Orientador: Susanne Rath / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T08:45:18Z (GMT). No. of bitstreams: 1 Peruchi_LiviaManiero_M.pdf: 2606610 bytes, checksum: 4b1e6756287ec6b3404f0fe6512fb307 (MD5) Previous issue date: 2010 / Resumo: Este trabalho teve como objetivo desenvolver e validar um método por cromatografia líquida de alta eficiência para a determinação de oito compostos ativos amplamente utilizados em protetores solares: benzofenona-3, octocrileno, metil benzilideno canfora, octil dimetil PABA, metoxicinamato de etilexila, butil metoxidibenzoilmetano, homosalato (usado nas suas duas formas isoméricas) e salicilato de etilexila. A separação dos compostos foi realizada em uma coluna cromatográfica ACE C18 (250 mm x 4.6 mm, 5 mm), na temperatura de 20 °C e fase movel composta por metanol:agua 88:12 v/v com eluição isocrática. A vazão foi de 1 mL min e a quantificação foi feita por padronização externa no comprimento de onda máximo de cada composto. O tempo da corrida cromatográfica foi de 18 minutos. O preparo de amostra consistiu basicamente de diluição e filtração anterior quantificação. Os parâmetros considerados na validação do método foram: faixa linear, linearidade, sensibilidade, precisão intra e inter-ensaio e exatidão. O método foi aplicado em treze amostras de diferentes fabricantes disponíveis comercialmente. O número de compostos ativos variaram entre 1 e 5 em uma mesma amostra. As concentrações dos compostos estão na faixa de 0,9-10% (m/m) e estão de acordo com o limite máximo permitido pela ANVISA. Este trabalho teve tambem como objetivo avaliar a potencialidade do uso de fluorescência de raios-X para determinar o FPS (fator de proteção solar) de protetores solares utilizando métodos quimiométricos. Para isso foram selecionadas varias amostras de um mesmo fabricante com diferentes FPS. Os espectros de raios-X obtidos foram tratados com a ferramenta quimiométrica PCA (Principal Component Analysis) para a análise exploratória dos dados e então construiu-se um modelo de calibração por PLS (Partial Least Squares). / Abstract: This work describes the development and validation of a HPLC-DAD method for determination of eight sunscreen agents: benzophenone-3, octocrylene, octyl methoxycinnamate, octyl salicylate, homosalate (used in two isomeric forms), butyl metoxydibenzoylmethane, 4-metylbenzylidene camphor and octyl dimetyl PABA in sunscreen formulations. The separation of the eight compounds were achieved using a ACE C18 column (250 mm x 4.6 mm, 5 mm), column temperature 20 °C, and a mobile phase of 88:12 (v/v) methanol-water with isocratic elution. The flow rate was 1 mL/min and quantitation was performed by external calibration at the maximum wavelength of each compound. Total run time was 18 minutes. The sample preparation was simple and consisted basically of dilution and filtration before quantitation. The critical points of the method are the column temperature, composition of the C18 stationary phase and the composition of the mobile phase. The validation parameters comprised: linear range, linearity, selectivity, intra-day and inter-day precision, and accuracy, and were in accordance with the aim of the method. Thirteen samples of sunscreen emulsions (SPF 30) of different manufacturer were analyzed. The number of the sunscreen agents varied between one and five in a same sample. The concentrations of all compounds were in the range of 0.9 to 10% (m/m) and were in accordance with the current Brazilian legislation. This work has also evaluated the potential of use of X-ray fluorescence to determine the SPF (sun protection factor) of sunscreens using chemometric methods. For this purpose, several samples from the same manufacturer (same components) with different FPS were selected. The X-ray spectra obtained were treated with a chemiometric tool PCA (Principal Component Analysis) for exploratory data analysis and then built a calibration model by PLS (Partial Least Squares). / Mestrado / Mestre em Química

Com o avanço no desenvolvimento industrial sustentável estão sendo exploradas novas aplicações de uso dos subprodutos agroindustriais. O bagaço de uva obtido a partir da vinificação ou produção de sucos mantém importantes quantidades de polifenóis em suas cascas, sementes e engaço após o processamento, úteis para proteção da pele contra os raios ultravioleta. Neste contexto, o objetivo do nosso estudo foi caracterizar quimicamente o extrato do bagaço de uva Cabernet Sauvignon e avaliar a sua segurança e eficácia clínica em fotoprotetor tópico. Nesta dissertação, o extrato hidroetanólico (70% v/v) do bagaço de uva total, incluindo cascas, sementes e engaços de Vitis vinifera L., foi obtido por percolação seguido de liofilização. Os ensaios divididos em duas etapas: i) In vitro: determinação dos fenólicos totais (FT) usando Folin-Ciocalteu e expresso em equivalentes de ácido gálico (GAE); flavonoides por meio da reação com tricloreto de alumínio e expresso em quercetina; atividade antioxidante do extrato e das formulações através da desativação de radicais livres de DPPH• expressa em equivalentes de Trolox (TE); identificação dos principais compostos fenólicos do extrato bruto por espectrometria de massa (HPLC/ESI-MS/MS); desenvolvimento de nove formulações usando o delineamento experimental; medição dos valores de transmitância das formulações referentes ao fator de proteção solar (FPS), fotoestabilidade e fator de proteção UVA (FP-UVA) através do equipamento Labsphere UV-2000S® e ii) Em seres humanos, apenas duas formulações foram avaliadas clinicamente, C sem extrato e com filtros UVA e UVB: butilmetoxidibenzoilmetano, etil-hexilmetoxicinamato e etil-hexildimetil PABA (11,5% p/p) e D com extrato (bagaço de uva 10% p/p) e filtros UV. Inicialmente, a segurança dermatológica, irritabilidade e sensibilização; fototoxicidade e fotossensibilização foram avaliadas pelo Teste de Contato Repetitivo em Humanos (HRIPT). Posteriormente, a eficácia fotoprotetora clínica foi testada na pele de dez voluntários. O teor de FT encontrado no extrato de bagaço de uva foi de 141,11 ± 3,38 mg GAE.g-1 e de flavonoides 3,01 ± 0,14 mg QE.g-1. A eficácia antioxidante das soluções metanólicas com extrato e fotoprotetor na concentração de 1 mg.mL-1 em peso seco em pH 5 e 7 foram aproximadamente: 707 µmol TE.g-1 e 520 µmol TE.g-1, respectivamente. Isto significa uma queda em torno de 26,45% da capacidade antioxidante do extrato quando incorporado à formulação. Foram identificadas por espectrometria de massa dezenove substâncias fenólicas, entre elas dímeros e trímeros de procianidinas, di-hidroflavonol, flavonóis e antocianidinas. Os resultados demonstraram efeito sinérgico entre os filtros UV e extrato vegetal no FPS e efeito antagônico com a variação do tempo de irradiação sobre as respostas do FPS, atividade antioxidante, comprimento de onda crítico, proteção UVA, proteção UVB e razão UVA/UVB. A melhor combinação eficiência-resposta foi detectada na formulação D com um aumento do FPS in vitro em cerca de 210%. Os testes de segurança não induziram qualquer reação adversa. A eficácia fotoprotetora clínica de D foi 21% (10,20 - 12,30) superior em relação à formulação C, demonstrando maior eficiência na proteção UVA. Sendo assim, C e D foram consideradas seguras para uso tópico e D estatisticamente superior tanto na proteção UVA quanto UVB comparado à amostra só associada de filtros. Logo, o bagaço de uva é um promissor ingrediente sustentável multifuncional útil para o uso em protetor solar. / With the advance in sustainable industrial development, new applications of agro-industrial by-products are being explored. Grape pomace obtained from winemaking or juice production keeps important amounts of polyphenols in their skins, seeds and stalks after processing that are useful for protection of skin against ultraviolet rays. In this context, the objective of our study was to chemically characterize Cabernet Sauvignon pomace extract and to evaluate its safety and clinical efficacy in topical photoprotector. The hydroethanolic extract (70% v/v) of the Vitis vinifera L. whole grape pomace, including seeds, skins and stalks, was obtained by percolation after lyophilization. The tests were divided into two stages: i) In vitro: total phenols (TF) using Folin-Ciocalteu and expressed in Gallic Acid Equivalent (GAE); flavonoids by reaction with aluminum trichloride and expressed as quercetin; antioxidant activity of the extract and formulations by inhibition by DPPH• expressed as Trolox equivalents (TE); identification of the main phenolic compounds of the crude extract by mass spectrometry (HPLC/ESI-MS/MS); development of nine formulations using experimental design and evaluated the SPF, photostability and UVA protection factor (UVA-PF) through the Labsphere UV-2000S® equipment; ii) In humans, only two formulations were clinically evaluated, C without extract and with UVA and UVB filters: butilmetoxidibenzoilmetano, etil-hexilmetoxicinamato and etil-hexildimetil PABA (11.5% w/w) and D with extract (10% w/w grape pomace) and filters UV. Initially, the dermatological safety, irritability and sensitization; phototoxicity and photosensitization were evaluated by the Human Repeat Insult Patch Test (HRIPT). After, the clinical photoprotective efficacy was tested on the skin of ten volunteers. The FT content found in the dried extract was 141.11 ± 3.38 mg GAE.g-1 and flavonoids 3.01 ± 0.14 mg QE.g-1. The antioxidant potential of the methanolic solutions with extracts and photoprotectors at the concentration of 1 mg.ml-1 in dry weight and at pH 5 and 7 were around: 707 µmol TE.g-1 and 520 µmol TE.g-1, respectively. This means a drop of about 26.45% of the antioxidant capacity of the extract when incorporated into the formulation. Mass spectrometry identified nineteen phenolic substances, among them procyanidins dimers and trimmers, di-hydroflavonol, flavonols and anthocyanin. The results showed a synergistic effect between the UV filters and the herbal extract in the SPF and the antagonistic effect with the variance of the irradiation time in the SPF responses, antioxidant activity, critical wavelength, UVA protection, UVB protection and UVA/UVB ratio. The best efficiency-response combination was detected in the D formulation with an in vitro SPF increase of about 210%. Safety tests did not induce any adverse reaction. The clinical efficiency of D photoprotection was 21% (10.20 - 12.30) higher than the C formulation, demonstrating high efficiency in UVA protection. Thus, C and D were considered safe for topical use and D statistically superior in both UVA and UVB protection to the only combined sample of filters. Therefore, grape pomace is a promising multifunctional sustainable ingredient qualified to be used in sunscreen industry.

