A carne bovina é considerada um alimento altamente nutritivo, sendo uma fonte de proteínas e vitaminas, além de minerais tal como ferro e zinco. Por outro lado, a carne vermelha atualmente tem sido associada a doenças cardiovasculares e ao câncer. No entanto, essa associação vem sendo contestada, pois a carne de ruminantes bem como o leite são fontes naturais do ácido linoléico conjugado (CLA, do inglês \"conjugated linoleic acid\"), o qual possui várias propriedades benéficas, como atividade anticarcinogênica, redução de gordura corporal, entre outras. Essas propriedades têm sido observadas em estudos com animais modelos, mas também pesquisas apontam tais benefícios para os humanos. Vários estudos têm sido realizados para aumentar a produção de CLA pelos ruminantes no Brasil. Nesse contexto, se faz necessário o desenvolvimento de métodos rápidos e eficazes para a determinação de CLA em carnes de ruminantes e no leite, pois o método atual é baseado na análise dos ésteres metílicos dos ácidos graxos por cromatografia gasosa, que envolve várias etapas, sendo um método laborioso. Assim, o principal objetivo deste trabalho foi o desenvolvimento de uma metodologia rápida, baseada na técnica de ressonância magnética nuclear de hidrogênio (RMN de 1H) para a determinação do teor do CLA na gordura de carne bovina. Para isso foi avaliada a influência dos principais parâmetros experimentais de RMN de 1H, como a largura do pulso de radiofrequência, o tempo de repetição, método de excitação seletiva, entre outros parâmetros que podem interferir na razão sinal/ruído e na reprodutibilidade das medidas. Os resultados mostraram que a utilização da RMN de 1H para a determinação do teor de CLA em carne bovina, além de ser coerente com os dados obtidos por cromatografia gasosa, representa uma abordagem mais rápida e simples para a determinação do teor de CLA em carne bovina. / Beef is considered a very nutritive food, since it is a source of proteins and vitamins, besides minerals such as iron and zinc, on the other hand it has been associated to heart diseases and cancer. However, this association has been contested because ruminant meat as well as milk, is a natural source of conjugated linoleic acid (CLA), that has several benefic properties such as anticarcinogenic activity, reduction of body fat and others. These properties have been observed in studies with animals and can be extended to humans. Several studies have been done to increase the concentration of CLA in Brazilian ruminant meat. In this context, it is necessary to develop fast and effective analytical methods to determine CLA in ruminant meat and milk, because the current method, based on the analysis of fatty acid methyl esters by gas chromatography (GC), involves several stages, being laborious. Thus, the main purpose of this work was the development of a fast methodology, based on hydrogen nuclear magnetic resonance technique (1H NMR) to determine CLA content in beef fat. In consequence, it was evaluated the influence of main experimental parameters from 1H NMR, such as radiofrequency pulse width, repetition time, method of selective excitation, between others that may interfere in signal-to-noise ratio and reproducibility. The results indicated that the use of 1H NMR spectroscopy to determine CLA content in beef have high correlation to data obtained by gas chromatography, representing a much faster and simpler methodology to determine CLA content in beef.

Nesta dissertação, visamos o entendimento de processos intermediários que regem a transferência de energia e determinam as propriedades ópticas de polímeros conjugados, a fim de encontrar meios para aumentar a eficiência de emissão e o tempo de vida dos ?LED?s? orgânicos. Estudamos especificamente o polímero PPV, poli(p-fenileno vinilideno), sintetizado através de novo método desenvolvido no Grupo de Polímeros do Instituto de Física de São Carlos, por Marletta e colaboradores[1], na forma de filmes finos depositados pelas técnicas ?spincast? e de automontagem (LbL). Para o trabalho utilizamos técnicas espectroscópicas de luminescência, excitação seletiva e absorbância. Por meio de técnicas de engenharia molecular e através do ordenamento induzido da rede polimérica, avaliamos o peso que têm os eventos intermediários à emissão. Estiramos gradualmente filmes de PTHT/PPV depositados sobre Teflon, sob um eixo preferencial, e constatamos a dependência da polarização da luz emitida com processos de transferência de energia e com a anisotropia da matriz polimérica. Realizamos a separação das cadeias do copolímero a fim de analisar separadamente a transferência de energia entre os segmentos conjugados pertencentes a cadeias distintas (processos intercadeia) ou ao longo da cadeia (processos intracadeia). Esta separação intercadeia e intracadeia resultaram em um significativo aumento da eficiência da emissão, assim como um deslocamento da banda de emissão para o azul, privilegiando a emissão de segmentos de menor conjugação e que participavam apenas nos processos de relaxação de energia e transferência da excitação e não dos estados emissivos finais. Separamos os segmentos conjugados dentro da própria cadeia do copolímero, regulando o comprimento de conjugação, através da incorporação de DBS. Aqui, verificamos, os processos de transferência intracadeia concorrem em igual peso com processos intracadeia na migração energética em polímeros conjugados. Concluímos que o processo limitante da eficiência de emissão em polímeros conjugados e dispositivos é a eficiente transferência de energia entre cadeias ou ao longo da cadeia para centros supressores de energia. / The main goal of this work is the understanding of intermediated energy relaxation processes that are governed by Energy Transfer. Such processes strongly affect the optical properties of conjugated polymers, reducing the emission efficiency and the life time of OLEDs. We study specifically the polymer poly(p-phenylene vinylene), PPV, synthesized through the new method developed by Marletta and co-workers [1]. The films were prepared by Spincast and self-assembly (Layer-by-Layer) techniques on