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No. of bitstreams: 1 Diseertassão _NATALIA_IMPRESSA_15 janeiro 2018_AN vancouver_CORRIGIDA_Repósitório.doc: 2779648 bytes, checksum: 02c7a7808d0127cdc16506f50f009392 (MD5) Previous issue date: 2017-11-28 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Objetivo: o presente trabalho teve como objetivo a síntese enzimática de lipídeos estruturados a partir dos óleos de semente de uva e algodão, especificamente os triglicerídeos dietéticos do tipo MLM (médio:longo:médio), ou seja, aqueles que possuem ácidos graxos de cadeia média (M), em posições sn-1 e sn-3, e de cadeia longa (L), na posição interna da molécula de triacilglicerol. Métodos: fez-se a caracterização das matérias primas (óleos de semente de uva e algodão) e dos TAGs (triglicerídeos) modificados em relação aos índices de acidez, peróxido, perfil em ácidos graxos por cromatografia gasosa e determinação da posição sn-2. Determinou-se as atividades de hidrólise e de esterificação das lipases empregadas. Utilizou-se um planejamento de experimentos (DCCR- Central Composite Rotatable Design) para verificar a influência de razão molar e temperatura sobre o grau de incorporação (GI) do ácido graxo de cadeia média. Por fim fez-se a caracterização hidrodinâmica do reator de leito fixo e/ou empacotado. Resultados: os resultados mostraram que as matérias primas estão dentro dos padrões de especificação (0,6 mg KOH/g para acidez e 10 meq/kg para peróxido), fornecendo valores semelhantes, independentemente do óleo analisado. Os óleos foram ainda caracterizados quanto à composição em ácidos graxos por cromatografia gasosa. Ambos apresentaram altas quantidades de ácidos graxos insaturados, ressaltando-se o essencial ácido linoleico (C18:2n6). Em seguida, foram efetuadas reações de acidólise, visando-se à seleção do ácido graxo e do biocatalisador. Para o óleo de uva, foram obtidos valores de grau de incorporação (GI, %) que variaram de 23,62±1,34 a 34,53±0,05%. Os melhores resultados foram obtidos empregando-se C10 como ácido graxo e a lipase Lipozyme RM IM (34,53±0,05%). Para o óleo de algodão, os melhores resultados de GI também foram obtidos empregando-se C10:0 e a lipase Lipozyme RM IM (36,63±0,23%), e o GI variou de 22,92±4,35 a 36,63±0,23%. Finalmente, realizou-se um planejamento de experimentos (DCCR) que avaliou a influência de razão molar e temperatura sobre o grau de incorporação, observando-se que apenas razão molar obteve influência significativa sobre o grau de incorporação. Com relação às reações de acidólise em leito fixo, estas foram conduzidas empregando-se tempo espacial de 1 hora, e o GI máximo foi em torno de 35% para ambos os óleos. Conclusão: diante do exposto, foi possível sintetizar triglicerídeos dietéticos do tipo MLM a partir dos óleos de semente de uva e algodão, utilizando reatores de tanque agitado e leito fixo. / Objective: the objective of the present work was the enzymatic synthesis of structured lipids from grape and cottonseed oils, specifically the MLM type dietary triglycerides, that is, those with medium chain fatty acids (M), in positions sn-1 and sn-3, and long-chain (L), in the internal position of the triacylglycerol molecule. Methods: The raw materials (grape and cottonseed oils) and the modified TAGs (triglycerides) were characterized in relation to the acid, peroxide, fatty acid profile by gas chromatography and the sn-2 position determination. The hydrolysis and esterification activities of the lipases employed were determined. A DCCR (Central Composite Rotatable Design) was used to verify the influence of molar ratio and temperature on the degree of incorporation (ID) of the medium chain fatty acid. Finally, the hydrodynamic characterization of the fixed bed reactor and / or packaged was performed. Results: The results showed that the raw materials are within the specification standards (0.6 mg KOH / g for acidity and 10 meq / kg for peroxide), providing similar values regardless of the oil analyzed. The oils were further characterized for fatty acid composition by gas chromatography. Both presented high amounts of unsaturated fatty acids, emphasizing the essential linoleic acid (C18: 2n6). Then, acidolysis reactions were carried out, aiming at the selection of the fatty acid and the biocatalyst. For the grape oil, values of degree of incorporation (ID,%) ranging from 23.62±1.34 to 34.53±0.05% were obtained. The best results were obtained using C10:0 as fatty acid and