Com o avanço no desenvolvimento industrial sustentável estão sendo exploradas novas aplicações de uso dos subprodutos agroindustriais. O bagaço de uva obtido a partir da vinificação ou produção de sucos mantém importantes quantidades de polifenóis em suas cascas, sementes e engaço após o processamento, úteis para proteção da pele contra os raios ultravioleta. Neste contexto, o objetivo do nosso estudo foi caracterizar quimicamente o extrato do bagaço de uva Cabernet Sauvignon e avaliar a sua segurança e eficácia clínica em fotoprotetor tópico. Nesta dissertação, o extrato hidroetanólico (70% v/v) do bagaço de uva total, incluindo cascas, sementes e engaços de Vitis vinifera L., foi obtido por percolação seguido de liofilização. Os ensaios divididos em duas etapas: i) In vitro: determinação dos fenólicos totais (FT) usando Folin-Ciocalteu e expresso em equivalentes de ácido gálico (GAE); flavonoides por meio da reação com tricloreto de alumínio e expresso em quercetina; atividade antioxidante do extrato e das formulações através da desativação de radicais livres de DPPH• expressa em equivalentes de Trolox (TE); identificação dos principais compostos fenólicos do extrato bruto por espectrometria de massa (HPLC/ESI-MS/MS); desenvolvimento de nove formulações usando o delineamento experimental; medição dos valores de transmitância das formulações referentes ao fator de proteção solar (FPS), fotoestabilidade e fator de proteção UVA (FP-UVA) através do equipamento Labsphere UV-2000S® e ii) Em seres humanos, apenas duas formulações foram avaliadas clinicamente, C sem extrato e com filtros UVA e UVB: butilmetoxidibenzoilmetano, etil-hexilmetoxicinamato e etil-hexildimetil PABA (11,5% p/p) e D com extrato (bagaço de uva 10% p/p) e filtros UV. Inicialmente, a segurança dermatológica, irritabilidade e sensibilização; fototoxicidade e fotossensibilização foram avaliadas pelo Teste de Contato Repetitivo em Humanos (HRIPT). Posteriormente, a eficácia fotoprotetora clínica foi testada na pele de dez voluntários. O teor de FT encontrado no extrato de bagaço de uva foi de 141,11 ± 3,38 mg GAE.g-1 e de flavonoides 3,01 ± 0,14 mg QE.g-1. A eficácia antioxidante das soluções metanólicas com extrato e fotoprotetor na concentração de 1 mg.mL-1 em peso seco em pH 5 e 7 foram aproximadamente: 707 µmol TE.g-1 e 520 µmol TE.g-1, respectivamente. Isto significa uma queda em torno de 26,45% da capacidade antioxidante do extrato quando incorporado à formulação. Foram identificadas por espectrometria de massa dezenove substâncias fenólicas, entre elas dímeros e trímeros de procianidinas, di-hidroflavonol, flavonóis e antocianidinas. Os resultados demonstraram efeito sinérgico entre os filtros UV e extrato vegetal no FPS e efeito antagônico com a variação do tempo de irradiação sobre as respostas do FPS, atividade antioxidante, comprimento de onda crítico, proteção UVA, proteção UVB e razão UVA/UVB. A melhor combinação eficiência-resposta foi detectada na formulação D com um aumento do FPS in vitro em cerca de 210%. Os testes de segurança não induziram qualquer reação adversa. A eficácia fotoprotetora clínica de D foi 21% (10,20 - 12,30) superior em relação à formulação C, demonstrando maior eficiência na proteção UVA. Sendo assim, C e D foram consideradas seguras para uso tópico e D estatisticamente superior tanto na proteção UVA quanto UVB comparado à amostra só associada de filtros. Logo, o bagaço de uva é um promissor ingrediente sustentável multifuncional útil para o uso em protetor solar. / With the advance in sustainable industrial development, new applications of agro-industrial by-products are being explored. Grape pomace obtained from winemaking or juice production keeps important amounts of polyphenols in their skins, seeds and stalks after processing that are useful for protection of skin against ultraviolet rays. In this context, the objective of our study was to chemically characterize Cabernet Sauvignon pomace extract and to evaluate its safety and clinical efficacy in topical photoprotector. The hydroethanolic extract (70% v/v) of the Vitis vinifera L. whole grape pomace, including seeds, skins and stalks, was