Submitted by Evandro Jardim dos Santos (evandro.jardim@hotmail.com) on 2017-06-14T14:14:59Z No. of bitstreams: 1 EvandroSantos_PGAD_TUPA_02_2017.pdf: 1763486 bytes, checksum: f4acab8ef7858bcc1607f79f3029e5be (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-06-19T13:48:44Z (GMT) No. of bitstreams: 1 santos_ej_me_tupa.pdf: 1763486 bytes, checksum: f4acab8ef7858bcc1607f79f3029e5be (MD5) / Made available in DSpace on 2017-06-19T13:48:44Z (GMT). No. of bitstreams: 1 santos_ej_me_tupa.pdf: 1763486 bytes, checksum: f4acab8ef7858bcc1607f79f3029e5be (MD5) Previous issue date: 2017-02-16 / O urucum é considerado um dos mais importantes corantes naturais, atuando não só como colorífico, mas também agregando propriedades nutricionais aos produtos que o utilizam. Apesar da importância, poucos estudos são desenvolvidos acerca da sua cadeia produtiva. Visando a preencher essa lacuna, este trabalho teve o objetivo de compreender a estrutura e o funcionamento do Sistema Agroindustrial (SAG) do urucum na Microrregião de Dracena, no estado de São Paulo. A seleção desse SAG, nessa região, deveu-se pela falta de trabalhos científicos acerca desse produto, nessa abordagem, e pela sua representatividade geográfica na produção nacional e estadual. Para a realização desse trabalho, foi utilizado um estudo exploratório de caráter qualitativo. A metodologia envolveu uma pesquisa bibliográfica e uma pesquisa de campo. Esta última contou com a realização de entrevistas junto aos agentes chaves do SAG do urucum na região estudada. Em um contexto socioeconômico, identificouse que o cultivo do urucum é uma alternativa de produção agrícola para a região estudada. Trata-se de uma atividade característica da pequena produção e adotada, em sua maioria, por produtores caracterizados pela agricultura familiar. Os resultados mostraram alguns desafios associados ao SAG do urucum, tais como: a falta de produtos defensivos aprovados para o urucum, a incipiência no desenvolvimento de máquinas e implementos específicos para a cultura, a escassez de mão de obra para o manejo e a colheita, bem como a preocupação com a continuidade da atividade agrícola das próximas gerações dos produtores rurais. A baixa organização e cooperação entre os produtores rurais para a comercialização do urucum reduz o poder de barganha e enfraquece o setor de produção de matéria-prima. Foram identificadas e analisadas três tipos de transações que envolvem o relacionamento entre fornecedores e compradores de urucum. Tais transações relacionam-se, respectivamente, a dois tipos de estrutura de governança: o mercado spot e a estrutura híbrida. Observou-se que as estruturas não promovem a coordenação entre os agentes, o que leva a custos de transação e menor eficiência. Conclui-se que, embora o mercado de corantes naturais e, especificamente, o do urucum seja crescente e promissor, o SAG ainda carece de melhorias na sua organização e coordenação. / Annatto is considered one of the most important natural dyes, acting not only as colorific, but also adding nutritional properties to the products that use it. Although it is an important crop, few studies are developed regarding the chain organization. In order to fulfill this gap, this work aimed at understanding the structure and functioning of the Agroindustrial System (SAG) of annatto in the Microregion of Dracena, in the state of Sao Paulo. The selection of this SAG in this particular region was due to the lack of academic work regarding this product under supply chain approach and due to its geographical representativeness in national and state production. For the accomplishment of this work, an exploratory study of qualitative character was used. The methodology involved a bibliographical research and a field research. This last one counted on the accomplishment of interviews with the key agents of the SAG of annatto in the studied region. In a socioeconomic context, it was identified that the cultivation of annatto is an alternative of agricultural production for the region studied. This activity is characteristic of small-scale production and it is mostly cultivated by family farmers. The results reveled some challenges associated with SAG of annatto, such as: the lack of approved agrochemical products for annatto cultivation; the incipience in the development of specific machines and implements for the culture; the scarcity of hand labor for handling and harvesting; and the concern with the continuity of the agricultural activity by the next generations of the rural farmers. The low organization and cooperation among farmers for the commercializing annatto reduces bargaining power and weakens the production sector. When analyzing the relations between farmers and its dealers three types of transactions involving the relationship between buyers and buyers of annatto have been identified and analyzed. These transactions were of two types of governance structure: the spot market and the hybrid structure. It was observed that the structures have not been able to promote coordination between agents, which have led to transaction costs and lower efficiency. It is concluded that, although the market for natural dye, and specifically for annatto, is growing and promising, the SAG still needs to improve its organization and coordination.

