Orientadores: Telma Teixeira Franco, Ana Carolina Deckmann / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T08:47:54Z (GMT). No. of bitstreams: 1 VargasTapia_Eulalia_M.pdf: 2747166 bytes, checksum: 033342e772fb86dbb8d3a20cf75af774 (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foram desenvolvidos estudos visando o melhoramento genético da linhagem de levedura Lipomyces starkeyi DSM 70296, visando sua utilização na biossíntese de precursores de biocombustíveis a partir de fontes renováveis. Inicialmente foram verificados os parâmetros de mutagênese. O melhoramento genético foi conduzido por mutagênese aleatória de DNA por irradiação ultravioleta. O tempo de exposição foi ajustado de forma a assegurar uma taxa de sobrevivência celular não superior a 5%, para obter indivíduos contendo elevado acúmulo de mutações no DNA. Os mutantes foram selecionados com o uso da cerulenina agente interferente ao metabolismo de interesse, de forma que fossem identificados os mutantes cujas alterações genéticas pudessem estar promovendo efeitos sobre este metabolismo. Os mutantes que demonstraram crescimento normal em meio de cultura suplementado com cerulenina foram considerados bons candidatos para estudos aprofundados. Nesta etapa foram selecionados 90 mutantes, dos quais foram selecionados os oito melhores candidatos para estudo através de fermentação em frascos agitados. A avaliação de desempenho fermentativo foi conduzida a partir da avaliação dos índices de crescimento e produtividade de lipídeo utilizando meio de cultura contendo xilose como única fonte de carbono. A fermentação da cepa padrão foi conduzida nas mesmas condições para permitir uma análise comparativa. Os resultados obtidos mostraram que um dos mutantes (identificado como A1) apresentou aumento significativo nos índices de produtividade de biomassa e lipídeo em relação à cepa padrão (teste de Tukey com 95% de significância). Este mutante foi então selecionado para estudo aprofundado através da fermentação em biorreator utilizando a mesma composição de açúcares observada em bagaço de cana-de-açúcar (30% glicose: 70% xilose), conforme determinado em outros estudos conduzidos em nosso laboratório. Novamente, a fermentação da cepa padrão foi conduzida nas mesmas condições para permitir a análise comparativa. Os resultados confirmaram que o mutante A1 apresenta maior produtividade tanto em biomassa (88 g/L) quanto em fração de lipídeo (54,6%), em comparação à cepa padrão (76 g/L e 47,5%, respectivamente). Estes resultados indicam a viabilidade da estratégia de mutagênese aleatória aliadas à seleção de mutantes por cerulenina para o melhoramento genético desta levedura oleaginosa, visando sua aplicação no processo de biossíntese de precursores de biocombustíveis de segunda geração / Abstract: In this work it were performed studies aiming the genetic improvement of the yeast Lipomyces starkeyi strain DSM 70296 for its utilization in the biosynthesis of biofuels' precursors from renewable sources (sugarcane bagasse). Initially, we defined the parameters of mutagenesis. The genetic breeding was carried out by random mutagenesis of DNA by ultraviolet irradiation. The exposure time was adjusted to ensure a cell survival rate not exceeding 5%, in order to obtaining individuals presenting high rates of DNA mutations. The mutants were selected by using cerulenin, an compound displaying effects on the metabolism of interest (biosynthesis of lipids). Thus, the selected mutants are potentially carriers of genetic alterations in this particular metabolism. The mutants demonstrating normal growth in culture medium supplemented with cerulenin were considered good candidates for in-depth studies. In this step we selected 90 mutants, of which eight were considered the best candidates for further studies by fermentation in shake flasks. The evaluation of fermentative performance was carried out based on growth and lipid productivity rates using culture medium containing xylose as sole carbon source. The fermentation of the wild-type strain was conducted under the same conditions to allow a comparative analysis. The results showed that the mutant identified as A1 presented a significant increase in the productivity rates of both biomass and lipid in comparison to wild-type strain (Tukey test with 95% significance). This mutant was then selected for detailed study by fermentation in bioreactor using the same carbohydrate composition observed in sugarcane bagasse (30% glucose: 70% xylose), as previously determined by other studies in our laboratory. Again, fermentation of the wild-type and the mutant A1 was performed under the same conditions in order to allow a comparative analysis. The results confirmed that the A1 mutant presents an increased productivity of both biomass (88 g/L) and lipids (54.6%) when compared to the wild-type strain (76 g/L and 47.5%, respectively). These results indicate the feasibility of random mutagenesis strategy coupled with mutant selection employing cerulenin for the genetic improvement of the oleaginous yeast L. starkeyi, focusing its use in the biosynthesis of precursors of second generation biofuels / Mestrado / Desenvolvimento de Processos Químicos / Mestra em Engenharia Química