different substrates. The optical characterization of the polymeric material was carried out by photoluminescence, selective excitation spectroscopy and UV-Vis absorbance measurements. With the use of molecular engineering techniques and by changing the polymeric order induced by uniaxial stretch of the films deposited on a flexible substrate, it was possible to infer the weight of intermediary events in final emission process. A special issue of this work was the study of the optical properties of thin PPV films deposited on flexible Teflon substrates under very low deformation levels. Optical data of low stretched conjugated polymers on transparent substrates were not previously available in the literature. Continuous axial stretch was applied at room temperature to very thin PPV films enabling simultaneous luminescence and absorbance polarization measurements. The optical properties of polymeric light emitting devices are strongly dependent on the structural order of the polymer chains and the energy transport mechanism between the conjugated segments. We demonstrate that such low stretched films presents a very efficient isotropic-to-polarized conversion regarding the fact we are dealing with energy transfer between luminescent chromophore of same species. We also carried out chain separation of conjugated segments of a PPV copolymer in order to analyze two Energy Transfer kinds: one that occurs among PPV segments in different chains (interchain processes) and the other involving the Energy Transfer between PPV segments along the same PPV chain (intrachain processes). To account for the interchain separation of the PPV segments we diluted the PPV chain in an inert polymeric matrix. The novelty, however, lies in the precise control of the separation of PPV segments along the chain by using a copolymer with sequences of conjugated PPV and non-conjugated PTHT distributed randomly along the polymer chain. The efficiency increase together with the spectral blue shif with the segment separation show that inter- and intrachain exciton mobility is enhanced by low range Förster Energy Transfer. For the case of samples without chain separation, it is easier for excitons to move around by energy transfer process and find quenching defects before their radioactive decay. For diluted or low conjugated samples, excitons will not reach defects before recombination since Energy Transfer is suppressed. Thus, we verify, the Intrachain Energy Transfer process have the same influence as for Interchain process produced by the energy migration among conjugated polymers segments. From a more fundamental point of view, the establishment of a controlled ordering and separation of the polymeric chains may reduce effects such as the luminescence quenching that strongly reduce the emission efficiency in organic devices.

Orientador: Teresa Dib Zambon Atvars / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-24T04:00:22Z (GMT). No. of bitstreams: 1 Quites_FernandoJunior_D.pdf: 4476724 bytes, checksum: ad6fd1bd74a45cdc5e9333e1f66da8c0 (MD5) Previous issue date: 2013 / Resumo: Nesta Tese as propriedades foto e eletroluminescentes de diferentes polímeros conjugados foram abordadas: poli[(9,9-dioctilfluoreno-2,7-diil)-alt-co-(9,9-di-{5 f-pentanil}-fluoreno-2,7-diil)] (PFP) emissor na região do azul, poli[(9,9-dihexilfluoreno-2,7-diil)-alt-co-(bitiofeno)] (F6T2) emissor na região do verde e poli[2-metóxi-5(3 f,7 f-dimetiloctilóxi)1-,4-fenilenovinileno] (MDMO-PPV) emissor na região do vermelho. Primeiramente foram preparados materiais híbridos orgânico-inorgânico baseados em PFP e siliconas (polímeros de silício). Devido à presença de grupos vinílicos laterais na cadeia do PFP, estes foram ligados quimicamente às siliconas através da reação de hidrossililação produzindo dois tipos de siliconas: uma com menor grau (PDHS-PDVS-l-PFP-X) e outra com maior (PDHSS-PDVS-h-PFP-X) grau de reticulação. As propriedades fotofísicas destes materiais híbridos foram comparadas com o polímero PFP na forma de filme e em soluçõoes de THF e de diferentes polissiloxanos usados na reação de hidrossililação. Através de medidas de fotoluminescência no estado estacionário e medidas dinâmicas verificou-se que as cadeias de PFP estão desordenadas em solução e no filme fino e nas siliconas com menor grau de reticulação (PDHS-PDVS-l-PFP-X) independente da quantidade de PFP usada. Entretanto, nas siliconas híbridas com maior grau de reticulação (PDHSS-PDVS-h-PFP-X) uma fase cristalina, conhecida como fase a, foi formada. Além disso, nestes híbridos foram observados agregados emitindo em regiões de mais baixa energia quando a quantidade de PFP foi aumentada (PDHSS-PDVS-h-PFP-X, com X = 2 e 3). Portanto, a força dirigente para a formação da fase cristalina a pode ser pensada como uma combinação de interações p -p entre a cadeia principal planar do polímero e interações hidrofóbicas dos grupos laterais no ambiente mais confinado causado pelas cadeias das siliconas com maior grau de reticulação (PDHSS-PDVS-h-PFP-X). Após o estudo detalhado das propriedades fotofísicas do PFP tanto em solução como no estado sólido, blendas poliméricas baseadas neste polímero e no copolímero F6T2 foram preparadas. As investigações fotofísicas mostraram que há uma eficiente transferência de energia do doador PFP para o receptor F6T2 nestas blendas (PFP/F6T2). A transferência de energia se dá pelos processos não radiativo (mecanismo do tipo Förster) e radiativo. Foram também preparados diodos eletroluminescentes usando as blendas poliméricas de PFP/F6T2 como camada ativa (configuração do diodo ITO/PEDOT:PSS/blenda polimérica/Ca/Al) com a intenção de produzir dispositivos poliméricos emissores de luz branca (WPLEDs). Nestes dispositivos foi observada uma transferência de energia do PFP para o F6T2 e uma eficiente recombinação de cargas sendo favorecida nos domínios do copolímero F6T2, impossibilitando a preparação de WPLEDs empregando este dois componentes na mesma camada ativa. Como a preparação de WPLEDs foi comprometida usando blendas de PFP e F6T2, devido a eficiente recombinação de cargas nos domínios do F6T2, foi proposta