Lipozyme RM IM lipase (34.53 ± 0.05%). For cotton oil, the best ID results were also obtained using C10 and Lipozyme RM IM lipase (36.63 ± 0.23%), and ID ranged from 22.92 ± 4.35 to 36.63 ± 0.23%. Finally, an experiment planning (DCCR) was carried out, which evaluated the influence of molar ratio and temperature on the degree of incorporation, observing that only molar ratio had a significant influence on the degree of incorporation. In relation to the fixed bed acidolysis reactions, these were conducted using 1 hour spatial time, and the maximum ID was around 35% for both oils. Conclusion: in view of the above, it was possible to synthesize MLM type dietary triglycerides from the grape and cottonseed oils, using batch and fixed bed reactors. / CNPq: 446371/2014-9

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 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.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work had as main objective the development of nanostructured formulations containing rutin, using nanoparticles prepared with alternative vegetables oils. In the first chapter it was demonstrated the feasibility of preparing nanocapsules and nanoemulsions using grape seed or almond kernel oil. Nanocapsule suspensions and nanoemulsions were prepared by the interfacial deposition of preformed polymer and spontaneous emulsification, respectively. All formulations presented nanometric mean size, polydispersity index below 0.30, negative zeta potential, pH values between 6.5 and 7.5 remaining stable after 6 storage months. These formulations promoted the protection of the active against UV degradation, regardless of the type of the oily phase or vesicle. In the second chapter, formulations prepared with grape seed oil were selected for the development of rutin-loaded nanoparticles, as well as to evaluate its in vitro antioxidant activity and photostability. All formulations presented nanometric size, low polydispersity index, acid pH values, negative zeta potential and encapsulation efficiency close to 100 %. Nanoparticles were able to protect rutin against UV photodegradation, if compared to rutin ethanolic solution. In the study of the in vitro antioxidant activity, rutin-loaded nanocapsules and nanoemulsions showed a lower rutin decay rate compared to the rutin ethanolic solution when exposed to UV radiation in the presence of OH radical. However, its presence in nanocapsules led to a prolonged in vitro antioxidant activity compared to the rutin-loaded nanoemulsions. Finally, in the third chapter we studied the development of hydrogels containing rutin (free or associated to polymeric nanocapsules). Their activity on the cutaneous wound healing in rats was evaluated. The developed formulations showed adequate properties regarding their cutaneous administration. In vivo response concerning the healing effect of hydrogels was evaluated by the regression of skin lesions after six days of treatment. Markers of oxidative stress in the lesions of rats were also evaluated, as levels of lipid peroxidation analyzed by the method of thiobarbituric acid reactive substances (TBARS), determination of protein carbonyls levels, total proteins levels, glutathione (GSH) levels, vitamin C and evaluation of the antioxidant enzyme catalase (CAT). This last chapter showed for the first time the feasibility of the dermatological use of such formulations containing rutin to promote the in vivo wound healing. / Este trabalho teve como principal objetivo o desenvolvimento de formulações nanoestruturadas contendo rutina, a partir de nanopartículas contendo óleos vegetais até então não estudados no preparo destas formulações. No primeiro capítulo foi demonstrada a viabilidade de preparar nanocápsulas e nanoemulsões contendo o óleo de semente de uva e de amêndoas doce como fase oleosa. As suspensões de nanocápsulas e nanoemulsões foram preparadas pelo método da deposição interfacial do polímero pré-formado e emulsificação espontânea, respectivamente. Todas as formulações apresentaram tamanho médio nanométrico, índice de polidispersão inferior a 0,30, potencial zeta negativo e valores de pH entre 6,5 e 7,5, permanecendo estáveis após 6 meses de armazenamento. As formulações promoveram a fotoproteção do ativo frente à degradação UV, independente do tipo de fase oleosa e do tipo de vesícula. No segundo capítulo, as formulações contendo o óleo de semente de uva foram selecionadas para o estudo do desenvolvimento de nanopartículas