A conscientização da população com relação aos malefícios da radiação ultravioleta (UV) levaram à adoção de hábitos preventivos, com destaque para a utilização diária de formulações fotoprotetoras. Ainda que os filtros solares tradicionais sejam efetivos na absorção ou reflexão da radiação UV, sabe-se que a sua atuação contra os radicais livres é limitada, fator que exige a incorporação de compostos antioxidantes às preparações, visando proteção cutânea de excelência. O presente trabalho objetivou o desenvolvimento e avaliação de formulações multifuncionais contendo os filtros solares bemotrizinol e octil triazona, acrescidos do composto bioativo ácido ferúlico - reconhecido pelas suas propriedades antioxidante e fotoprotetora. As formulações foram desenvolvidas de acordo com um delineamento experimental do tipo fatorial (DoE 23) e avaliadas por meio de metodologias in vitro, in vivo e ex vivo para determinação de sua eficácia fotoprotetora e potencial antioxidante. As emulsões foram consideradas estáveis, seguras, com valor de pH biocompatível com a pele e viscosidade aparente adequada ao uso proposto. O delineamento experimental comprovou o potencial antioxidante e fotoprotetor do ácido ferúlico, visto que a presença deste promoveu aumento de até 90% na atividade antioxidante in vitro das formulações, bem como acréscimo de 32% no Fator de Proteção Solar (FPS) in vivo e 24% no Fator de Proteção UVA (UVA-PF). Por meio do ensaio ex vivo, a formulação contendo o ácido ferúlico apresentou tendência em aumentar a atividade antioxidante natural da pele, comparativamente à formulação contendo apenas os filtros solares e à pele não tratada; ademais, houve queda no potencial antioxidante da pele após a exposição à radiação UV, enfatizando a necessidade de proteção cutânea frente aos danos oxidativos. Os resultados comprovaram os efeitos antioxidante e fotoprotetor combinados do ácido ferúlico, em especial quando em sinergismo com filtros solares, tornando o composto bioativo um candidato promissor no desenvolvimento de formulações multifuncionais inovadoras, seguras e eficazes contra os efeitos nocivos decorrentes da exposição solar. / The public awareness regarding the harmful effects of ultraviolet (UV) radiation led to preventive habits, especially the daily use of sunscreens. Although traditional solar filters are effective in UV radiation absorption or reflection, it is known that their activity against free radicals is restricted, an aspect that requires the incorporation of antioxidants to preparations, aiming superior skin protection. Here, we developed and evaluated multifunctional formulations containing the sunscreens bemotrizinol and ethylhexyl triazone plus the bioactive compound ferulic acid - known for its antioxidant and photoprotective properties. Formulations were developed according to a factorial experimental design (DoE 23) and evaluated using in vitro, in vivo and ex vivo methods to determine its photoprotective effectiveness and antioxidant potential. The emulsions were considered stable, safe, with pH value biocompatible with the skin and apparent viscosity suitable for the proposed use. The experimental design evidenced the photoprotective and antioxidant potential of ferulic acid, once its presence increased to 90% the in vitro antioxidant activity of the formulations, as well as 32% increase in the in vivo Sun Protection Factor (SPF) and 24% increase in the UVA Protection Factor (UVA-PF). Through the ex vivo assay, the formulation containing ferulic acid tended to increase the natural antioxidant activity of the skin, compared to the formulation containing only UV filters or the untreated skin; moreover, there was a decrease in the antioxidant potential of the skin after UV radiation exposure, emphasizing the need for skin protection against oxidative damage. The results confirmed the antioxidant and photoprotective effects of ferulic acid, especially when in synergy with UV filters, making the bioactive compound a promising candidate in the development of innovative, safe and effective multifunctional formulations against the harmful effects of sun exposure.