uma metodologia empregando dois materiais poliméricos com propriedades de emissão de luz diferentes: um composto eletroluminescente, neste caso foi usado o PFP e outro composto fotoluminescentes (para isto foi escolhido o MDMO-PPV). Nesta metodologia foi construido um diodo EL baseado no polímero PFP (ITO/PEDOT/PSS:PFP/Ca/Al) que emitiu luz azul-esverdeada. Na face oposta deste dispositivo (onde há a saída de luz, substrato de quartzo/ITO) foi colocado um filme fino (depositado sobre um substrato de quartzo) do polímero MDMO-PPV. Este filme absorve na região da eletroemissão esverdeada do PFP, ou seja, a luz emitida pelo PFP e capaz de excitar as moléculas de MDMO-PPV, e ambos os componente emitem fazendo surgir uma emissão de luz branca. A cor branca foi confirmada pela coordenada de cromaticidade CIE (x = 0.35 e y = 0.31). / Abstract: In this work the photo and electroluminescent properties of the different conjugated polymers were investigated: poly[(9,9-dioctylfluorene-2,7-diyl)-alt-(9,9-di(pent-4-en-1-yl)fluorene-2,7-diyl)]) (PFP) blue emitter, poly [(9,9-dihexilfluoreno-2 ,7-diyl)-alt-co-(bithiophene)] (F6T2) green emitter and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] ( MDMO -PPV ) red emitter. Firstly, we prepared organic-inorganic hybrid materials based on silicones and PFP polymer. The presence of vinyl moieties in the side chain of PFP react with Si-H groups of the silicone by the hydrosilylation producing two types of silicones: with lower (PDHS-PDVS-l-PFP-X) and higher (PDHSS-PDVS-PFP-h-X) crosslinking degree. The photophysical properties of these hybrid materials were compared with PFP polymer in film form and in the solutions of THF and of the different polysiloxanes used in the hydrosilylation reaction. Based on the steady-state and dynamic photoluminescence data, PFP chains are disordered in solutions, in the film and in the silicones with a lower degree of crosslinking (PDHS-PDVS-l-PFP-X) independent of the amount of PFP used. Nevertheless, in the hybrids with a higher degree of crosslinking (PDHSS-PDVS-PFP-h-X) the crystalline a-phase of the polyfluorene was formed. Aggregates emitting in longer wavelengths are only formed when other crystalline phases are present in PDHSS-PDVS-h-PFP-X (X = 2 and 3) silicones. The driving force for this formation is probably a combination of p - p interaction between the planar backbone and the hydrophobic interactions of the lateral groups in the poor solvent in a more confined environment such as brittle PDHSS-PDVS-h-PFP. After detailed study of the photophysical properties of PFP both in solution and in the solid state, polymer blends based on this polymer and in the F6T2 copolymer were prepared. The photophysical investigations showed that there is an efficient energy transfer from the donor (PFP) to the acceptor (F6T2) in these blends (PFP/F6T2). The energy transfer occurs by non-radiative process (Förster-type mechanism) and radiative. Electroluminescent diodes were also studied using polymer blends of PFP/F6T2 as active layer (device configuration: ITO/PEDOT:PSS/polymer blend/Ca/Al) with the intention of produce white polymer light-emitting diodes (WPLEDs). In these diodes was also observed an efficient energy transfer from the PFP to F6T2, and the charge recombination was favored in the dominions of the F6T2 copolymer. The higher transfer energy from donor to acceptor in these diodes compromised the blue light and the withe light using this polymer in the same active layer do not produced. Thus, white-emitting electroluminescent diode was obtained with a single layer of an electro-active greenish component (PFP) and an external photoluminescent (PL) red-emitting material (MDMO-PPV), in a diode configuration of ITO/PEDOT-PPS/PFP/Ca/Al//MDMO-PPV. A thin film of this PL component was deposited onto a glass plate and mounted on the opposite face of a glass/ITO substrate. The MDMO-PPV polymer electronic absorption matches the greenish electroemission of the PFP. The white color, based on the CIE color coordinates (x = 0.35 e y = 0.31), was obtained by the red emission of the external MDMO-PPV film and the blue-greenish EL emission from the formed PFP diode. White emission was produced by adjusting the absorbance of the layer thickness and the blue-greenish component until it reached the CIE white coordinates. / Doutorado / Quimica Inorganica / Doutor em Quimica

Orientador: Mário Roberto Maróstica Júnior / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T19:40:33Z (GMT). No. of bitstreams: 1 Marques_AnneyCastro_D.pdf: 1629886 bytes, checksum: bb0b5aff44e4b4964882ed30eee5c23a (MD5) Previous issue date: 2013 / Resumo: As mudanças no estilo de vida da população, tais como as alterações no hábito alimentar e o maior sedentarismo, levam ao aumento da prevalência de doenças crônicas não transmissíveis, entre as quais se destaca a obesidade. Com o intuito de controlar esse grande problema de saúde pública, vários compostos bioativos têm sido investigados. O ácido linoleico conjugado (CLA), família de isômeros do ácido linoleico, apresenta diversas funções biológicas positivas, tais como anticarcinogênico, imunomodulador e regulador do balanço energético e da composição corporal. Apesar de sua potencialidade na redução do peso corporal, o CLA também apresenta efeitos biológicos adversos (resistência à insulina e aumento da oxidação lipídica), os quais limitam sua utilização. Os fitosterois, lipídios encontrados em alimentos de origem vegetal, reduzem os níveis de colesterol sérico, a inflamação e o risco de doenças cardiovasculares. Por se tratarem de substâncias com comprovado efeito biológico, é possível que a interação entre CLA e fitosterois melhore ou potencialize seus efeitos. Este trabalho teve como objetivo investigar a ação destes compostos na prevenção da obesidade induzida por dieta rica em gordura. Quarenta camundongos Swiss machos receberam dietas hiperlipídicas suplementadas com CLA e/ou fitosterois, na concentração de 2%, por nove semanas. Foram avaliados ingestão energética, ganho de peso, composição corporal, perfil lipídico sérico (colesterol total, HDL-colesterol, triglicérides