A cor dos alimentos é um dos principais fatores que influenciam na preferência dos consumidores. Os corantes naturais além da coloração podem oferecer benefícios à saúde humana. A norbixina é um carotenoide que pode ser produzido a partir da saponificação de bixina presente nas sementes de urucum. Tal composto apresenta propriedades funcionais que estão relacionadas a promoção de uma vida saudável, pois atua como protetor celular, é comumente usado como corante natural em produtos processados, entretanto, sua estrutura química torna-o susceptível à degradação por fatores ambientais como oxigênio, luz e alta temperatura. A microencapsulação é uma alternativa para melhorar a estabilidade e solubilidade deste carotenoide. Neste trabalho foram encapsulados cristais de norbixina com 100% de pureza (comprimento de onda de 453 nm) usando a técnica de secagem por atomização (spray drying). Foram utilizados goma arábica (GA) e maltodextrina (MD) em diferentes proporções como materiais de parede. As diferentes formulações (MD:GA 100:0; 85:15; 65:35; 50:50; 35:65; 15:85; 0:100) foram preparadas com a mesma quantidade de núcleo (norbixina) e percentual de sólidos solúveis totais. A formulação com 100% GA mostrou a maior eficiência de microencapsulamento (74,91% - 226,40 μg/g) e foi avaliada a sua atividade antioxidante da pelo método ABTS (77,77 ± 0,59 μmol TE/g microcápsula), verificou-se que a norbixina mantem a sua atividade antioxidante depois do processo de microencapsulamento O estudo de estabilidade das microcápsulas de norbixina (MCN) foi conduzido em sistema modelo aquoso a temperaturas de 60, 90 e 98°C por 300 min. A cinética de degradação seguiu uma reação de primeira-ordem. A energia de ativação (Ea) requerida para degradação foi de 15,08 kcal/mol, o dobro da Ea requerida para a norbixina livre. As MCN mostraram uma alta estabilidade térmica. Finalmente, as MCN foram aplicadas em bebidas isotônicas sabor tangerina. Utilizando os parâmetros de cor do sistema CIELab foi possível obter a coloração laranja com uma baixa concentração de norbixina (2,86 ± 0,02 μg norbixina/mL). A bebida isotônica (BIT) adicionada de MCN mostrou estabilidade sob condições aceleradas de armazenamento (luz e aquecimento), pois os resultados indicaram um maior tempo de vida média (29,71 dias) em comparação com a BIT adicionada de norbixina não encapsulada (6,56 horas). De acordo com essa pesquisa, os dados obtidos indicaram a potencialidade da utilização da microencapsulação para aumentar a estabilidade da norbixina e assim obter um corante natural com efetiva aplicação em matrizes modelo aquoso (bebidas). / Color is one of the main attributes in processed food that influences their preference and acceptance directly from consumers. Besides, of their ability of coloration, the natural dyes can offer benefits in human health. The norbixin is a carotenoid that can be produced from saponification of bixin present in annatto seeds. This compound shows functional properties that are related to the promotion of a healthy life, since it acts as cellular protectors, and is commonly used as a natural dye in processed food, however, its chemical structure makes it susceptible to degradation by environmental factors such as light, oxygen, and high temperature. Microencapsulation is used to improve the stability and solubility of the carotenoid. In this study, were encapsulated crystals of norbixin with 100% of purity (wavelength of 453 nm) by spray drying. Gum arabic and maltodextrin were used in different proportions as wall materials. The different formulations (MD:GA 100:0; 85:15; 65:35; 50:50; 35:65; 15:85; 0:100) were prepared with the same quantity of core (norbixin) and total solids soluble percentage. The formulation with 100% of arabic gum shows a high microencapsulation efficiency (74.91% - 226.40 μg/g of microcapsules) and was evaluated it antioxidant activity with ABTS assay (77.77 ± 0.59 μmol TE/g microcapsules), was verified that norbixin keep its antioxidant activity after microencapsulation process The stability study of norbixin microcapsules (MCN) was carried out in aqueous model system at temperatures of 60, 90 and 98°C for 300 min. Thermal degradation kinetics in aqueous model systems followed a first order kinetic reaction. The activation energy (Ea) required for degradation was Ea = 15.08 kcal/mol, double than required for free