Foram estudadas trinta e uma cepas fúngicas não identificadas, as quais foram denominadasX1 a X31. O potencial fotoprotetor foi avaliado pela medida espectrofotométrica da absorçãodos extratos na região do UV (280-400 nm). Os extratos com os melhores perfis de absorção em cultura estacionária foram X1, X2, X6, X12, X13, X18, X19, X22, X24 e X31 e, em cultura agitada X4 e X17. A reprodutibilidade do processo foi avaliada e as cepas fúngicas que apresentaram coeficiente de variação menor que 15% foram selecionadas para o estudo de fotoestabilidade. A fotoestabilidade dos extratos foi avaliada pela medida da viabilidade celular de fibroblastos L929 tratados com extratos previamente irradiados sob radiação UVA (11,2 J/cm2) e UVB (3,43 J/cm2) e extratos não irradiados, bem como, pela comparação das áreas sob as curvas de absorção na região do UV dos extratos irradiados e não irradiados. Os extratos selecionados para o estudo de fotoestabilidade foram X4, X12, X19, X22, X24 e X31. Os extratos não irradiados apresentaram os seguintes valores deIC50 para viabilidade celular (citotoxidade): X4-130µg/ml, X19-20µg/ml, X22-10 µg/ml e X24-60µg/ml. Após a radiação UVA e UVB, os extratos apresentaram redução significativa da viabilidade celular em relação ao IC50 dos extratos não irradiados. Sob luz UVB, os extratos X12 (IC50 35µg/ml) e X31 (IC50 70µg/ml) mantiveram a mesma porcentagem de redução da viabilidade celular quando comparado ao IC50 dos extratos não irradiados. No entanto após exposição à luz UVA, o extrato X12 aumentou a viabilidade celular de 50% (quando não irradiado) para 75% (irradiado). Enquanto que o extrato X31, mesmo após a radiação UVA, manteve a mesma redução de 50% da viabilidade celular. Nessa etapa os extratos selecionados foram os X12 e X31. O espectro de absorção na região do UV obtido para o extrato X12 mostrou uma redução da absorbância de 28,3% sob radiação UVB e de 60% sob radiação UVA em relação ao extrato não irradiado. O extrato X31 apresentou uma redução da absorbância de 17,6% e30% sob radiação UVB e UVA respectivamente, em relação ao extrato não irradiado. Os fungos selecionados foram identificados por PCR, sugerindo que o fungo X12 seja o Aspergillus terreus e o X31 seja o Talaromyces pinophilus. Por fim, foi feita a identificação da substância ativa do extrato X12 empregando a técnica de desreplicação, a qual fez o uso da instrumentação analítica acoplada UHPLC-DAD-(ESI)-HRMS associada ao banco de dados Chapman& Hall\'s Dictionary of Natural Products (DNP). No extrato X12 o composto majoritário foi identificado como sendo a citreoviridina. Assim, os resultados do presente trabalho permitiu estabelecer um procedimento para a seleção de fungos produtores de compostos absorvedores de radiação UV, que poderia ser aplicado na obtenção de novos filtros orgânicos naturais para protetores solares. / It were studied thirty-one fungal strains not identified, which were named X1 to X31. The photoprotective potential was assessed spectrophotometrically by measuring absorption of the extract in the UV region (280-400 nm). The extracts that presented the best absorption profiles in stationary culture were X1, X2, X6, X12, X13, X18, X19, X22, X24 and X31, and X4 and X17 in stirred culture. The reproducibility of the process was evaluated and fungal strains that showed a coefficient of variation lower than 15% were selected for the study of photostability. The photostability of the extracts was assessed by measuring cell viability of L929 fibroblasts treated with extracts previously irradiated under UVA light (11,2 J/cm2) and UVB (3,43 J/cm2) and not irradiated extracts, as well as by comparison of the areas under the curves of absorption in the UV region of the irradiated and non-irradiated extracts. The extracts selected for the study of photostability were X4, X12, X19, X22, X24 and X31. The non-irradiated extracts showed the following IC50 values for cell viability (cytotoxicity): X4- 130?g/ml X19-20?g/ml, X22-10/ml and X24-60?g/ml. After UVA and UVB radiation, the extracts showed significant reduction in cell viability compared to the IC50 of the unirradiated extracts. Under UVB light, the X12 extracts (IC50 35?g/ml) and X31 (IC50 70mg/ml) maintained the same percentage