delivery and permeation of the active agent, and a possible ocular irritation of the stable formulations were evaluated.

A combinação de agentes quimiopreventivos com diferentes mecanismos de ação tem sido considerada uma estratégia promissora para a prevenção do câncer. Dentre os diversos compostos bioativos em alimentos, destacam-se a tributirina, um pró-fármaco do ácido butírico presente em laticínios e produzido pela fermentação de fibras dietéticas, e o óleo de linhaça, fonte de ácido alfa linolênico. Nesse contexto, foi avaliada a atividade quimiopreventiva de lipídios estruturados obtidos a partir da interesterificação enzimática de tributirina e óleo de linhaça durante a fase de promoção inicial da hepatocarcinogênese experimental. Ratos Wistar machos submetidos ao modelo do hepatócito resistente receberam diariamente, por via intragástrica (i.g), maltodextrina, óleo de linhaça, tributirina, a mistura não esterificada ou lipídios estruturados durante a fase de promoção inicial. O tratamento com lipídios estruturados demonstrou atividade quimiopreventiva comparável à da tributirina, mesmo resultando em menor concentração hepática de ácido butírico. Tanto a tributirina quanto os lipídios estruturados não inibiram a proliferação celular em lesões preneoplásicas, mas induziram a apoptose naquelas em remodelação. Os efeitos inibitórios da tributirina em fases iniciais da hepatocarcinogênese experimental estão relacionados ao aumento da acetilação de histonas e à modulação de processos de translocação nuclear da p53. No presente estudo, foi observado aumento substancial da razão nuclear/citoplasmática de p53 e importina-alfa em fígados de animais submetidos ao modelo e tratados com tributirina, mas não nos tratados com lipídios estruturados. Por outro lado, o tratamento com lipídios estruturados reduziu a expressão dos oncogenes Bcl2, Ccnd2, Pdgfa, Vegfa e aumentou a expressão dos genes supressores de tumor Cdh13, Fhit e Socs3. Assim, embora o potencial quimiopreventivo dos lipídios estruturados seja comparável ao da tributirina, os resultados sugerem que o novo composto não exibe atividade de HDACi, e que seus efeitos inibitórios na hepatocarcinogênese possam ser atribuídos à modulação da expressão de oncogenes e genes supressores de tumor. / Combination of chemopreventive agents with different mechanisms of action has been considered a promising strategy to cancer prevention. Among several bioactive food compounds, tributyrin, a butyric acid prodrug obtained from dairy products and dietetic fiber fermentation, and flax seed oil, a rich source of alpha linolenic acid have shown chemopreventive potential. Here, we evaluated the chemopreventive activity of structured lipids obtained by enzymatic interesterification of tributyrin and flax seed oil during the early promotion phase of experimental hepatocarcinogenesis. Male Wistar rats subjected to the resistant hepatocyte model were treated daily, i.g, with maltodextrin, flax seed oil, tributyrin, non-sterified blend, or structured lipids. Treatment structured lipids showed similar chemopreventive activity compared to tributyrin, even when structured lipids yielded lower concentrations of butyric in the liver. Tributyrin and structured lipids did not inhibit cell proliferation in preneoplastic lesions, but both of them induced apoptosis in remodeling preneoplastic lesions. In addition, histone acetylation and p21 restored expression tributyrin molecular mechanisms were related to modulation of p53 nuclear shuttling mechanisms. In the present study, it was observed a substantial increase in p53 nuclear/cytoplasmic ratio and importin-alpha in preneoplastic livers of tributyrin treated rats, but not in those treated with structured lipids. In contrast, treatment structured lipids downregulated expression of major oncogenes Bcl2, Ccnd2, Pdgfa, and Vegfa; and upregulated expression of critical tumor suppressor genes, Cdh13, Socs3 and Fhit. Hence, although structured lipids and tributyrin show similar chemopreventive potential, the results suggest that the new compound does not exhibit HDACi activity, and that its inhibitory effects may be attributed to the modulation of oncogenes and tumor suppressor genes expression.