obtained by percolation after lyophilization. The tests were divided into two stages: i) In vitro: total phenols (TF) using Folin-Ciocalteu and expressed in Gallic Acid Equivalent (GAE); flavonoids by reaction with aluminum trichloride and expressed as quercetin; antioxidant activity of the extract and formulations by inhibition by DPPH• expressed as Trolox equivalents (TE); identification of the main phenolic compounds of the crude extract by mass spectrometry (HPLC/ESI-MS/MS); development of nine formulations using experimental design and evaluated the SPF, photostability and UVA protection factor (UVA-PF) through the Labsphere UV-2000S® equipment; ii) In humans, only two formulations were clinically evaluated, C without extract and with UVA and UVB filters: butilmetoxidibenzoilmetano, etil-hexilmetoxicinamato and etil-hexildimetil PABA (11.5% w/w) and D with extract (10% w/w grape pomace) and filters UV. Initially, the dermatological safety, irritability and sensitization; phototoxicity and photosensitization were evaluated by the Human Repeat Insult Patch Test (HRIPT). After, the clinical photoprotective efficacy was tested on the skin of ten volunteers. The FT content found in the dried extract was 141.11 ± 3.38 mg GAE.g-1 and flavonoids 3.01 ± 0.14 mg QE.g-1. The antioxidant potential of the methanolic solutions with extracts and photoprotectors at the concentration of 1 mg.ml-1 in dry weight and at pH 5 and 7 were around: 707 µmol TE.g-1 and 520 µmol TE.g-1, respectively. This means a drop of about 26.45% of the antioxidant capacity of the extract when incorporated into the formulation. Mass spectrometry identified nineteen phenolic substances, among them procyanidins dimers and trimmers, di-hydroflavonol, flavonols and anthocyanin. The results showed a synergistic effect between the UV filters and the herbal extract in the SPF and the antagonistic effect with the variance of the irradiation time in the SPF responses, antioxidant activity, critical wavelength, UVA protection, UVB protection and UVA/UVB ratio. The best efficiency-response combination was detected in the D formulation with an in vitro SPF increase of about 210%. Safety tests did not induce any adverse reaction. The clinical efficiency of D photoprotection was 21% (10.20 - 12.30) higher than the C formulation, demonstrating high efficiency in UVA protection. Thus, C and D were considered safe for topical use and D statistically superior in both UVA and UVB protection to the only combined sample of filters. Therefore, grape pomace is a promising multifunctional sustainable ingredient qualified to be used in sunscreen industry.

A nanotecnologia se aplica a diversos setores da ciência, sendo que na área cosmética os investimentos tem reforçado a ideia de que produtos nanotecnológicos proporcionam vantagens reais aos consumidores. A exposição excessiva a luz solar pode causar efeitos indesejáveis como eritemas e câncer de pele, logo, os filtros solares são usados como auxilio na prevenção de tais efeitos. O p-metoxicinamato de octila e a benzofenona-3 são filtros UV químicos que absorvem radiação UVB e UVA respectivamente, ambos são amplamente empregados em produtos fotoprotetores. A crescente exigência do consumidor e os avanços no conhecimento sobre a obtenção e estabilidade dos sistemas dispersos viabilizam o desenvolvimento de veículos diferenciados, como as nanoemulsões, que alem da inerente estabilidade apresentam aspecto sensorial agradável e alta capacidade de espalhabilidade. Um método eficiente para se obter nanoemulsão, empregando baixa energia de emulsificação e da temperatura de inversão de fases (Phase Inversion Temperature, PIT), baseado na mudança de solubilidade dos tensoativos não iônicos etoxilados com a variaço da temperatura. Foram objetivos do presente estudo: desenvolvimento de nanoemulsão contendo p-metoxicinamato de octila e benzofenona-3, empregando o método da PIT; determinação do tamanho de partícula e a distribuição de tamanhos por meio de espectrometria acústica; determinação da eficácia fotoprotetora in vitro por espectrofotometria de refletância difusa com esfera de integração; e a avaliação da