of cell viability reduction when compared to the IC50 of the unirradiated extracts. However after exposure to UVA light, X12 extract increased the cell viability from 50% (when not irradiated) to 75% (irradiated). While X31 extract even after the UVA irradiation, remained the same 50% of reduction in cell viability. At this stage the selected extracts were X12 and X31. The absorption spectrum in the UV region obtained for X12 extract showed a decrease in absorbance of 28.3% under UVB and 60% under UVA radiation relative to non-irradiated extract. The X31extract showed a reduction in absorbance of 17.6% and 30% in UVA and UVB radiation, respectively, compared to non-irradiated extract. The selected fungi were identified by PCR, suggesting that X12 fungus is Aspergillus terreus and X31 is the Talaromyces pinophilus. Finally it was identified the active substance of X12 extract employing dereplication technique which makes use of coupled analytical instrumentation UHPLC-DAD- (ESI) HRMS associated to the Chapman and Hall\'s Dictionary of Natural Products (DNP) database. The majority compound of X12 extract was identified as the citreoviridin. Thus, the results of this study allowed us to establish a procedure for the selection of producers of UV absorbing compounds from fungi, which could be applied in obtaining new natural organic filters for sunscreens.

Non melanoma skin cancer (NMSC) is a serious condition caused by chronic ultraviolet (UV) exposure that leads to DNA damage in skin. UV radiation has the potential to lead to DNA damage, which triggers biochemical pathways within a cell. The result is that the cell either undergoes cell cycle arrest, giving the cell time to repair DNA damage, or apoptosis. Sunscreen is the most commonly used treatment for preventing UV induced skin damage, but it involves a number of undesirable and toxic side effects including damaging the dermis, premature aging of skin and underweight child births. This has led to interest in finding safer alternatives to prevent UV damage without the negative side effects of sunscreen. In particular, bovine milk sphingomyelin (SM) is a compound that has the potential to protect against UV damage without any of the dangerous side effects of sunscreen. Here we present the use of SM for UV protection of human keratinocytes (KRTs) to prevent DNA mutations that result from UV exposure. In particular, analysis of the expression of DNA damage biomarkers p21 and p53 was done to determine the potential of SM to prevent DNA damage associated with UV exposure. Both non-SM treated KRTs and KRTs treated with 0.1% SM media 24 hours prior to UV radiation were fixed and IF-stained at 24 hours following 40 mJ/cm2 of UV exposure. Significant differences in both p21 and p53 were observed between the SM treated and non-SM treated cells at the UV dosage level (via t-test; p

The efficacy of ozone and ultraviolet light, used in combination, to inactivate Listeria monocytogenes in fresh (9% NaCl, 91.86% transmittance at 254 nm) and spent chill brines (20.5% NaCl, 0.01% transmittance at 254 nm) was determined. Preliminary studies were conducted to optimize parameters for the ozonation of "fresh" and "spent" brines. These include diffuser design, comparison of kit to standard methods to measure residual ozone, studying the effect of ozone on uridine absorbance and determining presence of residual listericidal activity post ozonation. An ozone diffuser was designed using 3/16 inch PVC tubing for the ozonation of brines. The sparger was designed to facilitate better diffusion and its efficiency was tested. The modified sparger diffused 1.44 ppm of ozone after 30 minutes of ozonation and the solution had an excess of 1 ppm in 10 minutes of ozonating fresh brine solution (200ml). Population levels of L. monocytogenes were determined at various time intervals post-ozonation (0, 10, 20, 60 min) to determine the presence of residual listericidal activity. The population post ozonation (0 minutes) was 5.31 Log CFU/ml and was 5.08 Log CFU/ml after a 60 minute interval. Therefore, residual antimicrobial effect was weak. Accuracy of the Vacu-vial Ozone analysis kit was evaluated by comparing the performance of the kit to the standard indigo colorimetric method for measuring residual ozone. The kit was inaccurate in determining residual ozone levels of spent brines and 1% peptone water. Uridine was evaluated as a UV actinometric tool for brine solutions that were ozonated before UV treatment. The absorbance of uridine (A262) decreased after ozonation from 0.1329 to 0.0512 for standard 10 minutes UV exposure duration. Absorbance of uridine was influenced by ozone indicating that the presence of ozone may hamper UV fluence