<p>Cilj ove doktorske disertacije je dobijanje vi&scaron;estrukih V₁/U/V₂ emulzija kao nosača aktivnih materija u dvostepenom postupku, pri čemu se za drugi korak pripreme koristi tehnika membranskog emulgovanja (ME), na membrani od sinterovanog stakla implementiranoj u ćeliju sa me&scaron;anjem. Proces ME koristi se u svrhu unapređenja karakteristika formiranih emulzija, u smislu bolje kontrole veličine i raspodele veličina formiranih kapi, koje mogu da dovedu do razlika u stepenu inkapsulacije aktivnih materija u unutra&scaron;njoj vodenoj fazi, u odnosu na proces u kome se za drugi korak pripreme emulzija koristi tehnika homogenizacije.<br />Kompletna optimizacija sastava V₁/U emulzija, koja obuhvata određivanje koncentracije hidrofobnog emulgatora (PGPR), lipofobne materije (NaCl) i tikvinog ulja kao sekundarne aktivne komponente, rezultirala je formiranjem stabilnih nanoemulzija sa pobolj&scaron;anim nutritivnim svojstvima. Nutritivno unapređeni emulzioni sistemi optimizovanog sastava kori&scaron;ćeni su za inkapsulaciju primarnih aktivnih komponenata (vodenog i etanolnog ekstrakata belog luka) u cilju za&scaron;tite bioaktivnih sastojaka i maskiranja neprijatnog mirisa i ukusa. Nakon definisanja sastava svih faza vi&scaron;estrukih emulzija, koje ukljuĉuje određivanje tipa hidrofilnog emulgatora i njegove koncentracije, kao i ispitivanja uticaja dodavanja osmotskog regulatora (glukoze) u spolja&scaron;nju vodenu fazu na stabilnost sistema i difuziju lipofoba, formirane su vi&scaron;estruke emulzije sa unetim aktivnim komponentama membranskim emulgovanjem u ćeliji sa me&scaron;anjem. Sistematiĉna karakterizacija membrane od sinter stakla kao ekonomski opravdanog membranskog materijala, dala je mogućnost njegove primene u procesu. Detaljno ispitivanje uticaja procesnih parametara (transmembranskog pritiska i brzine me&scaron;anja) i vi&scaron;ekriterijumska optimizacija procesa ME, dovela su do formiranja vi&scaron;estrukih emulzija sa užom raspodelom veličina kapi, koja je indirektno uticala i na pobolj&scaron;anje zadržavanja inkapsuliranog materijala u unutra&scaron;njosti emulzija tokom vremena, u odnosu na emulzije pripremljene u postupku homogenizacije.</p> / <p style="text-align: justify;">The aim of this doctoral thesis was to prepare multiple W/O/W emulsions with encapsulated active substances in both phases, by a two-step process, where the stirred cell membrane emulsification (ME) process, with a sintered glass filter disk as a membrane, was used as the second step, instead of conventional process (homogenization). The ME process was employed in order to improve the characteristics of the formed emulsions, in terms of better control of the size and droplet size distribution, that can change the encapsulation degree of active ingredients in the internal aqueous phase.<br />The complete optimization of W/O emulsion composition, which includes determination of optimal contents of a hydrophobic emulsifier (PGPR), a lipophobic substance (NaCl) and pumpkin seed oil as an active component of the oil phase, resulted in the formation of stable nanoemulsions with improved nutritional properties. This nutritionally enhanced emulsion was used to encapsulate primary active ingredients (aqueous and ethanol garlic extract), in order to protect instable bioactive compounds of the extracts and mask the unpleasant smell and taste. After defining the composition of all phases of multiple emulsions, which includes determination of a suitable hydrophilic emulsifier and its optimal content, as well as examining the effect of addition of an osmotic regulator (glucose) in the external aqueous phase on the emulsion stability and lipophobe diffusion, multiple emulsions with encapsulated active components were formed by membrane emulsification in the stirred cell. The complete characterization of the sintered glass as an economically favourable membrane material, gave the possibility of its application in the process. Investigation of the influence of process parameters (transmembrane pressure and impeller rotation speed) and multiobjective optimization of ME, led to the formation of the multiple emulsions with a narrow droplet size distribution, which had improved retention of encapsulated material in the internal water phase over time, relative to the emulsions prepared by the homogenization process.</p>