e ácidos graxos livres), leptina sérica, testes de tolerância à glicose e à insulina, via da insulina no fígado e no tecido adiposo (proteínas Akt, FoxO e JAK-2), inflamação no fígado, tecido adiposo e hipotálamo (JNK, IL-1?, IL-6, IL-10 e TNF-?), além da modulação dos receptores ativados por proliferadores peroxissômicos (PPARs) ? e ? no fígado, tecido adiposo e hipotálamo. Os dados paramétricos foram submetidos à análise de variância (ANOVA) e os dados não paramétricos foram analisados pelo teste de Kruskal-Wallis. Quando aplicável (p < 0,05), foram realizados os respectivos testes post-hoc (Tukey ou Dunns). A suplementação concomitante de CLA e fitosterois não alterou a ingestão energética, mas reduziu significativamente o ganho de peso, e aumentou a concentração de massa magra e de minerais. Foram reduzidos os níveis de massa gorda, de leptina sérica e dos PPARs no fígado e no tecido adiposo dos animais. Neste grupo não se observou alteração no perfil lipídico. Apesar dos animais terem desenvolvido resistência à insulina, a utilização de CLA mais fitosterois apresentou efeito sinérgico, com redução da inflamação hepática e melhora na via insulínica no fígado e no tecido adiposo, em relação ao grupo obeso. A suplementação de CLA e fitosterois reduziu, em camundongos, os danos causados pela ingestão de dieta hiperlipídica, entretanto mais estudos são necessários para compreender os mecanismos de ação e definir as melhores doses / Abstract: The changes in the population lifestyle, such as bad eating habits and more sedentarism, led to increased prevalence of chronic diseases, including obesity. Various compounds have been investigated in order to control this major public health problem. Conjugated linoleic acid (CLA), a family of isomers of linoleic acid, has various positive biological functions, such as anticarcinogenic, immunomodulatory and energy balance and body composition regulations. Despite the potential in reducing body weight, CLA also has adverse biological effects (insulin resistance and increased fat oxidation), which limit it use. Phytosterols, lipids found in vegetable foods, reduce serum cholesterol levels, inflammation and cardiovascular disease risk. CLA and phytosterols are related to substances with proven biological effect. It is possible that the interaction between then improves and/or enhance these effects. This study aimed to investigate the action of these compounds in the prevention of obesity induced by high-fat diet. Forty male Swiss mice received a high-fat diet supplemented with CLA and/or phytosterols, at a concentration of 2%, for nine weeks. Energy intake, weight gain, body composition, serum lipid profile (total cholesterol, HDLcholesterol, triglycerides and free fatty acids), serum leptin, glucose and insulin tolerance tests, insulin pathway in liver and adipose tissue (Akt, FoxO and JAK-2 proteins), inflammation in liver, adipose tissue and hypothalamus (JNK, IL-1?, IL-6, IL-10 and TNF-?), and modulation of peroxisomal proliferator activated receptors (PPARs) ? and ? in liver, adipose tissue and hypothalamus were assessed. Parametric data were subjected to analysis of variance (ANOVA) and nonparametric data were analyzed by Kruskal-Wallis test. When applicable (p <0.05) were performed its post-hoc tests (Tukey or Dunns). Concomitant supplementation of phytosterols and CLA did not alter energy intake, but significantly reduced weight gain, and increased lean mass and minerals concentration. Fat mass, serum leptin and PPARs, in liver and adipose tissue, were reduced in the animals. In CLA plus phytosterols group there was no change in lipid profile. Although the animals have developed insulin resistance, the use of CLA plus phytosterols showed a synergistic effect, with reduction in hepatic inflammation and improvement in the insulin pathway in liver and adipose tissue, compared to the obese group. CLA and phytosterols supplementation reduced, in mice, the damage caused by the intake of high-fat diet, however, more studies are needed to understand the mechanisms of action and define the best doses / Doutorado / Nutrição Experimental e Aplicada à Tecnologia de Alimentos / Doutora em Alimentos e Nutrição

Made available in DSpace on 2014-08-20T14:38:45Z (GMT). No. of bitstreams: 1 Tese_Julcemar_Kessler.pdf: 2191437 bytes, checksum: 7c7e8ea41a4fa00311d93dacf76e9cfa (MD5) Previous issue date: 2012-05-21 / The study aimed to evaluate the effect of age at slaughter on chemical composition, cholesterol and fatty acid profile of meat goats from region Alto Camaquã . A total of 30 goats, 15 were aged 8-9 months and 15 with 11-12 months of age. Of each goat were evaluated Longissimus dorsi (LD), Triceps brachii (TB), Infraspinatus (IS) and Biceps femoris (BF) to determine the proximate composition (moisture, protein, ash and lipids), cholesterol and fatty acids profile acids. The experimental design was completely randomized with a factorial 2 x 3 (ages two and three regions). There was significant interaction between age and the region of slaughter (muscle) studied. Goats slaughtered younger have higher concentrations of moisture and mineral matter on the back, shoulder and leg (P <0.05) compared to older animals. Since fat content were higher in goats slaughtered older (P <0.05). For cholesterol, only the leg of goats slaughtered younger levels were lower than other regions (P <0.05). There was no difference in the total cholesterol to goats slaughtered older (P> 0.05) in different regions of the carcass. Goats slaughtered older (11-12 months) had higher levels of C12:0, C14:0, C15:0, C16:0 and C18:0 (P <0.05) in muscle (LD). As for the muscles (TB) and (IS) there was no difference in C15:0 and C16:0. The same was observed for the muscle (BF) (P> 0.05). For the fatty acid C18:1 trans-9 and C18:1 trans-11, the goats slaughtered older had higher concentrations (P <0.05) in LD and BF muscles. While the muscles TB and IS only statistical difference (P <0.05) for C18: 1 trans-9, higher in older animals slaughtered. Regarding the content of polyunsaturated acids C18:2, C18:3, C20:3, C20:4, C20:5, C22:5 