norbixin. MCN showed a high thermal stability with longer shelf life. Finally, the MCN were applied in isotonic tangerine soft drinks without exceeding the use of food additives regulations. Based on the parameter of CIELab system was possible to get an orange tonality by using a lower concentration of norbixin (2.86 ± 0.02 μg norbixin/mL). The isotonic beverage (BIT) added of MCN shows a stability during storage on accelerated conditions (heat and light) since the results indicated a high half-life time (29.71 days) when was compared with an BIT added of norbixin non-encapsulated (6.56 hours). According to this research, the results obtained showed the potential of the use of microencapsulation to increase the stability of norbixin, thus obtaining a natural dye with an effective application in aqueous matrix, mainly in beverages.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / Este trabalho apresenta um estudo e caracterizaÃÃo de corantes com flores de plantas coletadas na regiÃo Nordeste do Brasil, tais como: a Sida cordifolia (malva branca), a Catharanthus roseus (boa noite) e a Torenia fournieri (amor-perfeito-de-verÃo), Allamanda catÃrtica (alamanda da flor grande) e Cobaea scandens (sino de catedral). Foi estudado e observado a influÃncia dos flavonoides na sensibilizaÃÃo dos corantes naturais por meio de um protÃtipo de cÃlula fotovoltaica, com vidros condutores com um filme de SnO2:F produzidos por spray PirÃlise. As plantas foram submetidas a um tratamento de lavagem. Foram maceradas e imersas em um solvente extrator. ApÃs alguns dias, foram concentradas no rotaevaporador a uma velocidade 160 rpm em temperatura ambiente por 40 minutos. Este corante foi aplicado sobre uma camada de TiO2 e entÃo a cÃlula foi testada sob a luz solar. Os valores obtidos foram: Torenia fournieri, corrente de curto-circuito = 0,44 mA e tensÃo de circuito aberto = 0,16 V; Catharanthus roseus, corrente de curto-circuito = 0,43 mA e tensÃo de circuito aberto = 0,14 V; Sida cordifolia, corrente de curto-circuito = 0,22 mA e tensÃo de circuito aberto = 0,19 V; Allamanda catÃrtica, corrente de curto-circuito = 0,19 mA e tensÃo de circuito aberto = 0,12V; Cobaea scandens, corrente de curto-circuito = 0,32 mA e tensÃo de circuito aberto = 0,17V. Estes resultados podem fornecer mais dados para melhor entendimento e uso de novos corantes naturais em cÃlulas solares. / This paper presents a study and characterization of dyes with flowers of plants collected in the Northeast of Brazil, such as Sida cordifolia (malva branca), the Catharanthus roseus (boa noite), Torenia fournieri (amor-perfeito-de-verÃo), Alamanda cathartic (alamanda da flor grande) and Cobaea scandens (sino de catedral). Was studied and observed the influence of flavonoids in the sensitization of natural dyes by means of a prototype solar cell with conductive film with a glass of SnO2: F produced by spray pyrolysis. The conductive glass was obtained precursor solution (HCl/H2O) containing of tin II chloride dihydrate (SnCl2.2H2O), ammonium fluoride (NH4F) and a slide glass heated to 600 Â C. The solution was sprayed on the heated substrate. About conductive glass was deposited a layer of titanium dioxide (TiO2). The layer was obtained by dissolving in commercial TiO2 powder acetic acid (CH3CO2H) and Triton X. The electrolyte was a solution of iodine / triiodide into the intracellular regeneration cycle, the counter electrode was a layer made of graphite. The plants were treated with a by washing with deionized water, drying with heat gun and Silica Gel to absorb moisture. Were macerated and immersed in an organic solvent. After a few days, were concentrated in a rotary evaporator at a speed 160 rpm at room temperature for 40 minutes. This dye was applied on the TiO2 layer and then the cell was tested under sunlight. The values obtained were: Torenia fournieri, short-circuit current = 0.44 mA and open circuit voltage V = 0.16; Catharanthus roseus, short-circuit current = 0.43 mA = 0 and open-circuit voltage, 14 V, Sida cordifolia, short-circuit current = 0.22 mA and open circuit voltage V = 0.19; Allamanda cathartic, short-circuit current = 0.19 mA and open circuit voltage V = 0.12; Cobaea scandens, short-circuit current = 0.32 mA and open circuit voltage = 0.17 V. These results may provide more data for better understanding and use of new natural dyes in solar cells.