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / The purpose of this thesis was to investigate the feasibility of using the honey bee (Apis mellifera L.) for pollination and yield increment in Jatropha curcas L. crops. Therefore, the floral biology and pollination process of J. curcas were studied as well as the foraging behavior and pollination efficiency of A. mellifera in this crop by the introduction of four colonies in a hectare. The work was carried out in a five years-old commercial plantation comprising 10ha, in the state of PiauÃ, (08Â32â19,0âS and 43Â56â19,7âW, 220 meters above sea level), Brazil, from March to July, 2009. Flowers were presented in protogynous inflorescences and the anthesis and most of pollen presentation took place mainly in the morning shift. Inflorescences last, in average, 20 days, with female flowers concentrating in the first third of the period and male flowers predominating in the second third, in a relation of 18.1:1 male/ female flower. Although this may favor xenogamy, the stigma receptivity lasts for, at least, five days ensuring the flower to reach the period of most pollen release in its own inflorescence, facilitating the occurrence of geitonogamy. Flowers pollinated up to four days after anthesis did not differ (p>0.05) in fruit setting to those pollinated in the first, second or third day after anthesis. Foraging by A. mellifera occurs throughout the day and peaks between 13h00min and 15h00min and is characteristic of nectar harvesting both in male and female flowers. Only one visit by A. mellifera to J. curcas flowers set 100% producing results similar (p>0,05) to those from manual xenogamy (96%), manual geitonogamy (94%) and open pollination (93%). However, only one visit by a bee was not enough to maximize the oil content per seed (213mg) in comparison to the open pollination and geitonogamy treatments (both 250mg). Besides that, it was possible to observe that geitonogamy led to greater oil production than xenogamy (237mg). It is concluded that A. mellifera is an efficient pollinator of this crop. The introduction of four honey bee colonies per hectare maximize oil production and produce the best results for all parameters studied. Furthermore, only one visit by the honey bee to J. curcas flowers was enough to prevent pollination deficit in this crop. / O objetivo desta tese foi investigar a possibilidade da utilizaÃÃo de Apis mellifera L. na polinizaÃÃo e incremento de produtividade da cultura do pinhÃo manso (Jatropha curcas L.). Para tanto, foi estudado a biologia floral e a polinizaÃÃo do pinhÃo manso bem como o comportamento forrageiro e a eficiÃncia polinizadora de Apis mellifera. O trabalho foi realizado em 10ha de plantio comercial jà estabelecido, com cinco anos de idade, no estado do PiauÃ, (08Â32â19,0âS e 43Â56â19,7âW e 220 metros de altitude), entre os meses de marÃo e julho de 2009. A antese das flores do pinhÃo manso, distribuÃdas em cimos com carÃter protogÃnico, ocorre basicamente no perÃodo matinal, bem como a maior oferta de pÃlen. As inflorescÃncias duram, em mÃdia, 20 dias, com maior concentraÃÃo de flores femininas no terÃo inicial e de masculinas, no terÃo mÃdio, com relaÃÃo de 18,1 flores masculinas para cada feminina. Embora esse fato favoreÃa a xenogamia, a receptividade do estigma por, pelo menos, cinco dias, garante a flor alcanÃar o perÃodo de maior oferta de pÃlen no prÃprio cimo, oportunizando a geitonogamia. As flores polinizadas atà o quarto dia frutificam da mesma forma que aquelas polinizadas no primeiro, segundo e terceiro dias apÃs antese, nÃo havendo diferenÃas significativas. O forrageamento por A. mellifera ocorre durante todo o dia, com maior pico entre 13h00m e 15h00m e à tÃpico de coleta de nÃctar, tanto nas flores masculinas quanto nas femininas. Apenas uma visita da abelha Ãs flores acarreta em 100% de vingamento, mostrando resultado semelhante, (p>0,05), aos tratamentos de xenogamia manual (96%), geitonogamia manual (94%), e polinizaÃÃo aberta (93%). PorÃm, uma visita apenas, nÃo à suficiente para produzir maior quantidade de Ãleo por semente (213mg), em comparaÃÃo com o tratamento de polinizaÃÃo aberta, e por geitonogamia (250mg). AlÃm disto, foi possÃvel constatar que hà maior produÃÃo de Ãleo por geitonogamia e nÃo por xenogamia (237mg). Conclui-se que a Apis mellifera à um polinizador eficiente da cultura. Sua introduÃÃo, com quatro colÃnias por hectare, maximiza a produÃÃo de Ãleo e produz os melhores resultados para todos os parÃmetros avaliados. AlÃm disso, apenas uma visita da abelha melÃfera Ãs flores do pinhÃo manso à suficiente para prevenir dÃficit de polinizaÃÃo.