Made available in DSpace on 2017-05-12T14:36:25Z (GMT). No. of bitstreams: 1 Dissertacao_ Nyessia versao finalissima 15-04-2015.pdf: 1194358 bytes, checksum: 0a6089c54d46aca60776ce97f1474515 (MD5) Previous issue date: 2014-11-28 / The aim of this study was to optimize the production of xylanase by Penicillium crustosum using Plackett-Burman the Design (BDP) and Central Composite Rotational Design (CCRD), and its application in the bleaching process of kraft pulp. The PBD-12 was carried out to screening the significant variables of the compounds of the culture medium: NaNO3; KH2PO4; MgSO4 7H2O; KCl; Fe2(SO4)3, yeast extract, corn stover and initial pH under liquid static culture at 28 °C for 6 days. The variables corn stover, KH2PO4, and pH were significant at p <0.10 by DPB. Statistical analysis of the results obtained with CCRD exhibited the three variables (KH2PO4 0.15%, corn stover 2% and initial pH 6.0) that showed significant effects at p <0.05, and the maximum production of xylanase was 50 U/mL, 14 times higher compared to enzyme activity before optimization. The treatment of the kraft pulp with P. crustosum xylanase showed a significant reduction in kappa number (5.27 Kappa points and efficiency (35.04%). Thus, there is evidence of the potential application of xylanase produced by P. crustosum in the bleaching process of kraft pulp in paper industry / As xilanases são complexos enzimáticos pertencentes ao grupo das glicosidases, e são capazes de atuar em vários sítios da cadeia do xilano e degradá-lo em xilooligossacarídeos, xilotrioses, xilobioses e xiloses. As xilanases são utilizadas nos diversos setores industriais, como biobranqueamento de celulose, na melhoria da textura e do volume do pão, clareamento de sucos e vinho, melhoria do valor nutricional de ração de animais monogástricos. Este trabalho teve como objetivo otimizar a produção de xilanase pelo Penicillium crustosum utilizando o Delineamento Plackett-Burman (DPB) e Delineamento Composto Central Rotacional (DCCR), bem como aplicação da xilanase otimizada no processo de branqueamento da polpa de celulose. A seleção dos componentes de meio de cultivo: NaNO3; KH2PO4; MgSO4·7H2O; KCl; Fe2(SO4)3, extrato de levedura, palha de milho e pH inicial foi realizada utilizando DPB-12 em condições de cultivo líquido estacionário a 28ºC por 6 dias. As variáveis palha de milho, KH2PO4, e pH apresentaram efeitos significativos em p<0,10 por DPB. A análise estatística dos resultados obtidos com DCCR exibiram as três variáveis (KH2PO4 0,15 %, palha de milho 2% e pH inicial 6,0) que mostraram efeitos significativos em p<0,05, e a produção máxima de xilanase foi de 50 U/mL, 14 vezes superior em comparação à atividade enzimática antes da otimização. O tratamento da polpa celulósica com a xilanase de P. crustosum mostrou uma redução significativa do número kappa em 5,27 pontos e eficiência Kappa de 35,04%. Dessa forma, evidencia-se o potencial de aplicação da xilanase produzida por P. crustosum no processo de branqueamento da polpa kraft de Eucaliptos para indústria de papel e celulose

Made available in DSpace on 2017-07-10T13:59:28Z (GMT). No. of bitstreams: 1 Dissertacao_ Nyessia versao finalissima 15-04-2015.pdf: 1194358 bytes, checksum: 0a6089c54d46aca60776ce97f1474515 (MD5) Previous issue date: 2014-11-28 / SIM (não especificado) / The aim of this study was to optimize the production of xylanase by Penicillium crustosum using Plackett-Burman the Design (BDP) and Central Composite Rotational Design (CCRD), and its application in the bleaching process of kraft pulp. The PBD-12 was carried out to screening the significant variables of the compounds of the culture medium: NaNO3; KH2PO4; MgSO4 7H2O; KCl; Fe2(SO4)3, yeast extract, corn stover and initial pH under liquid static culture at 28 °C for 6 days. The variables corn stover, KH2PO4, and pH were significant at p <0.10 by DPB. Statistical analysis of the results obtained with CCRD exhibited the three variables (KH2PO4 0.15%, corn stover 2% and initial pH 6.0) that showed significant effects at p <0.05, and the maximum production of xylanase was 50 U/mL, 14 times higher compared to enzyme activity before optimization. The treatment of the kraft pulp with P. crustosum xylanase showed a significant reduction in kappa number (5.27 Kappa points and efficiency (35.04%). Thus, there is evidence of the potential application of xylanase produced by P. crustosum in the bleaching process of kraft pulp in paper industry / As xilanases são complexos enzimáticos pertencentes ao grupo das glicosidases, e são capazes de atuar em vários sítios da cadeia do xilano e degradá-lo em xilooligossacarídeos, xilotrioses, xilobioses e xiloses. As xilanases são utilizadas nos diversos setores industriais, como biobranqueamento de celulose, na melhoria da textura e do volume do pão, clareamento de sucos e vinho, melhoria do valor nutricional de ração de animais monogástricos. Este trabalho teve como objetivo otimizar a produção de xilanase pelo Penicillium crustosum utilizando o Delineamento Plackett-Burman (DPB) e Delineamento Composto Central Rotacional (DCCR), bem como aplicação da xilanase otimizada no processo de branqueamento da polpa de celulose. A seleção dos componentes de meio de cultivo: NaNO3; KH2PO4; MgSO4·7H2O; KCl; Fe2(SO4)3, extrato de levedura, palha de milho e pH inicial foi realizada utilizando DPB-12 em condições de cultivo líquido estacionário a 28ºC por 6 dias. As variáveis palha de milho, KH2PO4, e pH apresentaram efeitos significativos em p<0,10 por DPB. A análise estatística dos resultados obtidos com DCCR exibiram as três variáveis (KH2PO4 0,15 %, palha de milho 2% e pH inicial 6,0) que mostraram efeitos significativos em p<0,05, e a produção máxima de xilanase foi de 50 U/mL, 14 vezes superior em comparação à atividade enzimática antes da otimização. O tratamento da polpa celulósica com a xilanase de P. crustosum mostrou uma redução significativa do número kappa em 5,27 pontos e eficiência Kappa de 35,04%. Dessa forma, evidencia-se o potencial de aplicação da xilanase produzida por P. crustosum no processo de branqueamento da polpa kraft de Eucaliptos para indústria de papel e celulose