Esse trabalho objetivou investigar o potencial dos extratos aquosos das cascas de barbatimão (Stryphnodendron adstringens (Mart.) Coville) e sangra dágua (Croton urucurana Baill.) como corante natural têxtil. Os extratos foram caracterizados quanto ao pH, o teor de sólidos totais e a estabilidade no armazenamento. Os extratos foram liofilizados e avaliados por espectroscopia no infravermelho com transformada de Fourier (FTIR), termogravimetria (TG) e calorimetria exploratória diferencial (DSC). Foram realizados experimentos preliminares de tingimento em tecidos multifibra e em diferentes concentrações dos extratos. A partir desses experimentos, foram definidas as variáveis temperatura, tempo e concentração do extrato para o estudo do tingimento por planejamento experimental 2³, em tecidos 100 % algodão e 100 % lã. Os tecidos tingidos em condição otimizada, sem e com mordentes metálicos, foram avaliados quanto à cor, a solidez de cor à luz, à lavagem, à fricção e ao suor. Os efluentes foram coletados e caracterizados quanto ao pH, turbidez, sólidos totais dissolvidos (STD), oxigênio dissolvido, demanda bioquímica de oxigênio (DBO), demanda química de oxigênio (DQO) e teores de ferro e alumínio dissolvidos. Foram conduzidos ensaios bacteriológicos nos extratos aquosos, etanólicos e liofilizados e nos tecidos tingidos. Os resultados das análises por FTIR indicaram a presença de taninos, lignina e celulose nos extratos. Pelo estudo de estabilidade os extratos possuem duração de 42 dias. Nas análises por TG, os extratos obtiveram perda de massa total similares e não geraram alteração na degradação dos tecidos tingidos. Na análise por DSC os extratos obtiveram picos endotérmico e exotérmixo em temperaturas próximas. As melhores condições para o tingimento dos tecidos avaliados é em 98 °C, por 60 min e na concentração de 100 % do extrato. A solidez de cor dos tecidos tingidos variou de baixa a excelente. Os extratos liofilizados apresentaram propriedades antibacterianas. Os efluentes apresentaram valores de STD, DBO, DQO e alumínio e ferro dissolvidos acima dos limites determinados pela legislação nacional. De modo geral, os resultados obtidos indicam que os extratos das cascas de barbatimão e sangra dágua são promissores para serem utilizados como corantes naturais têxteis / This research aimed to investigate the potential of aqueous extracts of barbatimão (Stryphnodendron adstringens (Mart.) Coville) and sangra dágua (Croton urucurana Baill.) bark as natural textile dyes. The extracts were characterized for pH, total solids content and storage stability. The extracts were lyophilized and evaluated by Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG) and differential scanning calorimetry (DSC). Preliminary dyeing experiments were carried out on multifiber fabrics and at different extracts concentrations. From these experiments, the variables temperature, time and concentration of the extract for the study of dyeing by experimental design 2³ in 100 % cotton and 100 % wool fabrics were defined. Fabrics dyed in optimized condition, using metal mordants and with no mordents, were evaluated by colorimetry, color fastness to light, wash, rubbing and perspiration. The effluents were collected and characterized by pH, turbidity, total dissolved solids (TDS), dissolved oxygen, biochemical oxygen demand (BOD), chemical oxygen demand (COD) and dissolved iron and aluminum contents. Bacteriological tests were conducted on aqueous, ethanolic and lyophilized extracts and on dyed fabrics. The results of the FTIR analysis indicated the presence of tannins, lignin and cellulose in the extracts. By the stability study were found that the extracts have a duration of 42 days. In the TG analyzes, the extracts obtained similar total mass loss and did not generate alteration in the degradation of the dyed fabrics. In the DSC analysis the extracts obtained endothermic and exotherm peaks at near temperatures. The optimized dyeing for the evaluated fabrics is at 98 °C for 60 min and at the concentration of 100 % of the extract. The color fastness of the dyed fabrics ranged from low to excellent. Lyophilized extracts showed antibacterial properties. The wastewater showed values of TDS, BOD, COD and aluminum and iron dissolved above the limits determined by national legislation. In general, the results indicate that barbatimão and sangra dágua extracts are promising for use as natural textile dyes