influencia das variáveis, velocidade de agitação, concentração de glicerina e de cloreto de sódio no processo de desenvolvimento da nanoemulsão. A nanoemulsão apresentou valor da PIT de 72,0 °C, brilho azulado, fluidez e estabilidade por, pelo menos, 90 dias quando armazenada em temperatura ambiente (22,0 ± 2,0 °C). A distribuição de tamanhos de partícula apresentou perfil bimodal com medias de tamanhos de 10 nm (61%) e 4,5 µm (39%). A avaliação da eficácia fotoprotetora in vitro apresentou FPS igual a 8,0 ± 0,9, não alcançando o potencial de \"amplo espectro\". A velocidade de agitação, a concentração de glicerina e de cloreto de sódio influenciaram na PIT, mas não no tamanho de partícula ou eficácia fotoprotetora in vitro. Sendo que, a concentração de NaCl teve maior influencia na PIT, seguida pela concentração de glicerina e velocidade de agitação. / Nanotechnology applies to various sectors of science, and in the cosmetics area, investments have enhanced the idea that nanotechnology products provide real benefits to consumers. Excessive exposure to sunlight can cause side effects such as erythema and skin cancer, thus sunscreens are used in preventing such effects. The octyl methoxycinnamate and benzophenone-3 are chemical UV filters which absorbs UVB and UVA radiation respectively, both are widely used in sunscreens products. The increasing consumer demand and advances in knowledge about the production and stability of dispersed systems enable the development of differentiated vehicles, such as nanoemulsions, which besides the inherent stability, show pleasant sensorial aspect, and high spread ability. An efficient method for obtaining nanoemulsion, employing low energy of emulsification is the phase inversion temperature (Phase Inversion Temperature, PIT) based on the change in solubility of ethoxylated nonionic surfactants with temperature variation. The objectives of this study: development of nanoemulsion containing p-octyl methoxycinnamate and benzophenone-3, using the method of PIT; determination of particle size and size distribution by means of acoustic spectrometer; determination of in vitro photoprotective efficacy by diffuse reflectance spectrophotometer with integrating sphere; and evaluation of the influence of variables, speed of agitation, concentration of glycerin and sodium chloride in the development process of the nanoemulsion. The nanoemulsion showed the PIT value of 72.0 °C, bluish brightness, fluidity and stability for at least 90 days if stored at room temperature (22.0 ± 2.0 °C). The particle size distribution showed bimodal profile with average sizes of 10 nm (61%) and 4.5 m (39%). The evaluation of the in vitro photoprotective efficacy showed FPS equal to 8.0 ± 0.9, not reaching the potential of \"broad spectrum\". The speed of agitation, concentration of glycerin and sodium chloride affected the PITbut not in the particle size or in vitro photoprotective efficacy. Given that the NaCl concentration had greater influence on the ITP, then the glycerin concentration and agitation speed.

This thesis is focused on the phenomenon of corporate social responsibility (CSR). Opening parts of the work are devoted to the concept in general and its evolution in the context of other theories investigating the issue of responsibility in business as well. The part the work describes recommendations for the implementation process of the CSR concept into an organizational strategy. Following chapters are based on the stakeholder theory and a related specification of the CSR content within three thematic spheres - economic, social and environmental. A part of the work describes opportunities of CSR in a field of a human resources management. The last chapter describes utilization of CSR in the human resource management in the particular company. The chapter also contains recommendations based on the concept of CSR in order to bring positive effects to the company and employees, who are an important group of stakeholders. Key words: Corporate social responsibility, stakeholder theory, ethics, work-life balance, diversity management, working conditions, welfare service, outplacement.