contendo rutina, bem como avaliação de sua atividade antioxidante in vitro e fotoestabilidade. Após o preparo, todas as formulações apresentaram tamanho nanométrico de partículas, baixo índice de polidispersão, valores de pH ácido, potencial zeta negativo e eficiência de encapsulação próxima à 100%. As nanopartículas protegeram a rutina frente à fotodegradação UV, quando comparadas à solução etanólica. No estudo da atividade antioxidante in vitro, as nanocápsulas e nanoemulsões apresentaram uma menor taxa de decaimento da rutina comparada com a solução etanólica, quando expostas à radiação UV em presença do radical ·OH. No entanto, a presença das nanocápsulas levou a uma atividade antioxidante in vitro mais prolongada comparada com as nanoemulsões contendo rutina. Finalmente, no terceiro capítulo estudamos o desenvolvimento de hidrogéis contendo rutina livre ou associada a nanocápsulas poliméricas, avaliando a sua atividade sobre a cicatrização de lesões cutâneas em ratos. As formulações desenvolvidas apresentaram propriedades adequadas para aplicação tópica. A resposta in vivo do efeito cicatrizante foi avaliada através da regressão de lesões na pele após 6 dias de tratamento. Marcadores do estresse oxidativo nas lesões dos ratos foram também avaliados, como os níveis da peroxidação lipídica através do método de TBARS, níveis de proteína carbonilada, níveis de proteínas totais, níveis de glutationa (GSH), vitamina C e avaliação da enzima antioxidante catalase (CAT). Este terceiro capítulo demonstrou pela primeira vez a potencialidade do emprego dermatológico de hidrogéis contendo rutina para a promoção de cicatrização de feridas in vivo.

<p>Podizanje novih zasada i povećanje kapaciteta prerade<br />grožđa povećava količinu otpada sa kojim se suočava<br />industrija proizvodnje vina i rakije. Najbolji i najodgovorniji<br />način upravljanja otpadom je njegovo dalje iskori&scaron;ćenje<br />kao nusproizvoda. U ovoj disertaciji sagledavana je mogućnost iskori&scaron;ćenja<br />nusproizvoda iz različitih faza proizvodnje u vinarijama i<br />destilerijama za dobijanje semenki grožđa koje su<br />kori&scaron;ćene za proizvodnju hladno presovanog ulja. Hipoteza<br />se zasniva na činjenici da semenke grožđa raznih sorti iz<br />različitih faza proizvodnje vina (bela, roze ili crvena vina),<br />odnosno, rakije mogu imati sasvim različit hemijski sastav i<br />kvalitet koji svakako može da se reflektuje na kvalitet,<br />bioaktivne komponente i održivost hladno presovanog ulja.<br />Ovakav proizvod, obzirom da je dobijen hladnim<br />presovanjem, može biti veoma atraktivan za potro&scaron;ače,<br />zbog svojih specifičnih senzorskih i nutritivnih<br />karakteristika.<br />Za potrebe izrade disertacije prikupljeni su nusproizvodi<br />i pripremljeni su uzorci iz vinarija i destilerija fru&scaron;kogorskog<br />vinogorja. Dobijene su semenke i proizvedeno hladno<br />presovano ulje od semenki crnog grožđa sorte Merlot,<br />belog grožđa sorte Italijanski rizling i belog grožđa sorte<br />Sila, kao autohtone sorte vinove loze. Hladno presovana<br />ulja su proizvedena od semenki grožđa koje nisu pro&scaron;le<br />nikakav tretman, odnosno dobijene su nakon presovanja,<br />prilikom proizvodnje belih (Italijanski rizling i Sila) i roze<br />(Merlot) vina, zatim od semenki koje su pro&scaron;le proces<br />fermentacije prilikom proizvodnje crvenih vina (Merlot) i od<br />semenki koje su pro&scaron;le proces fermentacije i destilacije<br />prilikom proizvodnje rakije (Merlot, Italijanski rizling i Sila).<br />Pored navedenih semenki i ulja, pripremljen je i prosečan<br />proizvodni uzorak koji predstavlja uzorak dobijen od svih<br />prikupljenih semenki. Kao uporedni uzorci kori&scaron;ćeno je<br />nerafinisano i rafinisano ulje od semenki grožđa nabavljeno<br />na trži&scaron;tu. Za realizaciju postavljenog cilja, rad na izvođenju ove<br />disertacije obuhvatio je različite faze. U prvoj fazi<br />prikupljene su semenke grožđa i ispitivane su njihove<br />tehničko-tehnolo&scaron;ke karakteristika i kvalitet. Zatim su od<br />navedenih semenki proizvedena hladno presovana ulja.<br />U sledećim fazama, ovako dobijena uja, zajedno sa<br />uzorkom nerafinisanog i rafinisanog ulja od semenki<br />grožđa sa trži&scaron;ta ispitivana su sa aspekta senzorskog i<br />nutritivnog kvaliteta i praćene su razlike u održivosti ulja.<br />Izvr&scaron;ena je senzorska analiza, određivane su frakcije<br />pigmenata, karotenoidi i hlorofili, merena je transparencija,<br />a parametri boje ulja određivani su i instrumentalno.