A nanotecnologia é um fenômeno que se aplica a praticamente todos os etores da ciência, sendo que na área cosmética o elevado investimento neste campo tem reforçado a idéia de que os produtos nanotecnológicos proporcionam vantagens reais aos consumidores. A crescente exigência do consumidor e os avanços no conhecimento sobre a obtenção e estabilidade dos sistemas dispersos viabilizam o desenvolvimento de veículos diferenciados como, por exemplo, nanoemulsões, que além da inerente estabilidade, apresentam aspecto sensorial agradável, alta capacidade de espalhabilidade e hidratação. Existem dois métodos de obtenção das nanoemulsões: empregando baixa ou alta energia de emulsificação. O uso de óleos vegetais em produtos cosméticos tem sido intensamente valorizado, baseando-se no conceito de que são seguros e biocompatíveis. Podem ser utilizados em cosméticos com sua funcionalidade potencializada, sendo estes ricos em ácidos graxos essenciais, Ômega 3, Ômega 6, Ômega 9, fitosteróis, vitamina C e polifenóis (antocianinas). Alguns óleos vegetais têm poder antioxidante comprovado, previnem as oxidações biológicas e reduzem a formação de radicais livres responsáveis pelo dano celular, grande vilão do envelhecimento e das doenças crônico-degenerativas, como o câncer. Atualmente é crescente o interesse da pesquisa sobre a atividade de substâncias capazes de proteger a pele contra a radiação ultravioleta de forma eficaz. O metoxicinamato de octila é um filtro solar químico capaz de proteger a pele e conferir um fator de proteção solar ao produto final. Nesse estudo foram desenvolvidas nanoemulsões à base de óleos de oliva e semente de uva aditivadas de metoxicinamato de octila. Após a análise da estabilidade físico-química e caracterização das formulações, foram avaliados o potencial antioxidante das formulações, o efeito de proteção solar do sistema, liberação e permeação do ativo e uma possível irritação ocular das formulações que se mantiveram estáveis. / Nanotechnology is a phenomenon that is applied to mainly all sectors of science. In the cosmetic area the high investment has strengthened the idea that nanotechnology products offer real advantages to consumers. The growing demand of consumers and the advances in the knowledge about production and stability of dispersed systems enable the development of differentiated vehicles such as nano-emulsions, which besides their inherent stability, they have pleasant sensorial aspect, high spread ability and hydration power. There are two methods of nano-emulsions attainment: low or high energy of emulsifying. The use of vegetable oils in cosmetic products has had enormous and growing value, based in the concept that they are safe and biocompatible. They can be used in cosmetics with their functionality improved, being rich in essential fatty acids, Omega 3, Omega 6, Omega 9, phytosterols, vitamin C and polyphenols (anthocyanins). Some vegetable oils have proved antioxidant power, as well as they avoid biological oxidation and decrease the forming of free radicals responsible for cellular damage, which are the causes of aging and disease such as cancer. Nowadays, the interest of research about the activity of substances that protect the skin against ultraviolet irradiation in an efficacious way is growing. Octylmethoxycinnamate is a chemical sunscreen that can protect skin and offers sun protection factor to final product. In this study nano-emulsions were developed using olive oil and grape seed oil added with octylmethoxycinnamate. After the analysis of the physic-chemical stability and formulation characterization, the antioxidant potential of formulations, the effect of sun protection of the system, delivery and permeation of the active agent, and a possible ocular irritation of the stable formulations were evaluated.