determination accuracy in ozone-treated solutions. Upon completion of diffuser design and ozone/UV analysis studies, the effect of ozone-UV combination on L. monocytogenes in fresh and spent brines was evaluated. Ozonation, when applied for 5 minutes, caused a 5.29 mean Log reduction while 5 minutes of UV exposure resulted in a 1.09 mean Log reduction of L. monocytogenes cells in fresh brines. Ten minutes of ozonation led to a 7.44 mean Log reduction and 10 minutes of UV radiation caused a 1.95 mean Log reduction of Listeria in fresh brine. Spent brines required 60 minutes of ozonation for a 4.97 mean Log reduction in L. monocytogenes counts, while 45 minutes resulted in a 4.04 mean Log reduction. Ten minutes of UV exposure of the spent brines resulted in 0.30 mean Log reduction in Listeria cells. A combination of 60 minutes ozonation and 10 minute UV exposure resulted in an excess of 5 log reduction in cell counts. Ozonation did not cause a sufficient increase in the transmittance of the spent brine to aid UV penetration but resulted in apparent color change as indicated by change in L*a*b* values. Ozonation for sufficient time had considerable listericidal activity in fresh brines and spent brines and when combined with UV treatment, is effective reducing L. monocytogenes to undetectable levels in fresh brines. / Master of Science in Life Sciences

Humans are constantly exposed to different types of radiations. It has been suggested that low dose and low dose rate of γ-radiation as well as ultra violet A (UVA) induce oxidative stress in cells that may promote mutations. The mechanisms behind radiation-induced oxidative stress and its relation to genotoxicity and cancer induction are not well understood. In the majority of investigations, the DNA molecule has been studied as the target for mutations, however the results obtained in our group point out that DNA bases in the cytoplasm could also be a significant target. MTH1 and MYH are two of the key proteins of the repair pathway that prevent mutations arising from oxidized DNA bases. In this thesis, we studied the role of MTH1 and MYH in genotoxicity of UVA and γ-radiation. The adaptive response to low dose rates of γ-radiation was also investigated. MTH1 and/or MYH were knockdown in human lymphoblastoid TK6 cells. The clonogenic survival, mutant frequency and chromosomal aberration assays were performed following UVA or γ-radiation exposure. Our results indicated that acute exposure to UVA or γ-radiation affects cell survival and also increases the mutant frequency above the background. The mutant frequency in MTH1 deficient cells was higher than that in wild types after UVA exposure. Following γ-radiation exposure, a higher mutant frequency was observed in the MYH and MTH1 deficient cells, in comparison to either MYH or MTH1 deficient or wild type cells. No dose rate effect of γ-radiation for mutations was observed. An adaptive response to γ-radiation was observed at the mutation level in MCF-10A cells but not at the survival level. In summary, our results suggest that; a) MYH and MTH1 cooperatively protect cells against genotoxic effects of γ-radiation; b) MTH1 protects cells from UVA-induced mutations; c) low dose rates of γ-radiation may induce an adaptive response at the mutation level; d) there is no dose rate effect for γ-radiation at the mutation level. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript.</p>

Charles University in Prague Faculty of Pharmacy in Hradec Králové Department of Biophysics and Physical Chemistry Candidate: Denisa Mazouchová Supervizor: Mgr. Monika Kuchařová, Ph.D. Title of diploma thesis: Effect of ultraviolet radiation on the change the mechanical parameters of human skin This diploma thesis deals in theoretical part with the properties of human skin, the characteristics of the UV radiation and its effects on human skin. The practical part of the thesis focuses on the in vivo measurement of mechanical parameters of human skin after UV radiation. Mechanical characteristics of human skin were measured in 12 subjects before the application of UV radiation, immediately after application of UV and after 24 hours of rest skin. The experiment used a UV lamp with a wavelength of 370 nm emitted light. The monitored parameters were Hooke's and Newton's coefficients. Hooke's coefficient gives us the stiffness of the skin as a whole , Newton coefficient characterises its viscosity. For measurement of those parameters was used dynamic viscoelastomer. The experiment has been found out that no signifiant ganges of Hooke's and Newton's coefficients were not found immediately after the application of UV radiation of wavelength 370 nm, in 12 volunteers. Significant change occurred only in the...