<br />Nutritivni kvalitet ulja sagledavan je na osnovu sadržaja i<br />sastava bioaktivnih komponenti, pre svega tokoferola i<br />tokotrienola, fenola i sterola. Budući da ova jedinjenja<br />ispoljavaju značajne antioksidativne aktivnosti izvr&scaron;eno je i<br />ispitivanje antiradikalske aktivnosti uzoraka. Odživost ulja<br />od semenki grožđa sagledana je na osnovu početnog<br />kvaliteta i oksidativnog stanja, kao i rezultata ubrzanih<br />testova, kao &scaron;to je Rancimat test, Schaal-oven test i<br />fluorescentni test.<br />Na osnovu dobijenih rezultata, može se konstatovati da<br />su svi dobijeni uzorci semenki imali dobru skladi&scaron;nu vlagu,<br />koja, obzirom na mali sadržaj ulja u semenkama, može da<br />osigura čuvanje semenki u dužem periodu. Sadržaj ulja u<br />semenkama, pored uticaja sorte vinove loze, zavisi i od<br />uticaja procesa kome su podvrgnute semenke pre<br />presovanja (fermentacija, destilacija).<br />Senzorska analiza ulja od semenki grožđa pokazala je<br />značajne razlike u karakteristikama koje su posledica ne<br />samo načina dobijanja ulja (hladno presovano ili rafinisano), sorte vinove loze, već i postupka dobijanja,<br />porekla i kvaliteta semenki grožđa. Uslovi kojima su<br />semenke grožđa izložene u toku alkoholne fermentacije i<br />posebno destilacije utiču na formiranje specifične arome<br />hladno presovanog ulja. I pored toga &scaron;to se pojavljuje<br />izuzetno &scaron;irok spektar različitih aroma, mirisa i ukusa u ulju<br />i &scaron;to postoje značajne razlike u aromi ulja u zavisnosti od<br />sorte grožđa, moguće je prepoznati da li je hladno<br />presovano ulje dobijeno od semenki grožđa bez<br />fermentacije, posle fermentacije ili posle destilacije.<br />Takođe, sa aspekta boje ulja može se kazati da rafinisano<br />ulje od semenki grožđa ima svetlo žutu boju sa<br />zelenkastom nijansom, dok su hladno presovana ulja<br />intenzivnijih boja i kreću se od žuto-zelenkaste, preko<br />zelenkasto žute i svetlo zelenkaste do tamno zelene. Veći<br />udeo zelene boje imaju hladno presovana ulja od semenki<br />grožđa dobijenih posle destilacije.<br />U radu je pokazano da sadržaj pigmenata (karotenoida i<br />hlorofila) u velikoj meri zavisi od porekla semenki.<br />Postupak fermentacije doprinosi povećanju sadržaja<br />pigmenata, dok postupak destilacije, zbog visokih<br />temperatura ima negativan efekat.<br />Transparencija uzoraka hladno presovanih ulja od<br />semenki grožđa proizvedenih za potrebe disertacije kretala<br />se od 32,8% do 53,8%.<br />Sadržaj nezasićenih masnih kiselina u svim uzorcima<br />ulja od semenki grožđa veći je od 90%, pri čemu<br />dominantnu masnu kiselinu čini linolna, omega-6, masna<br />kiselina.<br />Sadržaj tokotrienola je veći od sadržaja tokoferola u uljima od semenki grožđa, a dominantni tokoferol je alfatokoferol.<br />Njegov sadržaj je veći u uzorcima ulja dobijenim<br />iz semenki nakon fermentacije i destilacije.<br />Sadržaj fenolnih jedinjenja, u zavisnosti od sorte, u<br />proseku je ne&scaron;to vi&scaron;i u hladno presovanim uljima dobijenim<br />od crvene sorte grožđa, ali uočava se i značajan porast<br />(akumulacija) fenola u hladno presovanim uljima dobijenim<br />iz semenki grožđa nakon procesa fermentacije i destilacije.<br />Najveći pojedinačni sadržaju u ulju od semenki grožđa ima<br />ursolna kiselina, a pored nje značajniji sadržaj, mada<br />mnogo manji, pokazuju rezveratrol, kemferol i vanilinska<br />kiselina.<br />Najzastupljeniji steroli ulja semenki grožđa su &beta;-<br />sitosterol sa udelom od 62,59-69,74%, stigmasterol sa<br />udelom od 12,13-15,00% i kampesterol sa udelom od 6,59-<br />11,94% u ukupnim sterolima. Na sadržaj fitosterola u<br />uljima od semenki grožđa nemaju uticaja procesi<br />fermentacije i destilacije kojima su podvrgnute semenke<br />pre preosvanja.<br />U radu je dokazan negativan uticaj procesa fermentacije<br />i destilacije kojima su povrgnute semenke grožđa na<br />antiradikalski potencijal dobijenih ulja. Antiradikalski<br />potencijal ulja od semenki grožđa zavisi i od sorte vinove<br />loze, kao i od načina dobijanja ulja (hladno presovano ili<br />rafinisano).<br />Procesi fermentacije i destilacije utiču i na osnovni<br />hemijski kvalitet dobijenih hladno presovanih ulja na način<br />da dovode do povećanja kiselinskog i peroksidnog broja.