A combinação de agentes quimiopreventivos com diferentes mecanismos de ação tem sido considerada uma estratégia promissora para a prevenção do câncer. Dentre os diversos compostos bioativos em alimentos, destacam-se a tributirina, um pró-fármaco do ácido butírico presente em laticínios e produzido pela fermentação de fibras dietéticas, e o óleo de linhaça, fonte de ácido alfa linolênico. Nesse contexto, foi avaliada a atividade quimiopreventiva de lipídios estruturados obtidos a partir da interesterificação enzimática de tributirina e óleo de linhaça durante a fase de promoção inicial da hepatocarcinogênese experimental. Ratos Wistar machos submetidos ao modelo do hepatócito resistente receberam diariamente, por via intragástrica (i.g), maltodextrina, óleo de linhaça, tributirina, a mistura não esterificada ou lipídios estruturados durante a fase de promoção inicial. O tratamento com lipídios estruturados demonstrou atividade quimiopreventiva comparável à da tributirina, mesmo resultando em menor concentração hepática de ácido butírico. Tanto a tributirina quanto os lipídios estruturados não inibiram a proliferação celular em lesões preneoplásicas, mas induziram a apoptose naquelas em remodelação. Os efeitos inibitórios da tributirina em fases iniciais da hepatocarcinogênese experimental estão relacionados ao aumento da acetilação de histonas e à modulação de processos de translocação nuclear da p53. No presente estudo, foi observado aumento substancial da razão nuclear/citoplasmática de p53 e importina-alfa em fígados de animais submetidos ao modelo e tratados com tributirina, mas não nos tratados com lipídios estruturados. Por outro lado, o tratamento com lipídios estruturados reduziu a expressão dos oncogenes Bcl2, Ccnd2, Pdgfa, Vegfa e aumentou a expressão dos genes supressores de tumor Cdh13, Fhit e Socs3. Assim, embora o potencial quimiopreventivo dos lipídios estruturados seja comparável ao da tributirina, os resultados sugerem que o novo composto não exibe atividade de HDACi, e que seus efeitos inibitórios na hepatocarcinogênese possam ser atribuídos à modulação da expressão de oncogenes e genes supressores de tumor. / Combination of chemopreventive agents with different mechanisms of action has been considered a promising strategy to cancer prevention. Among several bioactive food compounds, tributyrin, a butyric acid prodrug obtained from dairy products and dietetic fiber fermentation, and flax seed oil, a rich source of alpha linolenic acid have shown chemopreventive potential. Here, we evaluated the chemopreventive activity of structured lipids obtained by enzymatic interesterification of tributyrin and flax seed oil during the early promotion phase of experimental hepatocarcinogenesis. Male Wistar rats subjected to the resistant hepatocyte model were treated daily, i.g, with maltodextrin, flax seed oil, tributyrin, non-sterified blend, or structured lipids. Treatment structured lipids showed similar chemopreventive activity compared to tributyrin, even when structured lipids yielded lower concentrations of butyric in the liver. Tributyrin and structured lipids did not inhibit cell proliferation in preneoplastic lesions, but both of them induced apoptosis in remodeling preneoplastic lesions. In addition, histone acetylation and p21 restored expression tributyrin molecular mechanisms were related to modulation of p53 nuclear shuttling mechanisms. In the present study, it was observed a substantial increase in p53 nuclear/cytoplasmic ratio and importin-alpha in preneoplastic livers of tributyrin treated rats, but not in those treated with structured lipids. In contrast, treatment structured lipids downregulated expression of major oncogenes Bcl2, Ccnd2, Pdgfa, and Vegfa; and upregulated expression of critical tumor suppressor genes, Cdh13, Socs3 and Fhit. Hence, although structured lipids and tributyrin show similar chemopreventive potential, the results suggest that the new compound does not exhibit HDACi activity, and that its inhibitory effects may be attributed to the modulation of oncogenes and tumor suppressor genes expression.

Il rinnovato interesse nella coltivazione della canapa industriale non è stato supportato da studi approfonditi e generalmente si basa su esperienze dirette di coltivazione. Questo studio si prefigge come obbiettivo quello di sfruttare tutte la parti della pianta di canapa per migliorare l’economicità complessiva della sua coltivazione tramite l’uso di tecniche agronomiche e di pratiche post-raccolta. La Cannabis sativa ha un vasto campo di applicazioni, tra cui le più promettenti in termini di ritorno economico sono il cosmetico e il farmaceutico. I composti naturali più interessanti della Cannabis sono i cannabinoidi non-psicoattivi cannabidiolo (CBD) e cannabigerolo (CBG) presenti in elevate concentrazioni nelle foglie e nelle brattee di Cannabis. Altri metaboliti secondari prodotti dalla canapa e di grande interesse sono le cannflavine, una classe di prenil-flavonoidi caratteristico di questa specie. Nel primo e nel secondo capitolo la dinamica temporale di accumulo dei metaboliti secondari ad elevato valore aggiunto è stata monitorata per alcune delle varietà più comuni di canapa industriale ed è stata determinata la produzione potenziale di questi composti. Nel terzo capitolo una collezione di semi di canapa è stata valutata per le caratteristiche morfologiche e per il contenuto e la qualità dell’olio. Concludendo questo studio contribuisce allo sviluppo di una coltivazione della canapa per le molteplici destinazioni d’uso dei semi e del fitocomplesso. / Rapidly growing interest into industrial hemp cultivation is not supported by strong data and generally is referred to a limited experience on field cultivation. This study aims to exploit all the parts of hemp plant, in order to ameliorate the overall economy of its cultivation and by providing information on agronomic management and post-harvest operations. Cannabis sativa has a wide range of industrial applications and the most promising, in terms of economic revenues, are the cosmetic and pharmaceutics. The most interesting phytochemicals in Cannabis are the cannabinoids, in particular the non-intoxicating compounds cannabidiol (CBD) and cannabigerol (CBG), present at high concentration in the leaves and bracts of Cannabis. Some other promising secondary metabolites of hemp are cannflavins, a class of prenyl-flavonoids characteristic of this species. In the first and second chapter the time course accumulation of high added-value compounds was monitored for some of the most common industrial hemp cultivars, and the potential production was assessed. In the third chapter a collection of hemp seeds was evaluated for its morphological characteristics and for its oil content and quality. In conclusion this thesis contributes to a further development of multipurpose hemp cultivation for seed and phytocomplex production.