Illustrated exam paper for Josefin Tingvalls project Soft Society. Which is about investigating through cloth and textile our urban surrounding. The core question ; if I go out in an urban area and use textile as a recordmaterial, what traces and stories will I bring back? By looking at textileas a matter, craft and as a philosophical starting point in urban areas, what can it tell about our surrounding and our society? In the three mainchapters of the paper, Tingvall reflects upon important themes such as wandering and spectating, also exhibiting of process based craft, textilein urban areas and matter-based dyes and their relation to us. / Soft society

It has been observed that in certain cases the exposure of dyed fibres to aging techniques results in the strengthening of fibres. This thesis explores the hypothesis that the strengthening is due to radical cross-coupling reactions that could be initiated through metal ion mediated photodecarboxylation. The approaches taken in this research include kinetic experiments (using flash photolysis), examination of possible cross-coupling experiments (using species of opposite charge), and the design and examination of small molecule model systems. A flash photolysis system was developed and used in attempts to determine the rates of photochemical product formation for cobalt(III) amino acid complexes. Lower limits have been established for the rate of product formation in these systems. The lower limits are: 2 x 10⁷ s⁻¹ for [Co(bpy)2(gly)]²⁺; 2 x 10⁷ s⁻¹ for [Co(tpa)(gly)]²⁺; and 5 x 10⁶ s⁻¹ for [Co(tpa)(aib)]²⁺, where bpy is 2,2'-bipyridine; gly is glycinate; tpa is tris(2-pyridylmethyl)amine; and aib is aminoisobutyrate. In past studies, the rates of a series of cobalt(III) amino acid complexes were reported as being the same, and much slower. It is thought that in these cases it may not be the rate of the formation of product that was being measured, but rather the response time of the electronics that was being observed. In this thesis the results obtained for the rate for the aib complex were somewhat lower than those of the gly complexes. This may imply, for the aib complex at least, the rate of the formation of the metallocycle is being observed (and not the response times of the electronics or other limitations of the instrumentation), but the data is poor and there is considerable doubt about this. The steady state photolysis of opposite charged species [Co(bpy)2(gly)]²⁺ and [Co(EDTA)]⁻ is reported. The reactions were carried out on a small scale in deuterated solvent for NMR spectrometry analysis and also on a large scale for the possible isolation and characterisation of the products. Evidence was found for a different reaction occurring when both complexes were present. The exact nature of the product remains elusive. A model system was designed in which a dinuclear ligand would bind to two metal centres and a fibre mimic would be later added. Eight ligands are discussed that could potentially bind two octahedral metal centres. They all had a xylene spacing group linking the two polydentate sites together. Five of the ligands have two bidentate binding sites. The other three had two tridentate sites. The binding sites in three of the bis(bidentate) ligands were based on ethane-1,2- diamine (en). Two of these ligands produced hypodentate monocobalt and sundentate dicobalt complexes. The other two bidentate ligands were based on 2- aminomethylpyridine (ampy). Both of these ligands degraded in the complexation reaction conditions. The binding sites in the tridentate ligands were all based on tacn. Once again, the principal products isolated were hypodentate systems in which only one metal ion was coordinated by the ligands. There is a distinct pattern observed in the xylene spaced ligands to form hypodentate complexes with cobalt(III) metal centred complexes. There is evidence of the di-nuclear species from a reaction with a charcoal catalyst in the bis(bidentate) system. ¹H NMR spectrometry, ¹³C NMR spectrometry, elemental analysis, X-ray crystallography and UV-vis spectroscopy were used to study and characterise the complexes and ligands that were prepared in this project.