<br />Hladno presovana ulja od semenki grožđa pokazuju<br />dobru oksidativnu stabilnost. Rancimat test je pokazao razlike u indukcionom periodu hladno presovanih ulja od<br />semenki grožđa kao posledicu razlike u sorti, kao i u<br />načinu dobijanja semenki. Proces fermentacije utiče na<br />povećanje, a proces destilacije na smanjenje indukcionog<br />perioda.<br />Na osnovu svih dobijenih rezultata istraživanja može se<br />konstatovati da su hladno presovana ulja od semenki<br />grožđa pokazala različit nutritivni kvalitet i oksidativnu<br />stabilnost, zbog specifičnih razlika koje su posledica razlika<br />u sorti i poreklu semenki, tj. zbog specifičnog efekta<br />fermentacije i destilacije na semenke od kojih je ulje<br />proizvedeno, čime je i potvrđena hipoteza.</p> / <p>Raising new plantations and increasing the grape<br />processing capacity increases the amount of waste faced<br />by the wine and brandy industry. The best and most<br />responsible way of waste management is its further<br />exploitation as by-products.<br />In this dissertation, the possibility of using by-products from different stages of production in wineries and distilleries for<br />obtaining grape seeds, which were used for the production<br />of cold pressed oil, was examined. The hypothesis is<br />based on the fact that grape seeds of various varieties<br />from different stages of wine production (white, rose or red<br />wine), that is, brandy can have a completely different<br />chemical composition and quality that can certainly be<br />reflected on the quality, bioactive components and stability<br />of cold pressed oil.<br />Such a product, as it is obtained by cold pressing, can<br />be very attractive to consumers, due to its specific sensory<br />and nutritional characteristics.<br />For the needs of the dissertation, the by-products were<br />collected and samples were prepared from the wineries<br />and distilleries of the Fru&scaron;ka Gora vineyard. Seeds were<br />obtained and cold pressed oil produced from Merlot grape<br />seed, as representatives of red grape varieties, Italian<br />Riesling, as representatives of white grape varieties and<br />Sila, as new white grape varieties. Cold pressed oils were<br />produced from grape seeds that did not undergo any<br />treatment, that is, they were obtained after pressing, during<br />the production of white (Italian Riesling and Sila) and rose<br />(Merlot) wines, then from the seeds that were fermented<br />during the production of red wines (Merlot ) and seeds that<br />have undergone fermentation and distillation process<br />during the production of brandy (Merlot, Italian Riesling and<br />Sila). In addition to the mentioned seeds and oils, an<br />average production sample was prepared, which is a<br />sample obtained from all collected seeds. Unrefined and<br />refined grape seed oil purchased on the market was used<br />as comparative samples. For realization of the set goal, the work on the<br />performance of this dissertation encompassed different<br />phases. In the first phase, grape seed were collected and<br />their technical and technological characteristics and quality<br />were examined. Then cold-pressed oils were produced<br />from these seeds.<br />In the following phases, the resulting ear, together with a<br />sample of unrefined and refined grape seed oil from the<br />market, were examined from the aspect of sensory and<br />nutritional quality and differences in oil stability were<br />observed. Sensory analysis was performed, pigmentate<br />fractions, carotenoids and chlorophylls were determined,<br />transparency was measured, and oil color parameters<br />were also determined instrumentally. The nutritive oil<br />quality was examined based on the content and<br />composition of bioactive components, primarily tocopherols<br />and tocotrienols, phenols and sterols. Since these<br />compounds exhibit significant antioxidant activities, the<br />antiradical activity of the samples was also tested. The<br />stability of grape seed oils was examined based on the<br />initial quality and the oxidative state, as well as the results<br />of accelerated tests, such as Rancimat test, Schaal-oven<br />and fluorescence test.