Le rayonnement ultraviolet (UV) est un cancérigène pour lequel peu d’informations sur l’exposition des populations est disponible. L’intensité et les variations de l’exposition au rayonnement UV solaire, principale source d’exposition, a un impact sur la santé mais il est difficile de les surveiller. Le travail de cette thèse a permis de développer un outil pour une estimation quantitative de l’exposition individuelle à l’UV solaire pour l’épidémiologie. Nous avons créé un atlas des moyennes mensuelles d’irradiation journalière en Europe. Certaines données manquantes au niveau des pays nordiques en hiver ont dû être extrapolées. Nous avons vu que la saisonnalité est forte et que la répartition spatiale ne suit pas seulement le gradient de latitude. Par exemple, l’irradiation UV est plus élevée au sud des pays nordiques qu’au centre de l’Europe. Une enquête a été menée dans huit populations européennes afin d’estimer l’exposition individuelle. Ces populations ont des comportements différents vis-à-vis de l’exposition au soleil. Après une étape de modélisation pour estimer les données d’irradiation UV manquantes au nord de la Norvège sur l’ensemble de l’année, nous avons pu quantifier l’exposition chronique et l’exposition pendant les vacances dans trois populations (française, italienne et norvégienne). L’outil développé au cours de cette thèse pourra être utilisé pour de futures études épidémiologiques qui permettront de connaître l’exposition au rayonnement ultraviolet solaire de populations et de mieux comprendre son rôle dans l’étiologie de diverses maladies, telles que les cancers cutanés. / Ultraviolet radiation (UV) is a carcinogenic agent for which little information on human exposure is available. The intensity and the changes of solar UV exposure, which is the main source of exposure, have an impact on health but are difficult to monitor. The work of this thesis led to the creation of a tool for quantitative estimation of individual exposure to solar UV that can be used in epidemiological studies. We created an atlas of monthly average daily radiation across Europe. Some missing values from the Nordic countries during winter had to be extrapolated. We observed a strong seasonality and characteristics in the spatial distribution which does not always follow the gradient of latitude. For instance, UV radiation is higher in the southern area of the Nordic countries than in central Europe. A survey was conducted in eight European populations to estimate individual exposure. These populations have different behaviours regarding sun exposure. After a step of modeling to estimate missing values in northern Norway throughout the year, we quantified chronic and holiday exposure in three populations (France, Italy and Norway). The tool developed during this thesis will be used for future epidemiological studies that will contribute to improving the knowledge about UV exposure in populations and better understanding its role in the aetiology of various diseases, such as skin cancers.

As propriedades dos extratos vegetais vêm sendo cada vez mais investigadas, suscitando o interesse em aliar o potencial destes para minimizar efeitos do fotoenvelhecimento da pele decorrentes da ação dos radicais livres à fotoproteção proporcionada pelos filtros solares. Apesar do uso difundido de vários extratos vegetais, alguns deles, como a Matricaria chamomilla, ainda carecem de estudos acerca de suas propriedades e efeitos biológicos na pele, especialmente quando este é veiculado em formulações dermocosméticas. Assim, esse trabalho teve por objetivo a avaliação da estabilidade e da eficácia pré-clínica de formulações fotoprotetoras contendo o extrato de Matricaria chamomilla ou dos componentes isolados do vegetal, a-bisabolol e apigenina, na proteção de danos causados pela radiação ultravioleta (UV). Para tal, verificou-se a estabilidade dos ativos veiculados em formulação com FPS previamente determinado, bem como outras formulações de protetor solar foram desenvolvidas e a estas adicionadas extrato de camomila ou alfa-bisabolol, sendo testados por centrifugação, pH e análise visual. A estabilidade física das formulações mais estáveis foi analisada por estudos reológicos. A estabilidade