and C22:6 were higher in young kids (P <0.05) in the muscle LD. While TB and IS the C20:4 and C20:5 were higher in older kids. BF in the C18: 2 cis9, trans-11 (CLA) was higher in older kids (P <0.05), other muscles in this fatty acid did not differ (P> 0.05). With the progress of the slaughter of goats rises the amount of protein and fat, but cholesterol does not change. The regions of the substrate showed different chemical composition. There is direct relationship between age at slaughter increased with fat saturation and concentration of conjugated linoleic acid. The goat meat is a source of fat omega 3 and 6, showing a relationship beneficial to health. / O trabalho teve como objetivo avaliar o efeito da idade de abate sobre a composição química, colesterol e perfil de ácidos graxos da carne de cabritos criados na região do Alto Camaquã. Foram utilizados 30 cabritos, sendo 15 com idade de 8 9 meses e 15 com 11 12 meses de idade. De cada cabrito foram avaliados os músculos Longissimus dorsi (LD), Triceps brachii (TB), Infraspinatus (IS) e Biceps femoris (BF) para determinação da composição centesimal (umidade, proteína, matéria mineral e lipídios), colesterol e perfil de ácidos graxos. O delineamento utilizado foi o inteiramente casualizado, com arranjo fatorial 2 x 3 (duas idades e três regiões). Houve interação significativa entre a idade de abate e a região (músculo) estudada. Cabritos abatidos mais jovens apresentam maior concentração de umidade e matéria mineral no lombo, paleta e perna (P<0,05) em relação aos animais mais velhos. Já os teores de gordura foram superiores nos cabritos abatidos mais velhos (P<0,05). Para o colesterol, somente na perna de cabritos abatidos mais jovens os teores foram inferiores as demais regiões (P<0,05). Não houve diferença em relação ao colesterol total para cabritos abatidos mais velhos (P>0,05) nas diferentes regiões da carcaça. Cabritos abatidos mais velhos (11 12 meses) apresentam maiores teores de C12:0, C14:0, C15:0, C16:0 e C18:0 (P<0,05) no músculo (LD). Enquanto, para os músculos (TB) e (IS) não houve diferença para C15:0 e C16:0. O mesmo foi observado para o musculo (BF) (P>0,05). Para os ácidos graxos C18:1 trans-9 e C18:1 trans-11, os cabritos abatidos mais velhos apresentaram maiores concentrações (P<0,05) nos músculos LD e BF. Enquanto nos músculos TB e IS somente houve diferença estatística (P<0,05) para C18:1 trans-9, superior nos animais abatidos mais velhos. Em relação aos ácidos poliinsaturados os teores de C18:2, C18:3, C20:3, C20:4, C20:5, C22:5 e C22:6 foram superiores nos cabritos mais jovens (P<0,05) no músculo LD. Enquanto para TB e IS o C20:4 e C20:5 foram superiores nos cabritos mais velhos. No BF o C18:2 cis9, trans11 (CLA) foi superior nos cabritos mais velhos (P<0,05), nos demais músculos este ácido graxo não diferiu (P>0,05). Com o avanço da idade de abate dos cabritos eleva-se o teor de proteína e de gordura, porém o colesterol não se modifica. As regiões da carcaça apresentaram distinta composição química. Há relação direta entre a idade de abate com o aumento na saturação da gordura e concentração do ácido linoleico conjugado. A carne de cabrito é fonte de gordura ômega 3 e 6, apresentando uma relação benéfica a saúde.

Made available in DSpace on 2014-08-20T14:38:50Z (GMT). No. of bitstreams: 1 Tese_Marcele_Sousa_Vilanova.pdf: 948050 bytes, checksum: 7a7d6aa129c7207e116bace94c372823 (MD5) Previous issue date: 2011-02-21 / We tested the effect of two levels of ether extract based on rice oil concentrate, 30 Saanen goats during early lactation. The feeding was based on the ratio of 60% forage (alfalfa hay), and 40% commercial concentrate with two levels of lipids (3% and 5%). The variables were: average milk production, behavior of the lactation curve, milk chemical composition and total time of lactation against the profile of saturated, monounsaturated and polyunsaturated. The increase in the percentage of ether extract oil-based rice did not affect milk production, which presented as mean ± 2658 379 mL milk / goat / day, between 11 weeks and the chemical composition of milk, which characterized by having 3.78 ± 0.59% fat, 3.10 ± 0.18% crude protein, 4.46 ± 0.20% lactose and 12.19 ± 0.72% of total solids. However significant (P <0.05) fatty acid profile of milk, reducing the concentrations of saturated fatty acids, palmitic acid C16: 0, myristic C14: 0, capric C10: 0 and lauric C12: 0, which were higher in 3% treatment (26.87, 8.60, 5.90 and 3.06% respectively) and increasing concentrations of unsaturated C16: 1, C17: 1 and C20: 1 (0.43, 0.12 and 0.10%, respectively). The inclusion of rice bran oil at levels of 3% and 5% of dry matter in the diet of goats does not affect milk production and the chemical composition until the 11th week of lactation, however, is able to alter the fatty acid profile of significantly. / Testou-se o efeito de dois níveis de extrato etéreo a base de óleo de arroz no concentrado de 30 cabras Saanen durante a fase inicial de lactação. A alimentação baseou-se na relação 60% de volumoso (feno de alfafa), e 40% de concentrado comercial com dois níveis de extrato etéreo (3% e 5%). As variáveis estudadas foram: Produção, composição química, perfil de ácidos graxos saturados, mono e polinsaturados no leite. O aumento no percentual de extrato etéreo na ração não influenciou a produção de leite, que apresentou como média 2658±379 mL de leite/cabra/dia, no período de 11 semanas e nem a composição química do leite, que se caracterizou por ter 3,78 de gordura; 3,10 de proteína bruta; 4,46 de lactose e 12,19 de sólidos totais. O perfil de ácidos graxos do leite foi influenciado pelo acréscimo de extrato etéreo na ração. No tratamento de maior proporção houve um aumento das concentrações de ácidos graxos insaturados C18:1n 9c (Oléico) e C18:3n3, (25,79 e 0,80%, respectivamente) e no Ácido Linoléico Conjugada (CLA) que aumentou de 0,37 para 0,72% com o acréscimo de óleo; e uma redução dos ácidos graxos saturados: palmítico C16:0, mirístico C14:0, cáprico C10:0 e láurico C12:0, que foram maiores no tratamento 3% (26,87; 8,60; 5,90 e 3,06%, respectivamente).