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / The industrialisation of the twenty-first century and the worldwide population growth led to the high demand for energy. Fossil fuels are the leading contributor to the global energy, and subsequently, there is a high demand of fuels. The decrease of global fossil fuels and the environmental air pollution caused by these fuels are concerning. Therefore, eco-friendly and renewable fuel such as biodiesel is one the leading alternative. Chromatography and Spectroscopy are the most used analytical methods and proven reliable but are time-consuming, requires qualified personal, extensive samples preparation, costly and do not provide in-situ real-time monitoring. Fourier Transform Infrared (FTIR) has mainly been used for qualitative analysis of biodiesel, but not much work has been reported in real-time monitoring. This study focused on the modelling of in-situ real-time monitoring of the biodiesel production from sunflower oil using FTIR (Fourier Transform Infrared). The first part of the study investigated the effect of catalyst ratio and methanol to oil ratio on biodiesel production by using central composite design (CCD). Biodiesel was produced by transesterification using Sodium Hydroxide as a homogeneous catalyst. A laboratory-scale reactor consisting of; flat bottom flask mounted with a reflux condenser, a hot plate as heating element equipped with temperature, timer and stirring rate regulator was used. Key parameters including, time, temperature and mixing rate, were kept constant at 60 minutes, 60 oC and 600 RPM, respectively. From the results obtained, it was observed that the biodiesel yield depends on catalyst ratio and methanol to oil ratio. The highest yield of 50.65 % was obtained at a catalyst ratio of 0.5 wt% and methanol to oil mole ratio 10.5. The analysis of variances of biodiesel yield showed the R2 value of 0.8387. A quadratic mathematical model was developed to predict the biodiesel yield in the specified parameters range. The same set-up was used to produce waste margarine biodiesel using a homogeneous catalyst, potassium hydroxide (KOH). The effects of four reaction parameters were studied, these were: methanol to oil ratio (3:1 to 15:1), catalyst ratio (0.3 to 1.5 wt. %), temperature (30 to 70 oC), time (20 to 80 minutes). The highest yield of 91.13 % was obtained at 60°C reaction temperature, 9:1 methanol to oil molar ratio, 0.9 wt. % catalyst ratio and 60 minutes. The important biodiesel fuel properties were found to be within specifications of the American Standard Test Method specifications (ASTM). It was concluded that waste margarine can be used to produce biodiesel as a low-cost feedstock. The core of the study was performed using EasyMax Mettler Toledo reactor equipped with a DiComp (Diamond) probe. The quantitative monitoring of the biodiesel production was performed by building a quantitative model with multivariate calibration using iC Quant module from iC IR 7.0 software. Fourteen samples of known concentrations were used for the modelling which were taken in duplicate for model calibration and cross-validation, data were pre-processed using mean centring and variance scale, spectrum math square root and solvent subtraction. These pre-processing methods improved the performance indexes from 7.98 to 0.0096, 11.2 to 3.41, 6.32 to 2.72, 0.9416 to 0.9999, RMSEC, RMSECV, RMSEP and R2Cum, respectively. The R2 values of 1 (training), 0.9918 (test), 0.9946 (cross-validation) indicated the fitness of the model built. The model was tested against the univariate model; small discrepancies were observed at low concentration due to unmodelled intermediates but were quite close at concentrations above 18%. The software eliminated the complexity of the Partial Least Square (PLS) chemometrics. It was concluded that the model obtained could be used to monitor transesterification of sunflower oil at industrial and lab scale. The model thus obtained, a batch reactor setup, EasyMax Mettler Toledodo reactor was used, the experiments were designed and monitored using iControl software. The results were recorded and quantified using iC IR software based on the biodiesel calibrated monitoring model built. The optimisation of the biodiesel was performed using three key parameters (methanol to oil ratio, catalyst ratio and temperature) while keeping time at 60 minutes and mixing rate at 150RPM. The highest yield of 97.85 % was obtained at 60 oC, 0.85 wt % catalyst ratio and 10.5 methanol to oil mole ratio. The analysis of variances of biodiesel production showed the values of 0.9847, 0.9674 and 0.8749, for R-squared, adjusted R-squared and predicted R-squared, respectively. A quadratic mathematical model was developed to predict the biodiesel conversion in the specified parameters ranges. Using the Arrhenius equation, activation energy (Ea) and frequency factor were found to be 41.279 kJ.mole-1 and 1.08 x10-4 M-1. s-1, respectively. The proposed kinetics model was a pseudo-first-order reaction. It was concluded that the model obtained can be used for industrial and laboratory-scale biodiesel production monitoring.