A nanotecnologia se aplica a diversos setores da ciência, sendo que na área cosmética os investimentos tem reforçado a ideia de que produtos nanotecnológicos proporcionam vantagens reais aos consumidores. A exposição excessiva a luz solar pode causar efeitos indesejáveis como eritemas e câncer de pele, logo, os filtros solares são usados como auxilio na prevenção de tais efeitos. O p-metoxicinamato de octila e a benzofenona-3 são filtros UV químicos que absorvem radiação UVB e UVA respectivamente, ambos são amplamente empregados em produtos fotoprotetores. A crescente exigência do consumidor e os avanços no conhecimento sobre a obtenção e estabilidade dos sistemas dispersos viabilizam o desenvolvimento de veículos diferenciados, como as nanoemulsões, que alem da inerente estabilidade apresentam aspecto sensorial agradável e alta capacidade de espalhabilidade. Um método eficiente para se obter nanoemulsão, empregando baixa energia de emulsificação e da temperatura de inversão de fases (Phase Inversion Temperature, PIT), baseado na mudança de solubilidade dos tensoativos não iônicos etoxilados com a variaço da temperatura. Foram objetivos do presente estudo: desenvolvimento de nanoemulsão contendo p-metoxicinamato de octila e benzofenona-3, empregando o método da PIT; determinação do tamanho de partícula e a distribuição de tamanhos por meio de espectrometria acústica; determinação da eficácia fotoprotetora in vitro por espectrofotometria de refletância difusa com esfera de integração; e a avaliação da influencia das variáveis, velocidade de agitação, concentração de glicerina e de cloreto de sódio no processo de desenvolvimento da nanoemulsão. A nanoemulsão apresentou valor da PIT de 72,0 °C, brilho azulado, fluidez e estabilidade por, pelo menos, 90 dias quando armazenada em temperatura ambiente (22,0 ± 2,0 °C). A distribuição de tamanhos de partícula apresentou perfil bimodal com medias de tamanhos de 10 nm (61%) e 4,5 µm (39%). A avaliação da eficácia fotoprotetora in vitro apresentou FPS igual a 8,0 ± 0,9, não alcançando o potencial de \"amplo espectro\". A velocidade de agitação, a concentração de glicerina e de cloreto de sódio influenciaram na PIT, mas não no tamanho de partícula ou eficácia fotoprotetora in vitro. Sendo que, a concentração de NaCl teve maior influencia na PIT, seguida pela concentração de glicerina e velocidade de agitação. / Nanotechnology applies to various sectors of science, and in the cosmetics area, investments have enhanced the idea that nanotechnology products provide real benefits to consumers. Excessive exposure to sunlight can cause side effects such as erythema and skin cancer, thus sunscreens are used in preventing such effects. The octyl methoxycinnamate and benzophenone-3 are chemical UV filters which absorbs UVB and UVA radiation respectively, both are widely used in sunscreens products. The increasing consumer demand and advances in knowledge about the production and stability of dispersed systems enable the development of differentiated vehicles, such as nanoemulsions, which besides the inherent stability, show pleasant sensorial aspect, and high spread ability. An efficient method for obtaining nanoemulsion, employing low energy of emulsification is the phase inversion temperature (Phase Inversion Temperature, PIT) based on the change in solubility of ethoxylated nonionic surfactants with temperature variation. The objectives of this study: development of nanoemulsion containing p-octyl methoxycinnamate and benzophenone-3, using the method of PIT; determination of particle size and size distribution by means of acoustic spectrometer; determination of in vitro photoprotective efficacy by diffuse reflectance spectrophotometer with integrating sphere; and evaluation of the influence of variables, speed of agitation, concentration of glycerin and sodium chloride in the development process of the nanoemulsion. The nanoemulsion showed the PIT value of 72.0 °C, bluish brightness, fluidity and stability for at least 90 days if stored at room temperature (22.0 ± 2.0 °C). The particle size distribution showed bimodal profile with average sizes of 10 nm (61%) and 4.5 m (39%). The evaluation of the in vitro photoprotective efficacy showed FPS equal to 8.0 ± 0.9, not reaching the potential of \"broad spectrum\". The speed of agitation, concentration of glycerin and sodium chloride affected the PITbut not in the particle size or in vitro photoprotective efficacy. Given that the NaCl concentration had greater influence on the ITP, then the glycerin concentration and agitation speed.