It has been observed that in certain cases the exposure of dyed fibres to aging techniques results in the strengthening of fibres. This thesis explores the hypothesis that the strengthening is due to radical cross-coupling reactions that could be initiated through metal ion mediated photodecarboxylation. The approaches taken in this research include kinetic experiments (using flash photolysis), examination of possible cross-coupling experiments (using species of opposite charge), and the design and examination of small molecule model systems. A flash photolysis system was developed and used in attempts to determine the rates of photochemical product formation for cobalt(III) amino acid complexes. Lower limits have been established for the rate of product formation in these systems. The lower limits are: 2 x 10⁷ s⁻¹ for [Co(bpy)2(gly)]²⁺; 2 x 10⁷ s⁻¹ for [Co(tpa)(gly)]²⁺; and 5 x 10⁶ s⁻¹ for [Co(tpa)(aib)]²⁺, where bpy is 2,2'-bipyridine; gly is glycinate; tpa is tris(2-pyridylmethyl)amine; and aib is aminoisobutyrate. In past studies, the rates of a series of cobalt(III) amino acid complexes were reported as being the same, and much slower. It is thought that in these cases it may not be the rate of the formation of product that was being measured, but rather the response time of the electronics that was being observed. In this thesis the results obtained for the rate for the aib complex were somewhat lower than those of the gly complexes. This may imply, for the aib complex at least, the rate of the formation of the metallocycle is being observed (and not the response times of the electronics or other limitations of the instrumentation), but the data is poor and there is considerable doubt about this. The steady state photolysis of opposite charged species [Co(bpy)2(gly)]²⁺ and [Co(EDTA)]⁻ is reported. The reactions were carried out on a small scale in deuterated solvent for NMR spectrometry analysis and also on a large scale for the possible isolation and characterisation of the products. Evidence was found for a different reaction occurring when both complexes were present. The exact nature of the product remains elusive. A model system was designed in which a dinuclear ligand would bind to two metal centres and a fibre mimic would be later added. Eight ligands are discussed that could potentially bind two octahedral metal centres. They all had a xylene spacing group linking the two polydentate sites together. Five of the ligands have two bidentate binding sites. The other three had two tridentate sites. The binding sites in three of the bis(bidentate) ligands were based on ethane-1,2- diamine (en). Two of these ligands produced hypodentate monocobalt and sundentate dicobalt complexes. The other two bidentate ligands were based on 2- aminomethylpyridine (ampy). Both of these ligands degraded in the complexation reaction conditions. The binding sites in the tridentate ligands were all based on tacn. Once again, the principal products isolated were hypodentate systems in which only one metal ion was coordinated by the ligands. There is a distinct pattern observed in the xylene spaced ligands to form hypodentate complexes with cobalt(III) metal centred complexes. There is evidence of the di-nuclear species from a reaction with a charcoal catalyst in the bis(bidentate) system. ¹H NMR spectrometry, ¹³C NMR spectrometry, elemental analysis, X-ray crystallography and UV-vis spectroscopy were used to study and characterise the complexes and ligands that were prepared in this project.