Em experimentos que envolvam um fator quantitativo e um qualitativo, é aconselhável que, se detectado efeito significativo da interação entre os fatores na análise de variância, recorra-se a análise de regressão no desdobramento da mesma, no entanto nem sempre a utilização de modelos de regressão linear é a forma mais adequada para avaliar o efeito do fator quantitativo. Neste trabalho é apresentada a forma de ajuste de um modelo de regressão não linear em um experimento com medida repetida no tempo. No experimento considerou-se o ganho de peso, em quilos, de ovinos, machos e fêmeas, da raça Santa Inês em doze idades diferentes. Conduzido como parcela subdividida, pois fator tempo não foi aleatorizado, a análise variância necessita de correção dos graus de liberdade devido à condição de esfericidade não satisfeita. A correção de Geisser e Greenhouse (G-G) foi utilizada para os efeitos da interação e do tempo. O teste F na análise de variância apresentou resultado significativo para interação entre os fatores e, no desdobramento da interação, para avaliação do efeito do fator tempo em cada nível do fator sexo foi proposto o ajuste do modelo Gompertz bem como um teste de aderência para o modelo. Após o ajuste do modelo aos dados de peso de ovinos também foi considerado no estudo a comparação dos parâmetros das curvas de machos e fêmeas. Pela análise proposta foi possível concluir que o modelo univariado, com esquema de parcelas subdivididas, pode ser utilizado em experimentos de crescimento animal, porém sua aplicação está sujeita a verificação da condição de esfericidade. Também foi verificado que incorporar, no desdobramento de interações, o ajuste do modelo Gompertz é um procedimento viável e permitiu avaliar a real qualidade de ajuste do modelo aos dados. Com a comparação dos parâmetros das curvas ajustadas verificou-se que ovinos machos e fêmeas apresentam valores estatisticamente iguais para os parâmetros &alpha; e &gamma;, ambos relacionados com o peso ao nascer dos animais. O peso máximo esperado para fêmea (40,7kg) é estatisticamente inferior ao encontrado para os machos (57,3kg), no entanto, sua taxa de crescimento (0,011kg/dia para fêmeas) é superior (0,007kg/dia para machos), ou seja, as fêmeas atingem o peso de estabilização mais rapidamente que os machos. / In experiments involving a qualitative and a quantitative factor, it is advisable that if a significant interaction is detected between factors in the analysis of variance, one should perform regression analysis of the splitting factors. However, the use of linear regression models is not always the most appropriate way to assess the effect of the quantitative factor. This paper presents a way to fit a nonlinear regression model in an experiment with repeated measurements over time. In the experiment, the weight gain of male and female Santa Inês breed sheep, in pounds, in twelve different ages is measured. Conducted in a split-plot design, as the time factor was not randomized, the analysis of variance requires correction of the degrees of freedom, as the sphericity condition is not satisfied. The Greenhouse and Geisser correction (G-G) was used for the purposes of interaction and time. The F test in the analysis of variance showed a significant result for the interaction between the factors and the splitting of the interaction. In order to evaluate the effect of the time factor at each level of the gender factor, a Gompertz model was proposed, as well as a test of model adherence. After fitting the model to the data, a comparison study of the parameters for males and females was also made. For the proposed analysis, we concluded that the univariate model, with split-plot design, can be used in experiments of animal growth, but its application is prone to verification of the sphericity condition. They also found that the incorporation of the splitting of interactions, by adjusting the Gompertz model, is a viable procedure and allowed to evaluate the real quality of fit. By comparing the fitted parameter values, it was found that males and females have statistically identical values for the parameters &alpha; and &gamma;, both related to the birth weight of the animals. The maximum weight expected for a female (40.7 kg) is statistically lower than that found for the males (57.3 kg), however, their growth rate (0.011 kg / day for females) is greater than the males\' (0.007 kg / day for males), i.e., females reach weight stabilization faster than males.