química de formulações contendo extrato de camomila, apigenina e bisabolol foi determinada por Cromatografia Líquida de Alta Eficiência (HPLC). Estas formulações acrescidas de apigenina, extrato de camomila, ou alfa-bisabolol finalmente foram avaliadas no que tange à eficácia pré-clínica. Neste estudo, camundongos foram submetidos à radiação UV e o efeito protetor das formulações foi avaliado através de técnicas de biofísica nãoinvasiva e análise de imagem, que forneceram medidas de eritema, o teor de água do estrato córneo, a perda de água transepidérmica, ecogenicidade e espessura da derme. Os resultados permitiram selecionar as formulações fisicamente estáveisl para ambas as combinações de filtros UV associados contendo as substâncias ativas em estudo. No estudo de estabilidade química, a apigenina foi mais estável quando comparada às outras substâncias ativas em estudo e o bisabolol mostrou estabilidade química baixa. Todas as formulações foram eficazes na redução da perda de água transepidérmica. Os efeitos destas formulações na pele foram muito positivos, pois todas elas levaram a aumentos ecogenicidade e valores menores de espessura quando comparada às regiões irradiadas. Esses resultados mostraram efeitos significativos na melhoria do processo inflamatório causado pela radiação. Finalmente, as formulações desenvolvidas foram estáveis e eficazes na proteção da pele. Além disso, quando o extrato de camomila ou apigenina esteve presente na formulação fotoprotetora os efeitos foram mais pronunciados. / Particular plant extracts are being increasingly studied for their properties, in order to combine their potential to minimize skin photoaging effects from the action of free radicals with photoprotection provided by sunscreens. Despite of the widespread use of various plant extracts, some of them as it is the case of Matricaria chamomilla still need mored detailed studies especially on their properties and biological effects on skin, especially in dermocosmetic formulations. The aim of the present study was to assess the stability and the preclinical efficacy of sunscreen formulations containing M. chamomilla extract or its isolated components, alpha-bisabolol and apigenin, in the protection from damage caused by ultraviolet radiation. For this purpose, the physical stability in a pre-determined SPF formulation added of the active substances under study was determinated. Other sunscreen formulations were developed and supplemented with chamomile extract or alpha-bisabolol, and these were tested for centrifugation stability, pH and visual analysis. Physical stability of the most stable formulations was estimated by rheological measurements. The chemical stability of the formulations containing chamomile extract, apigenin, and bisabolol was determinated by High Efficiency Liquid Chromatography (HPLC). These formulations with chamomile extract, apigenin or alpha-bisabolol were finally evaluated in terms of preclinical efficacy. In this study, hairless mice were submitted to UV radiation and the protective effect of the formulations was evaluated using noninvasive biophysics techniques and image analysis, in which we obtained measures of erythema, the water content of stratum corneum, transepidermal water loss, the echogenicity and the thickness of the dermis. The results allowed selecting physicallystable formulations for both the combinations of UV-filters associated containing the actives substances under study. In the chemical stability study, the apigenin present in the extract was more stable when compared to the other active substances under study and the bisabolol showed a low chemical stabilitity. All the formulations were effective in the transepidermic water-loss reduction. The effects of these formulations on skin were very positive since all of them led to ecogenicity increases and lower thickness values when compared to irradiated regions. These results showed significant effects in the improvement of the inflammatory process caused by radiation. Finally, the formulations developed were stable and effective in the skin protection. In addition, when the chamomile extract or apigenin was present in the formulation the photoprotective effects were more pronounced.