Dye-sensitized Solar Cells (DSSC), also known as Grätzel cells, have been identified as a cost-effective, easy-to-manufacture alternative to conventional solar cells. While mimicking natural photosynthesis, they are currently the most efficient third-generation solar technology available. Among others, their cost is dominated by the synthetic dye which consists of efficient Ruthenium based complexes due to their high and wide spectral absorbance. However, the severe toxicity, sophisticated preparation techniques as well as the elevated total cost of the sensitizing dye is of concern. Consequently, the current global trend in the field focuses on the exploitation of alternative organic dyes such as natural dyes which have been studied intensively. The main attractive features of natural dyes are their availability, environmental friendly, less toxicity, less polluting and low in cost. This contribution reports on the possibility of using sepia melanin dye for such DSSC application in replacement of standard costly ruthenium dyes. The sepia melanin polymer has interesting properties such as a considerable spectral absorbance width due to the high degree of conjugation of the molecule. This polymer is capable of absorbing light quantum, both at low and high energies ranging from the infrared to the UV region. The comprehensive literature survey on Grätzel solar cells, its operating principle, as well as its sensitization by natural dyes focusing on sepia melanin has been provided in this master’s dissertation. The obtained results in investigating the morphology, chemical composition, crystalline structure as well as optical properties of sepia melanin samples using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy x-ray diffraction, X-ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Raman spectroscopy, UV-VIS absorption spectroscopy as well as Photoluminescence (PL) for Grätzel solar cell application have been reported. These results represent an important step forward in defining the structure of melanin. The results clearly show that sepia melanin can be used as natural dye to DSSC sensitization. It is promising for the realization of high cell performance, low-cost production, and non-toxicity. It should be emphasized here that natural dyes from food are better for human health than synthetic dyes. / Physics / 1 online resource (xii, 101 leaves) : illustrations / M. Sc. (Physics)

Dye-sensitized Solar Cells (DSSC), also known as Grätzel cells, have been identified as a cost-effective, easy-to-manufacture alternative to conventional solar cells. While mimicking natural photosynthesis, they are currently the most efficient third-generation solar technology available. Among others, their cost is dominated by the synthetic dye which consists of efficient Ruthenium based complexes due to their high and wide spectral absorbance. However, the severe toxicity, sophisticated preparation techniques as well as the elevated total cost of the sensitizing dye is of concern. Consequently, the current global trend in the field focuses on the exploitation of alternative organic dyes such as natural dyes which have been studied intensively. The main attractive features of natural dyes are their availability, environmental friendly, less toxicity, less polluting and low in cost. This contribution reports on the possibility of using sepia melanin dye for such DSSC application in replacement of standard costly ruthenium dyes. The sepia melanin polymer has interesting properties such as a considerable spectral absorbance width due to the high degree of conjugation of the molecule. This polymer is capable of absorbing light quantum, both at low and high energies ranging from the infrared to the UV region. The comprehensive literature survey on Grätzel solar cells, its operating principle, as well as its sensitization by natural dyes focusing on sepia melanin has been provided in this master’s dissertation. The obtained results in investigating the morphology, chemical composition, crystalline structure as well as optical properties of sepia melanin samples using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy x-ray diffraction, X-ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Raman spectroscopy, UV-VIS absorption spectroscopy as well as Photoluminescence (PL) for Grätzel solar cell application have been reported. These results represent an important step forward in defining the structure of melanin. The results clearly show that sepia melanin can be used as natural dye to DSSC sensitization. It is promising for the realization of high cell performance, low-cost production, and non-toxicity. It should be emphasized here that natural dyes from food are better for human health than synthetic dyes. / Physics / 1 online resource (xii, 101 leaves) : illustrations / M. Sc. (Physics)