<p>Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. </p><p>In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings.</p><p>To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of >95% for all monoterpenes and formed products included in the investigation.</p><p>Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆³-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation.</p><p>Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene. </p>

Chemicals in indoor air, either emitted from a source or from a reaction, have been suggested to cause ill health in buildings. However, no clear correlations between exposure and health effects have been made. In this thesis we studied the reaction between monoterpenes, a group of biogenic unsaturated C10 hydrocarbons, and ozone. Ozonolysis of monoterpenes was used as model reactions for unsaturated compounds in ambient air. Also the products formed from these reactions have been suggested as important participants in the occurrence of discomfort and ill health in buildings. To enable a reliable and sensitive measurement of ppb-ppt levels of monoterpenes and the formed products in the presence of ozone an evaluation of available scrubber materials was made. Potassium iodide was shown to remove ambient levels of ozone and have a recovery of &gt;95% for all monoterpenes and formed products included in the investigation. Experimental conditions showed to have a large impact on the initial steps of the ozonolysis, and also on the composition of the formed products. We showed that water plays an important and complex role both in the initial stage of ozonolysis of ∆3-carene and in the formation and composition of products from the ozonolysis of ∆-pinene. The use of experimental design facilitated the evaluation of the investigated reactions. We showed that the formation of OH radicals could be studied using multiple linear regression models and that the presence or absence of OH radicals had a profound impact on the formation of many of the formed products. We also made an observation of the lack of formed OH radicals in the ozonolysis of limonene and discussed probable causes of this observation. Despite the short reaction times and the ambient levels of ozone and monoterpenes used in our experiments we showed that a number of oxidation products were formed, and that the reaction rate is significantly increased in a ventilation system. This formation is underestimated by theoretical calculations and leads to high amounts of known irritants in the indoor air. We showed that theoretical calculations underestimate the formation of these oxidation products 3-13 times, depending on ventilation system and monoterpene.

The first chapter proposes multifractal analysis to measure inhomogeneity of regularity of 1H-NMR spectrum using wavelet-based multifractal tools. The geometric summaries of multifractal spectrum are informative summaries, and as such employed to discriminate 1H-NMR spectra associated with different treatments. The methodology is applied to evaluate the effect of sulfur amino acids. The second part of this thesis provides essential materials for understanding engineering background of a nano-particle fabrication process. The third chapter introduces a constrained random effect model. Since there are certain combinations of process variables resulting to unproductive process outcomes, a logistic model is used to characterize such a process behavior. For the cases with productive outcomes a normal regression serves the second part of the model. Additionally, random-effects are included in both logistics and normal regression models to describe the potential spatial correlation among data. This chapter researches a way to approximate the likelihood function and to find estimates for maximizing the approximated likelihood. The last chapter presents a method to decide the sample size under multi-layer system. The multi-layer is a series of layers, which become smaller and smaller. Our focus is to decide the sample size in each layer. The sample size decision has several objectives, and the most important purpose is the sample size should be enough to give a right direction to the next layer. Specifically, the bottom layer, which is the smallest neighborhood around the optimum, should meet the tolerance requirement. Performing the hypothesis test of whether the next layer includes the optimum gives the required sample size.