Inflation expectations have been of great interest to economists because they predict how agents in an economy set prices and react to changes in various macroeconomic variables. The existence of Keynesian liquidity traps in Japan and the United States have helped emphasize the importance of inflation expectations, especially when monetary policy is rendered ineffective and there is almost perfect substitutability between money and bonds due to the zero bound condition of interest rates. Given the canonical theories of rational and adaptive expectations, this paper will use a simple model of the economy to measure the effect of various macroeconomic variables on the formation of inflation expectations. It will test to see how consumers, economists and the market measure and forecast inflation both in the short and in the long run.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-05-19T11:18:30Z No. of bitstreams: 1 cintiaelenaleitezini.pdf: 1012817 bytes, checksum: 16d3eeb0ce6461fd408d038e2c23987e (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-06-27T18:41:38Z (GMT) No. of bitstreams: 1 cintiaelenaleitezini.pdf: 1012817 bytes, checksum: 16d3eeb0ce6461fd408d038e2c23987e (MD5) / Made available in DSpace on 2016-06-27T18:41:38Z (GMT). No. of bitstreams: 1 cintiaelenaleitezini.pdf: 1012817 bytes, checksum: 16d3eeb0ce6461fd408d038e2c23987e (MD5) Previous issue date: 2012-07-05 / A exposição inadequada a radiação solar ocasiona sérios danos a pele, como queimaduras, fotoenvelhecimento, queratose actínica e câncer, sendo por isso motivo crescente de preocupação por parte dos órgãos de saúde. Estima-se que no Brasil surjam 140.000 novos casos de câncer de pele em 2012. O principal mecanismo pelo qual a radiação UV danifica a pele é através da lesão ao DNA, que pode ser direta, por dimerização de suas bases, ou indireta, via ação de espécies reativas de oxigênio. Uma das formas de evitar os efeitos nocivos da radiação solar é a utilização de protetores solares. Estudos tem sido realizados com a finalidade de ampliar o fator de proteção solar (FPS) pela associação de extratos vegetais com filtros orgânicos. Vegetais ricos em compostos fenólicos e flavonóides são de particular interesse por estarem relacionados a atividade fotoprotetora e antioxidante. Nesse sentido, o presente trabalho teve o objetivo de avaliar o potencial fotoprotetor e a atividade antioxidante in vitro de extratos de Mikania glomerata, Ginkgo biloba, Matricaria chamomilla, Aquillea millefolium e Aesculus hippocastanum e das substâncias bioativas rutina e vanilina. Os teores de compostos fenólicos e flavonóides dos extratos foram determinados espectrofotometricamente e a atividade antioxidante de extratos, rutina e vanilina foi avaliada frente ao radical DPPH. Formulações em gel e emulsão O/A foram preparadas associando-se 5% do filtro orgânico ácido 2-fenilbenzimidazol-5-sulfônico a 3,5% v/v de extratos, 0,1% ou 0,25% de rutina ou vanilina e os valores de FPS determinados espectrofotometricamente pelo método de Mansur. O extrato de A. hippocastanum produziu a maior elevação de FPS do gel, enquanto a rutina 0,25% produziu o valor mais elevado de FPS da emulsão. O extrato de A. hippocastanum demonstrou o maior potencial fotoprotetor e antioxidante, podendo ser considerado promissor adjuvante em formulações de protetores solares. / Inadequate exposure to sun radiation causes serious skin damages, such as sunburn, photoaging, actinic keratosis and cancer, and therefore causes growing concern among health organizations. It is estimated that in Brasil 140.000 new cases of skin cancer will arise in 2012. The main mechanism in which the UV radiation damages the skin is through DNA lesion, which can be direct by dimerization of its bases, or indirectly via action of reactive oxygen species. One way to avoid the harmful effects of sun radiation is to apply sunscreens. Studies have been done aiming to increase the sun protection factor (SPF) by the association of plant extracts with organic filters. Plant extracts rich in phenolic and flavonoid compounds are of particular interest since they are related to photoprotective and antioxidant activities. Thus, this study aims to assess the potential photoprotection and the antioxidant activity in vitro of Mikania glomerata, Ginkgo biloba, Matricaria chamomilla, Aquillea millefolium and Aesculus hippocastanum extracts, also the bioactive substances rutin and vanillin. The phenolic and flavonoids compound levels of the extracts were settled by spectrofotometry and the extract’s antioxidant activity, rutin and vanillin, were evaluated against DPPH radical. Gel and O/W emulsion formulations were prepared by adding 5% of organic filter 2-phenylbenzimidazole-5-sulfonic acid to 3,5% v/v of extracts, 0,1% or 0,25% of rutin or vanillin and the SPF values determined spectrophotometrically by Mansur’s method. The extract of A. hippocastanum produced the highest elevation of gel SPF, while 0.25% rutin produced the highest value of emulsion SPF. The extract of A. hippocastanum showed the greatest potential photoprotective and antioxidant, it can be considered promising in formulations of sunscreens.