The present thesis is focused on the rational design of Diketopyrrolopyrrole based π- conjugated polymers for organic electronics. The thesis is organized into six different chapters and a brief description of the individual chapters is provided below. Chapter 1 briefly describes the physics governing the electronic processes occurring in organic photovoltaics (OPVs) and organic field-effect transistors (OFETs) followed by design rules for the synthesis of conjugated polymers for organic electronics. Diketopyrrolopyrrole (DPP) based π-conjugated materials and their development in OPVs and OFETs have been highlighted. Chapter 2 discusses the synthesis and characterization of a series of small molecules of DPP derivatives attached with different alkyl chains. Influence of side chains on the photophysical properties of these DPP derivatives have been studied by UV-visible spectroscopy and DFT calculations. Crystal structure studies revealed the effect of alkyl chains on the torsional angle, crystal packing, and intermolecular interactions such as π-π stacking. Chapter 3 reports the synthesis of novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPPDPP) based conjugated copolymers and their application in high mobility organic field-effect transistors. Effect of insulating alkyl chains on polymer thin film morphology, lamellar packing and π-π stacking interactions have been studied in detail. Investigation of OFET performance of these DPP-DPP copolymers with branched alkyl chains (N-CS2DPP-ODEH) resulted in low charge carrier mobilities as compared to the polymers (N-CS2DPP-ODHE) with linear alkyl chains. Polymer with triethylene glycol side chains (N-CS2DPP-ODTEG) exhibited a high field-effect electron mobility value of ~3 cm2V-1s-1 with a very low threshold voltage of ~2 V. Chapter 4 investigates the effect of torsional angle on the intermolecular interactions and charge transport properties of diketopyrrolopyrrole (DPP) based polymers (PPDPP-OD-HE and PPDPP-OD-TEG). Grazing incidence x-ray diffraction studies shows the different orientation of the polymer crystallites and lamellar packing involved in polymer thin films. Investigation of OFETs evidenced the effect of torsional angle on the charge transport properties where the polymer with higher torsional angle PPDPP-OD-TEG resulted in high threshold voltage with less charge carrier mobility compared to the polymer with lower torsional angle (N-CS2DPP-OD-TEG). Chapter 5 investigates the effect of photoactive material morphology on the solar cell device performance, and charge transfer kinetics by adding high boiling point processing additives. DPP based donor-acceptor (D-A) type low band gap polymers (PTDPPQ and PPDPPQ) have been synthesized and employed in bulk-heterojunction (BHJ) solar cells with the acceptor PC71BM. Addition of processing additive 1,8-diiodooctane (DIO) resulted in three order improvements in power conversion efficiency (PCE). Chapter 6 describes the design and synthesis of two diketopyrrolopyrrole based copolymers (PPDPP-BBT and PTDPP-BBT) for their application in organic devices such as field-effect transistors and bulk-heterojunction solar cells. Investigation of OFET performance of these DPP based copolymers displayed hole mobilities in the order of 10-3 cm2V-1s-1. The semiconductor-dielectric interface has been characterized by capacitance-voltage, and Raman scattering methods. In summary, the work presented in this thesis describes the synthesis and characterization of diketopyrrolopyrrole based new polymeric semiconductors. Effects of insulating side chains and torsional angle on the charge transport properties of these polymers in OFETs have been investigated. This work also describes the effect of solvent additives on the active layer morphology and BHJ solar cell device performance. The results described here show that these materials have potential application as active components in plastic electronics.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15364号 / 工博第3243号 / 新制||工||1488(附属図書館) / 27842 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 藤井 滋穂, 教授 米田 稔 / 学位規則第4条第1項該当

Cette thèse présente la conception, la synthèse et l'étude photophysique de divers dérivés d'azophénine comme modèles structurels mono-bloc pour l'éméraledine qui est une forme de polyaniline à valence mixte. L'azophénine est une molécule conjuguée en forme d'étoile contenant à la fois des résidus de quinone diimine et de phénylamine tous deux contenus dans l'émeraldine. Cependant l'azophénine et l'émeraldine sont tout deux reconnus pour ne pas être émissifs. Le défi était alors de donner des propriétés d’émissions à l'azophénine à température ambiante avant toute investigation photophysique. L'objectif à long terme étant de rendre la polyaniline, connu pour être peu dispendieuse, attractive en tant que matériau donneur efficace dans une cellule solaire de type « bulk-heterojunction ». En raison des problèmes de faible solubilité des polymères, l'utilisation de modèles beaucoup plus soluble est une nécessité. Les modifications structurelles considérées comprennent l'ancrage des fonctions pontées d'éthynyle en position para- des quatre groupes phényls d'azophénine. Ces fonctions sont des groupes aromatiques encombrés de type truxène, des composés organométalliques trans-bis(trialkylphosphine) platine(II), des colorants de porphyrines de zinc(II) et de Bodipy. Elles présentent toutes une fluorescence ou une phosphorescence, signal pouvant être utilisé pour mesurer les interactions électroniques entre ces groupements et le noyau central. Leurs propriétés photophysiques sont étudiées en détail en utilisant la spectroscopie d'absorption et d'émission UV-Visible stationnaire et ultra-rapide résolue dans le temps. La DFT