<br />On the basis of the obtained results, it can be concluded<br />that all the obtained seed samples had good storage<br />moisture, which, given the small content of oil in the seeds,<br />can ensure the storage of seeds for a longer period. The<br />content of oil in the seed, in addition to the influence of the<br />grape variety, depends on the influence of the process to<br />which the seeds are subjected to pressing (fermentation,<br />distillation). Sensory analysis grape seed oils showed significant<br />differences in characteristics that are due not only to the<br />method of obtaining oil (cold pressed or refined), grape<br />varieties, but also the method of obtaining, the origin and<br />quality of grape seed. The conditions for grape seeds<br />exposed during fermentation and especially distillation<br />affect the formation of a specific cold pressed oil. Although<br />an extremely wide range of different flavors, odors and<br />flavors in oil appear, and there are significant differences in<br />the aroma of the oil, depending on the grape variety, it is<br />possible to recognize whether the cold-pressed oil is<br />derived from the grape seed without fermentation, after<br />fermentation or after distillation. Also, from the aspect of oil<br />color it can be said that refined grape seed oil has a light<br />yellow color with a greenish shade, while cold pressed<br />grape seed oils have more intense colors range from<br />yellowish-greenish, over greenish yellow and light greenish<br />to dark green. A higher proportion of green color has cold<br />pressed grape seed oils obtained after distillation.<br />The thesis has shown that the content of pigments<br />(carotenoids and chlorophyll) depends to a great extent on<br />the origin of the seed. The fermentation process<br />contributes to increasing the content of pigments, while the<br />distillation process has a negative effect due to high<br />temperatures.<br />Transparency of cold pressed grape seed oils produced<br />for the dissertation ranged from 32.8% to 53.8%.<br />The content of unsaturated fatty acids in all samples of<br />grape seed oil is greater than 90%, with the dominant fatty<br />acid being linoleic, omega-6, fatty acid. The content of tocotrienols is higher than the content of<br />tocopherols in grape seed oils, and the dominant<br />tocopherol is alpha-tocopherol. Its content is higher in oil<br />samples obtained from the seed after fermentation and<br />distillation.<br />The content of phenol compounds, depending on the<br />variety, is somewhat higher in cold pressed oils obtained<br />from red grape varieties, but there is also a significant<br />increase in accumulation of phenol in cold pressed oils<br />obtained from the grape seed after the fermentation and<br />distillation process. The largest individual oil content of<br />grape seeds has ursolic acid, and besides it, significant<br />content, although much smaller, shows rezveratrol,<br />kemferol and vanillinic acid.<br />The most prevalent sterols of grape seed oils are &beta;-<br />sitosterol with a share of 62.59-69.74%, stigmasterol with a<br />share of 12.13-15.00% and campesterol with a share of<br />6.59-11.94% in total sterols. Fermentation and distilation<br />processes, to which the seeds have been exposed, have<br />no effect on the content of phytosterols in grape seed oils.<br />The paper has shown the negative influence of the<br />fermentation and distillation process, to which the seeds<br />have been exposed, onto the antiradical potential of the<br />obtained oils. The antiradical potential of grape seed oils<br />depends on grape varietes, as well as on the way oil is<br />obtained (cold pressed or refined).<br />Processes of fermentation and distillation also affect the<br />basic chemical quality of obtained cold pressed oils in such<br />a way as to increase the acid and peroxide values.<br />Cold pressed grape seed oils show good oxidative stability. The Rancimat test showed differences in the<br />induction period of cold pressed grape seed oils as a result<br />of the variation in the variety, as well as in the method of<br />obtaining the seed. The fermentation process affects the<br />increase, and the process of distillation decreases the<br />induction period.<br />Based on all the obtained results, it can be concluded<br />that cold pressed grape seed oils showed different<br />nutritional quality and oxidative stability due to specific<br />differences resulting from differences in variety and seed<br />origin, i.e. due to the specific effect of fermentation and<br />distillation processes on the seeds from which the oil was<br />produced, thus confirming the hypothesis.</p>