As doenças transmitidas por mosquitos representam uma das maiores causas de morbidade e mortalidade em todo o mundo, principalmente em países tropicais. O uso tópico de repelentes em determinadas situações torna-se a única alternativa para evitar o ataque por estes artrópodes. Os óleos de andiroba (Carapa guianensis) e copaíba (Copaifera sp.) possuem relatos de atividade repelente de insetos, podendo representar uma alternativa segura ao uso de repelentes sintéticos que apresentam riscos de toxidade em determinados casos. O objetivo desta pesquisa foi desenvolver nanoemulsões O/A, utilizando como fase oleosa os óleos de copaíba e andiroba, e testar in vivo a atividade repelente das mesmas frente ao mosquito Aedes aegypti, realizando um estudo comparativo com repelente comercial a base de DEET. Ensaios para avaliar os parâmetros físico-quimicos envolvidos no processo de obtenção das nanoemulsões, e estudos de sua estabilidade preliminar, também foram realizados. Os resultados apontam a viabilidade do método de emulsificação utilizando baixa energia na formação de nanoemulsões. A temperatura, velocidade de agitação, ordem de adição dos componentes e quantidade de tensoativo na formulação, demonstraram ser fatores críticos no processo. Foi possível obter três nanoemulsões estáveis com tamanho de glóbulos inferior a 300nm, sendo uma com 15% de óleo de andiroba; outra contendo 10% de óleo de copaíba e a terceira associando 10% de andiroba e 5% de copaíba. No ensaio repelente utilizando voluntários humanos, foi constatado que as nanoemulsões compostas de óleo de andiroba e óleo de andiroba adicionado de óleo de copaíba são capazes de repelir mosquitos Aedes aegypti por um período de 30 minutos, sendo estes resultados estatisticamente significativos em relação ao grupo controle. / Mosquito-borne diseases remain a major source of illness and death worldwide, particularly in tropical countries. Mosquito repellents may be one of the most effective tools for protecting humans from vector-borne diseases. In many circumstances, applying repellent to the skin may be the only feasible way to protect against insect bites. The oils from andiroba (Carapa guianensis seed oil) and copaíba (Copaifera oil) have been studied as possible mosquito repellents. These products can be represents a safe alternative in the use of synthetic repellent, that have toxic risks in some cases. The goals of this research were to development O/A nanoemulsion using andiroba seed oil and copaíba oil and test their repellent action in vivo against bites Aedes aegypti. This study compares the repel effectiveness of nanoemulsions developed in relation to the market product of DEET. Assays to evaluate the parameters involved physicist-chemistries in the process of attainment of the nanoemulsions, and studies of its preliminary stability, had been also carried through. The results showed viability of the emulsification method using low energy in the formation of nanoemulsions. The temperature, speed of agitation, order of addition of the components and amount of surfactant in the formulation, had demonstrated to be critical factors in the process. In this study, it was possible get three stable nanoemulsion with droplets size less than 300nm, using: 15% andiroba seed oil; 10% copaiba oil and mix of andiroba seed oil (10%) and copaíba oil (5%). The repellent test with human voluntaries proves that nanoemulsions with andiroba seed oil, and the mix of andiroba seed oil and copaiba oil, are able to repel Aedes aegypti for 30 minutes period, witch are statistic signification compared to the control group.