et la TDDFT sont également utilisés pour les optimisations des géométries (DFT) et pour déterminer la nature et les positions de l'absorption de la bande de transfert de charge (TDDFT). Le chapitre 2 présente la synthèse et la caractérisation d'un dérivé en étoile d'azophénine autour d’un noyeau truxène appelé TertTruQ. Le couplage de résidus encombrés de truxène avec de l'azophénine a amélioré l'activité photophysique du premier niveau singulet de ce dérivé à 77 K. Les hypothèses étant que le taux de désactivation non radiatif a diminué les rotations autour des axes des liaisons C-N en raison de la taille du truxène. De plus, cette nouvelle azophénine substituée s'est révélée être fluorescente à l'état solide à température ambiante. En raison de ces nouvelles observations, les propriétés d'émission des dérivés de l’éméraldine sont réexaminées. Une fluorescence faible à ~ 780 nm à 77 K, confirmée par le spectre d'excitation, a démontré la présence d'une faible émission de type fluorescence CT dans le proche-IR pour TertTruQ. Nous pouvons en conclure que l'azophénine fournit un modèle utile pour identifier quelle modification structurelle simple peut être effectuée pour rendre l’éméraldine émissive, si possible à température ambiante. De plus, lorsqu'une espèce non luminescente devient émissive, ce changement s'accompagne d'une augmentation de sa durée de vie à l’état excitée, propriétés recherchées pour des applications dans le domaine des cellules solaires. Ce travail a été publié dans Physical Chemistry Chemical Physics, 2017, 19, 21532-21539. Le chapitre 3 décrit la synthèse et la caractérisation des azophénines contenant du trans-bis(trialkylphosphine)diéthynyl-platine(II) formant les dérivés di- et tétra-substitués DiTruPtQ et TertTruPtQ. Les deux complexes présentent une fluorescence et une phosphorescence des "bras" organométalliques à 298 K en solution. En outre, l'effet d'atome lourd du platine permet d'explorer les propriétés de l’état triplet de l'azophénine. Cependant, la phosphorescence recherchée de l'état triplet CT n'a pas été considérée probablement en raison des processus rapides non radiatifs. Ce travail a été publié dans Organometallics, 2017, 36(3), 572-581. Le chapitre 4 présente l'effet du remplacement des ions H+ labiles sur le fragment HN^N par des fragments BF2+ pour former des cycles, fournissant ainsi un cadre plus rigide pour l'azophénine. En effet, la fluorescence CT proche-IR a été observée à 298 et 77 K. Cependant, malgré la présence de Pt dans les groupes pendants, aucune phosphorescence n'a été détectée. Les calculs de DFT ont suggéré que l'état triplet de plus faible énergie était très faible (0,975 eV (BQ) et 0,84 eV (TertPtBQ)) induisant une plus grande probabilité de processus non radiatifs, depeuplant ainsi efficacement l'état triplet. Ce travail a été accepté à Inorganic Chemistry, 2017. Le chapitre 5 présente les colorants fluorescents de porphyrine de zinc(II) et BODIPY bien connus, qui ont été liés à l'azophénine pour former DiBodipyQ, TertBodipyQ et PorBodipyQ. Le spectre d'absorption des BODIPY se situe dans une gamme où la porphyrine n'absorbe pas beaucoup. Ainsi, la combinaison de ces deux chromophores avec la formation d'une bande de CT faible permet d'améliorer la collecte du rayonnement solaire. Par conséquent, il était important de vérifier que l'énergie collectée pourrait facilement être transférée d'un chromophore à l'autre. En effet, on a observé 1BODIPY * → 1porphyrine zinc(II) et 1BODIPY * → 1CT (azophénine) avec une désactivation efficace de 1porphyrine zinc(II) ~~> 1CT (azophénine). Ce travail a été soumis à Chemistry: A European Journal. / Abstract: This thesis presents the design, synthesis and photophysical investigation of various azophenine derivatives as “one unit” structural models for emeraldine, a mixed-valence form of polyaniline. Azophenine is a star-shaped cross-conjugated molecule containing both quinone diimine and phenyl amine residues included in emeraldine but both, azophenine and emeraldine, are reported notoriously non-emissive. The challenge was to render azophenine emissive at room temperature prior any photophysical investigation. The long-term objective is to render polyaniline, in one form or the other, useful in bulk heterojunction solar cell in the active layer as it is not expensive. Because of solubility issues, the use of models becomes very appealing. The considered structural modifications include the anchoring of ethynyl-bridged functions at the para-position of the four phenyl groups of azophenine. These functions are the bulky truxene aromatic, the organometallic trans-bis(trialkylphosphine)platinum(II) pendent groups, and zinc(II)porphyrin and BODIPY dyes. All these functions exhibit fluorescence or phosphorescence, signal that can be used to monitor any electronic interaction between these pendent groups and the central core. Their photophysical properties were investigated in detail using steady-state and ultrafast time-resolved UV-vis absorption and emission spectroscopy. DFT and TDDFT were also employed for geometry optimizations (DFT) and nature and positions of the CT absorption (TDDFT). Chapter 2 introduces the synthesis and characterization of a truxene-based star-shaped azophenine derivative called TertTruQ. The coupling of bulky truxene residues with azophenine improved the photophysical activity of the lowest energy singlet excited state (i.e. CT state) of this derivative at 77 K. Speculations are that the rate for non-radiative deactivation, namely internal conversion, decreased upon slowing down the rotations around the N-C bonds due to the size of truxene. Moreover, this new substituted azophenine turned out to be fluorescent in the solid state at room temperature. Because of