This thesis contains three essays covering different topics in the field of statistics<p>and econometrics of survey data. Chapters one and two analyse two aspects<p>of the Survey of Professional Forecasters (SPF hereafter) dataset. This survey<p>provides a large information on macroeconomic expectations done by the professional<p>forecasters and offers an opportunity to exploit a rich information set.<p>But it poses a challenge on how to extract the relevant information in a proper<p>way. The last chapter addresses the issue of analyzing the opinions on the euro<p>reported in the Flash Eurobaromenter dataset.<p>The first chapter Measuring Uncertainty and Disagreement in the European<p>Survey of Professional Forecasters proposes a density forecast methodology based<p>on the piecewise linear approximation of the individual’s forecasting histograms,<p>to measure uncertainty and disagreement of the professional forecasters. Since<p>1960 with the introduction of the SPF in the US, it has been clear that they were a<p>useful source of information to address the issue on how to measure disagreement<p>and uncertainty, without relying on macroeconomic or time series models. Direct<p>measures of uncertainty are seldom available, whereas many surveys report point<p>forecasts from a number of individual respondents. There has been a long tradition<p>of using measures of the dispersion of individual respondents’ point forecasts<p>(disagreement or consensus) as proxies for uncertainty. Unlike other surveys, the<p>SPF represents an exception. It directly asks for the point forecast, and for the<p>probability distribution, in the form of histogram, associated with the macro variables<p>of interest. An important issue that should be considered concerns how to<p>approximate individual probability densities and get accurate individual results<p>for disagreement and uncertainty before computing the aggregate measures. In<p>contrast to Zarnowitz and Lambros (1987), and Giordani and Soderlind (2003) we<p>overcome the problem associated with distributional assumptions of probability<p>density forecasts by using a non parametric approach that, instead of assuming<p>a functional form for the individual probability law, approximates the histogram<p>by a piecewise linear function. In addition, and unlike earlier works that focus on<p>US data, we employ European data, considering gross domestic product (GDP),<p>inflation and unemployment.<p>The second chapter Optimal Combination of Survey Forecasts is based on<p>a joint work with Christine De Mol and Domenico Giannone. It proposes an<p>approach to optimally combine survey forecasts, exploiting the whole covariance<p>structure among forecasters. There is a vast literature on forecast combination<p>methods, advocating their usefulness both from the theoretical and empirical<p>points of view (see e.g. the recent review by Timmermann (2006)). Surprisingly,<p>it appears that simple methods tend to outperform more sophisticated ones, as<p>shown for example by Genre et al. (2010) on the combination of the forecasts in<p>the SPF conducted by the European Central Bank (ECB). The main conclusion of<p>several studies is that the simple equal-weighted average constitutes a benchmark<p>that is hard to improve upon. In contrast to a great part of the literature which<p>does not exploit the correlation among forecasters, we take into account the full<p>covariance structure and we determine the optimal weights for the combination<p>of point forecasts as the minimizers of the mean squared forecast error (MSFE),<p>under the constraint that these weights are nonnegative and sum to one. We<p>compare our combination scheme with other methodologies in terms of forecasting<p>performance. Results show that the proposed optimal combination scheme is an<p>appropriate methodology to combine survey forecasts.<p>The literature on point forecast combination has been widely developed, however<p>there are fewer studies analyzing the issue for combination density forecast.<p>We extend our work considering the density forecasts combination. Moving from<p>the main results presented in Hall and Mitchell (2007), we propose an iterative<p>algorithm for computing the density weights which maximize the average logarithmic<p>score over the sample period. The empirical application is made for the<p>European GDP and inflation forecasts. Results suggest that optimal weights,<p>obtained via an iterative algorithm outperform the equal-weighted used by the<p>ECB density combinations.<p>The third chapter entitled Opinion surveys on the euro: a multilevel multinomial<p>logistic analysis outlines the multilevel aspects related to public attitudes<p>toward the euro. This work was motivated by the on-going debate whether the<p>perception of the euro among European citizenships after ten years from its introduction<p>was positive or negative. The aim of this work is, therefore, to disentangle<p>the issue of public attitudes considering either individual socio-demographic characteristics<p>and macroeconomic features of each country, counting each of them<p>as two separate levels in a single analysis. Considering a hierarchical structure<p>represents an advantage as it models within-country as well as between-country<p>relations using a single analysis. The multilevel analysis allows the consideration<p>of the existence of dependence between individuals within countries induced by<p>unobserved heterogeneity between countries, i.e. we include in the estimation<p>specific country characteristics not directly observable. In this chapter we empirically<p>investigate which individual characteristics and country specificities are<p>most important and affect the perception of the euro. The attitudes toward the<p>euro vary across individuals and countries, and are driven by personal considerations<p>based on the benefits and costs of using the single currency. Individual<p>features, such as a high level of education or living in a metropolitan area, have<p>a positive impact on the perception of the euro. Moreover, the country-specific<p>economic condition can influence individuals attitudes. / Doctorat en Sciences économiques et de gestion / info:eu-repo/semantics/nonPublished

The paper examines the extent to which the prestige value of a retiree’s former occupation increases the likelihood that they will make a transition into volunteering after retirement. Following social production function theory, we assume that when a person retires, the prestige value attached to their former occupation fades. The fact that volunteering has the character of a collective good provides the opportunity to gain social prestige to offset the loss of occupational prestige. However, the extent of the incentive to volunteer will be distributed unequally across occupations: the higher the former occupational prestige value, the higher the perceived loss of prestige after retirement. Thus, doing a job with high prestige value increases the incentive to volunteer in retirement. This assumption is tested, using data taken from the German Socio-Economic Panel (GSOEP) 1992-2013. The sample contains 1,631 workers and 589 retirees, 278 of whom transitioned into volunteering during the observation window. Based on Kaplan-Meier-Failure-Estimates and complementary log-log hazard models, findings show a positive effect of occupational prestige on the transition into volunteering. Thus, the loss of high occupational prestige can be compensated by the social prestige associated with volunteering. Formal volunteering in retirement follows, albeit to a lesser extent, the logic of the occupational social strata.