O dióxido de titânio (TiO2) é atualmente um dos catalisadores mais utilizados para remoção de poluentes em efluentes, devido a sua alta estabilidade química, baixo custo, não toxicidade e possibilidade de ativação por radiação solar. O ferricianeto ()63− é um dos complexos cianometálicos mais estáveis gerados nos efluentes da mineração aurífera. Nesta pesquisa se apresenta o estudo de degradação deste complexo por meio de fotolise, fotocatálise com TiO2, e fotocatalise assistida com peróxido (H2O2). Para conferir a degradação do complexo foram analisados ao final do processo, parâmetros químicos como quantificação de cianeto livre, formação de amônia, nitrato, assim como precipitação de ferro metálico. Os ensaios foram feitos no Laboratório de Fotoquímica e Superfícies-LAFOS da Universidade Federal Rio Grande do Sul por meio de uma lâmpada de irradiação UV, o reagente utilizado foi o ferricianeto de potássio [K3Fe(CN)6] grau analítico, preparado como uma solução sintética em condições próximas do pH dos efluentes de mineradoras, a pesquisa foi conduzida em condições de pressão e temperatura ambiente (1 atm e 25°C), testando diferentes concentrações de TiO2 e um analise sob irradiação solar. A partir de uma solução de 100 mg L-1 o efeito da fotólise demostrou que o complexo estudado apresenta uma grande estabilidade uma vez que em condições de irradiação UV (λ>300nm) foi observada uma baixa taxa de degradação após um período de 24 h, abaixo de 20%, enquanto em um sistema de fotocatálise heterogênea com TiO2 em condições alcalinas foram obtidas degradações de até 70%. O melhor resultado se atingiu no sistema de fotocatalise assistida com peroxido, sendo usado 2.5 vezes menos peroxido do que é utilizado na indústria, alcançando 83% degradação para um dos complexos mais estáveis formado pelo cianeto, o ferricianeto. Foram avaliados diferentes parâmetros para analisar o comportamento e degradação do complexo ferricianeto, como por exemplo a adsorção em fase escura do complexo sobre o catalisador; efeito da dosagem de TiO2, ação do H2O2 em baixa concentração, incidência da radiação UV em diferentes fontes com potência de 120 e 200 W e finalmente com radiação solar. Os resultados obtidos mostraram a influência do TiO2 junto com irradiação UV para atingir a degradação do complexo e formação de produtos menos tóxicos. / Titanium dioxide (TiO2) is one of the most frequently used catalysts applied for effluent treatment by pollution removal due to its high chemical stability, low cost, non-toxicity and the solar power is capable to activated it. Ferricyanide ()63− is one of the most stable cyanometallic complexes generated in the gold mining effluents. This research presents the study degradation of this complex by means of photolysis, photocatalysis with TiO2, and photocatalysis assisted with peroxide (H2O2). In order to verify the degradation of the complex, chemical parameters such as quantification of free cyanide, formation of ammonia, nitrate, as well as precipitation of metallic iron were analyzed at the end of the process. The tests were conducted at LAFOS (Surface and Photochemistry Laboratory) at UFRGS (Federal University of Rio Grande do Sul), using a UV irradiation lamp, the reagent used was potassium ferricyanide [K3Fe(CN)6] analytical grade, prepared as a synthetic solution with pH close to what is found at mining companies effluents. The tests were performed at normal temperature and pressure (1 atm e 25°C), testing different concentrations of TiO2 and an analysis under solar irradiation. From a solution of 100 mg L-1 the photolysis effect showed that the complex studied feature a high stability since under UV irradiation conditions (λ> 300 nm) a low degradation rate was observed after a period of 24 h, below 20%, whereas in a heterogeneous photocatalysis system with TiO2 under alkaline conditions degradations of up to 70% were obtained. The best result was obtained in the peroxide assisted photocatalysis system, using 2.5 times less peroxide than is used by the industry, reaching 83% degradation to one of the most stable complexes formed by cyanide, ferricyanide. Different parameters were used to analyze the degradation of ferricyanide complex, such as adsorption in dark stage over the catalyst; low concentration of H2O2, effects from TiO2 dosage, UV radiation incidence from different sources of 120 and 200W and finally solar radiation. The results obtained show the TiO2 influence along with UV irradiation to achieve degradation of the complex and less toxic products.

This final thesis goal has been to try and develop a titanium dioxide coating for water purification. The coating should be used in a manufacturing industry on textiles. Water purification is achieved through photocatalysis with titanium dioxide and UV-radiation, where hydroxyl radicals form through oxidation. The kind of textile fiber chosen for the substrates is a polyester fiber. The substrates have been developed in several different shapes. Two different knitted patterns was developed, one flat patterned and one wavy patterned. Another kind of substrate was a spacer-type and there was also a substrate made from a PET-bottle. The different substrates were chosen to compare the different coatings effect on different surfaces and the different coatings were developed from two types of titanium dioxide. The coated substrates have been analyzed for hydroxyl radical generating properties. By testing a sample of water with titanium dioxide against a sample with water that had no additives, it was shown that titanium dioxide generates more hydroxyl radicals. The results of the work showed that the recipe containing 3 % titanium dioxide and 3 % acrylic binder showed good properties for water purification. In addition, the results showed a stronger effect for the wavy patterned substrate then the flat patterned, which is an interesting result that should be researched further in the future. / Program: Textilingenjörsutbildningen