these interesting new observations, the emission properties of emeraldine base form were re-examined. A weak fluorescence at ~780 nm at 77 K, confirmed by the excitation spectrum, demonstrated the presence a CT near-IR fluorescence for TertTruQ. Thus, azophenine provides a useful model to identify what simple structural modification that can be performed to render emeraline emissive, if possible at room temperature. Again, when a non-luminescent species becomes emissive, this change is accompanied by an increase of its excited state lifetime. Longer excited state lifetimes are more prone to solar cell applications. This work has been published in Physical Chemistry Chemical Physics, 2017. Chapter 3 describes the synthesis and characterization of trans-bis(trialkylphosphine)diethynyl-platinum(II)-containing azophenines forming the di- and tetra-substituted derivatives DiTruPtQ and TertTruPtQ. Both complexes exhibit fluorescence and phosphorescence of the organometallic “arms” at 298 K in fluid solution. Moreover, the heavy atom effect of platinum gave the possibility of exploring the triplet state properties of azophenine. However, the sought phosphorescence from the triplet CT state was not seen most presumably due to the fast non-radiative processes. This work has been published in Organometallics, 2017, 36(3), 572-581. Chapter 4 presents the effect of the replacement of the labile H+ ions on the HN^N moiety by BF2+ fragments to form cycles thus providing a more rigid framework for azophenine. Indeed, the CT near-IR fluorescence was observed both at 298 and 77 K. However, despite the presence of Pt in the pendent groups, no phosphorescence was detected. DFT computations suggested that the low-lying triplet state was very low (0.975 (BQ) and 0.84 eV) inducing a higher probability of non-radiative processes thus efficiently depleting the triplet state. This work has been submitted to Inorganice Chemistry. Chapter 5 introduces the well-known BODIPY and zinc(II)porphyrin fluorescent dyes, which were linked to azophenine to form DiBodipyQ, TertBodipyQ and PorBodipyQ. The absorption spectrum of Bodipy lies in a range where porphyrin does not absorb very much. So, the combination of these two chromophores along with the formation of a low-lying CT band improves the light collection of the solar radiation. Consequently, it was important to verify that the collected energy could easily transferred from one chromophore to another. Indeed, the 1Bodipy* → 1zinc(II)porphyrin and 1Bodipy* → 1CT(azophenine) were observed along with an efficient deactivation from 1zinc(II)porphyrin ~~> 1CT(azophenine).

Le développement du photovoltaïque organique(OPV), passe à la fois par des progrès technologiques et par l’élaboration de nouveaux matériaux photoactifs. Au sein des dispositifs se trouvent en général deux types de semi-conducteurs organiques, l’un accepteur d’électrons,l’autre donneur.Au cours de ce travail, différentes stratégies de rigidification par pontage covalent ont été appliquées à trois familles de donneurs moléculaires afin d’en étudier l’impact sur leurs propriétés électroniques. Dans un premier temps, deux séries de dérivés pontés du quaterthiophène substitué en positions terminales par des groupements dicyanovinyles ont été synthétisées. La présence d’un pont méthylène au niveau du bithiophène central induit un décalage du spectre d’absorption vers les faibles énergies en élevant le niveau HOMO de la molécule. Leur potentiel comme matériaux donneurs a, par la suite, été évalué au sein de dispositifs solaires. Ainsi, selon la longueur des chaînes alkyles introduites sur le pont, des rendements de photoconversion de 2% à 3,4% sont atteints en cellules bicouches. Puis, dans un second temps, l’utilisation de l’hétérocycle rigide thiéno[2,3-b]indole a permis de concevoir la plus petite molécule push-pull à atteindre 1%d’efficacité. Un rendement de 3,1% est obtenu lorsque le système conjugué est étendu d’une unité thiophène. Enfin, un donneur moléculaire construit autour d’un dithién-2-yldicyanoéthylène ponté, fonctionnalisé en périphérie par des unités triphénylamine, conduit à des cellules moins performantes (0,3%) que son homologue non ponté (1,1%). / The development of the so-called organic photovoltaics (OPVs) still requires technological as well as chemical advances through the elaboration of new photoactive materials. Active layer of devices is typically composed of two organic semiconductors, one electron-acceptor and one electron-donor respectively. During this work, rigidification by covalent bridging was applied to three different kinds of molecular donors to assess its impact on the materials electronic properties. First, two series of covalently bridged dicyanovinyl(DCV) end-capped quaterthiophene derivatives have been synthesized. A methylene bridge on the central bithiophene unit leads to a significant bathochromic shift of the absorption spectrum associated with a raising of the HOMO level. Their potential as donor material has been evaluated in solar cells. Power conversion efficiencies ranging from 2% to 3.4% can be achieved in bilayers structures according to the length of the alkyl chains introduced on the bridged bithiophene moiety. Then, the use of a rigid thieno[2,3-b]indoleheterocycle allowed us to design, synthesize and characterize the smallest push-pull molecule able to reach 1% efficiency. It is worth noting that extending the conjugation length of this molecule by adding one thiophene unit leads to an increase of the efficiency up to 3.1%. Finally, a molecular donor built from a bridged dithienyldicyanoethylene core functionalized at both sides by a triphenylamine unit was studied and led to less efficient OPV cells (0.3%) than its unbridged counterpart (1.1%).