In the first part of the thesis, we propose a new class of designs called multi-layer sliced Latin hypercube design (DSLHD) for running computer experiments. A general recursive strategy for constructing MLSLHD has been developed. Ordinary Latin hypercube designs and sliced Latin hypercube designs are special cases of MLSLHD with zero and one layer respectively. A special case of MLSLHD with two layers, doubly sliced Latin hypercube design, is studied in detail. The doubly sliced structure of DSLHD allows more flexible batch size than SLHD for collective evaluation of different computer models or batch sequential evaluation of a single computer model. Both finite-sample and asymptotical sampling properties of DSLHD are examined. Numerical experiments are provided to show the advantage of DSLHD over SLHD for both sequential evaluating a single computer model and collective evaluation of different computer models. Other applications of DSLHD include design for Gaussian process modeling with quantitative and qualitative factors, cross-validation, etc. Moreover, we also show the sliced structure, possibly combining with other criteria such as distance-based criteria, can be utilized to sequentially sample from a large spatial data set when we cannot include all the data points for modeling. A data center example is presented to illustrate the idea. The enhanced stochastic evolutionary algorithm is deployed to search for optimal design. In the second part of the thesis, we propose a new smoothing technique called completely-data-driven smoothing, intended for smoothing over irregular regions. The idea is to replace the penalty term in the smoothing splines by its estimate based on local least squares technique. A close form solution for our approach is derived. The implementation is very easy and computationally efficient. With some regularity assumptions on the input region and analytical assumptions on the true function, it can be shown that our estimator achieves the optimal convergence rate in general nonparametric regression. The algorithmic parameter that governs the trade-off between the fidelity to the data and the smoothness of the estimated function is chosen by generalized cross validation (GCV). The asymptotic optimality of GCV for choosing the algorithm parameter in our estimator is proved. Numerical experiments show that our method works well for both regular and irregular region smoothing. The third part of the thesis deals with uncertainty quantification in building energy assessment. In current practice, building simulation is routinely performed with best guesses of input parameters whose true value cannot be known exactly. These guesses affect the accuracy and reliability of the outcomes. There is an increasing need to perform uncertain analysis of those input parameters that are known to have a significant impact on the final outcome. In this part of the thesis, we focus on uncertainty quantification of two microclimate parameters: the local wind speed and the wind pressure coefficient. The idea is to compare the outcome of the standard model with that of a higher fidelity model. Statistical analysis is then conducted to build a connection between these two. The explicit form of statistical models can facilitate the improvement of the corresponding modules in the standard model.

Kognitiv beteendeterapi (KBT) har mest evidens vid social fobi, och på senare år har även guidad självhjälp baserad på KBT visat goda resultat. Acceptance and commitment therapy (ACT) är en del av den tredje vågens KBT och har visat lovande resultat vid ångestsyndrom. Företrädare för ACT har varnat för riskerna med tekniker för att utmana negativa automatiska tankar. Studien syftar till att med en single case experimentell design med multipel baslinje (N=9) studera effekterna av kognitiv omstrukturering (KO) och kognitiv defusion (KD) i form av guidad självhjälp på social ångest, socialt undvikande, psykologisk flexibilitet, defusion, samt frekvens av och trovärdighet hos negativa automatiska tankar. Resultaten visade att KO och KD inte enbart påverkade de processer som teorierna predicerar utan även den andra behandlingens processer.

Estimating reactivity ratios in multicomponent polymerizations is becoming increasingly important. At the same time, using cumulative models is becoming imperative, as some multicomponent systems are inherently so fast that instantaneous "approximate" models can not be used. In the first part of the thesis, triad fractions (sequence length characteristics) are employed in a multiresponse scenario, investigating different error structures and levels. A comparison is given between instantaneous triad fraction models and instantaneous composition model, which represent the current state-of-the-art. In the second part of the thesis, extensions are discussed with cumulative composition and triad fraction models over the whole conversion range, thus relating the problem of reactivity ratio estimation to the optimal design of experiments (i. e. optimal sampling) over polymerization time and conversion. The performance of cumulative multiresponse models is superior to that of their instantaneous counterparts, which can be explained from an information content point of view. As a side-project, the existence of azeotropic points is investigated in terpolymer (Alfrey-Goldfinger equation) and tetrapolymer (Walling-Briggs equation) systems.