Submitted by Deyse Queiroz (deysequeirozz@hotmail.com) on 2018-06-14T13:14:15Z No. of bitstreams: 1 DYEGO DA COSTA SANTOS - DISSERTAÇÃO PPGEA 2012..pdf: 41520705 bytes, checksum: 086b1fdd0714560722d1e4b02d15c2b0 (MD5) / Made available in DSpace on 2018-06-14T13:14:15Z (GMT). No. of bitstreams: 1 DYEGO DA COSTA SANTOS - DISSERTAÇÃO PPGEA 2012..pdf: 41520705 bytes, checksum: 086b1fdd0714560722d1e4b02d15c2b0 (MD5) Previous issue date: 2012-02 / Os grãos residuais de urucum constituem o subproduto da extração dos pigmentos bixina e norbixina na indústria de alimentos. Atualmente, a maioria desses grãos vem sendo descartada, o que gera a necessidade de aproveitamento desses resíduos, inclusive com estudos no sentido de incorporá-los à alimentação humana. Ante o exposto, objetivouse secar grãos residuais de urucum e farinhas de grãos residuais de urucum por meio convencional (secagem em estufa) e utilizando energia solar. Os grãos e as farinhas foram secados em estufa com circulação forçada de ar, nas temperaturas de 40, 50, 60 e 70 °C. Nas secagens por meio de energia solar foram utilizados dois secadores, um para secagem diurna, denominado secador solar, e o outro para secagem noturna, denominado Secador Acumulador de Calor para Secagem Noturna (ACSN). O secador ACSN é composto por dois circuitos de circulação de água independentes. No período diurno funcionava o circuito coletor solar/reservatório, o qual era interrompido durante a noite e aberto o circuito reservatório/câmara de secagem. Na secagem por exposição direta ao sol as amostras eram colocadas em bandejas em base de concreto recoberta com lona plástica (polietileno) preta. Para a representação da cinética de secagem dos grãos e das farinhas de urucum desidratados em estufa, secadores solar e noturno e por exposição direta ao sol foram empregados os modelos matemáticos de Aproximação da Difusão, Dois Termos, Midilli, Page e Thompson. Nas secagens convencionais, o aumento da temperatura de desidratação promoveu reduções nos tempos de secagem. A utilização do secador ACSN no período notumo evitou a absorção de água pelas amostras e promoveu sua secagem, o que possibilitou a obtenção de produto com menor teor de água. Para as amostras cuja secagem se iniciou no período notumo, a utilização do secador ACSN no período notumo possibilitou maiores taxas de secagem, em comparação com a testemunha, com obtenção de produto com menor teor de água. As secagens solares apresentaram tempos de desidratação menores que as observadas nas secagens convencionais. Os modelos de Aproximação da Difusão, Dois Termos, Midilli, Page e Thompson propiciaram bons ajustes aos dados experimentais da cinética de secagem das amostras de grãos e farinhas de grãos residuais de urucum com e sem óleo pelos métodos convencional e solar. / Residual annatto seeds are a subproduct derived from the extraction of bixin and norbixin pigments in the food industry. The fact that most of these seeds are typically discarded demonstrates the need for making better use of these residues, through studies aimed at incorporating them into the human diet. The objective of this study was to dry residual annatto seeds and annatto seed powder using conventional means (oven-drying) and solar energy. The seeds and powder were oven dried with forced air circulation at temperatures of 40, 50, 60 and 70 °C. Two dryers were used in the solar energy method, one for daytime drying, called a solar dryer, and the other for nighttime drying, denominated a heat accumulator for nighttime drying (ACSN). The ACSN dryer is composed of two independent water circulation circuits. The solar collector circuit/reservoir was in operation in the daytime. This was interrupted during the night, whereupon the reservoir circuit/drying chamber was opened. In solar drying, samples were collected in concrete trays covered with a black plastic tarp (polyethylene). Diffusion approximation, two term, Midilli, Page and Thompson mathematical models were used to represent the drying kinetics of annatto seeds and powder dried in an oven and solar and nighttime dryers, as well as by direct exposure to the sun. In conventional drying, an increase in temperature promoted reductions in drying time. Using the ACSN dryer at night avoided water absorption by the samples, promoting their drying and resulting in a product with lower water content. For samples dried at night, employing the ACSN dryer led to greater drying rates compared to the control sample, generating a product with lower water content. Solar dryers exhibited shorter drying times than those observed in conventional dryers. Diffusion Approximation, Two Term, Midilli, Page and Thompson models showed a good fit to experimental data derived from the drying kinetics of annatto seed samples and residual powder, with and without oil, using conventional and solar methods.