Radical reactions play central roles in regulating regional air quality and global climate. Some potentially important gas phase radical reactions are being investigated in this research project, including Cl reactions with acetone, butanone, 3-pentanone, pyridine, and dimethyl selenide (DMSe), HO2 complex formation and dissociation with formic and acetic acids, and reactive and non-reactive quenching of O(1D) by the potent greenhouse gases SO2F2, NF3, and SF5CF3. The involved radicals are generated by laser flash photolysis (LFP). Temporal profiles of either the radical reactant or a product are monitored in "real time" using atomic resonance fluorescence spectroscopy (RF), time-resolved UV-visible absorption spectroscopy (TRUVVAS), or tunable diode laser absorption spectroscopy (TDLAS), allowing kinetic and mechanistic information of these reactions to be obtained. These studies provide new knowledge of the investigated radical reactions and facilitate a better understanding of their significance in atmospheric chemistry.

Made available in DSpace on 2014-06-11T19:25:25Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-01-15Bitstream added on 2014-06-13T18:26:25Z : No. of bitstreams: 1 almeida_mgj_me_arafcf_parcial.pdf: 82683 bytes, checksum: 49424d5182616aaa8e926f756efd65e1 (MD5) Bitstreams deleted on 2015-02-09T14:35:42Z: almeida_mgj_me_arafcf_parcial.pdf,Bitstream added on 2015-02-09T14:36:22Z : No. of bitstreams: 1 000710077.pdf: 903439 bytes, checksum: 7ad6ad625787ddd4aff6f1d6cad4169e (MD5) Bitstreams deleted on 2015-02-09T17:15:05Z: 000710077.pdf,Bitstream added on 2015-02-09T17:15:41Z : No. of bitstreams: 1 000710077.pdf: 903439 bytes, checksum: 7ad6ad625787ddd4aff6f1d6cad4169e (MD5) / A tendência atual na indústria cosmética é o desenvolvimento de produtos multifuncionais, ou seja, aqueles com capacidade de apresentar diferentes funções, possibilitando diferentes resultados para o consumidor. Seguindo esta tendência, ativos naturais são alternativas interessantes como substitutos a um único composto ativo, uma vez que são matrizes complexas e apresentam diversos componentes que podem possuir diferentes mecanismos de ação e, assim, conferir ao produto mais de uma função. Por este motivo, nos últimos anos o uso de extratos naturais tem crescido muito nesta área. Com o aumento da aplicação de extratos naturais em produtos cosméticos, há também a necessidade de estudos que comprovem sua eficácia e segurança. Uma das principais funções buscadas em produtos cosméticos é a ação antienvelhecimento, ou seja, a capacidade dos produtos em atuar neutralizando radicais livres. Neste contexto, o objetivo deste trabalho foi avaliar a eficácia e segurança do extrato de Ascophyllum nodosum, além de desenvolver um sistema emulsionado para sua incorporação e verificar a eficácia deste sistema. Os resultados de citotoxicidade mostraram que este extrato pode ser utilizado com segurança na concentração proposta (1,2% m/m). Além disso, foi avaliado, por metodologias in vitro, o potencial antioxidante e o potencial de inibir a atividade da tirosinase, sendo verificado que o extrato de A. nodosum apresenta a capacidade de atuar neutralizando radicais livres e inibindo a atividade enzimática da tirosinase no processo de melanogênese. Apesar de serem necessários estudos complementares para garantir a eficácia, o fitocosmético desenvolvido com o extrato aquoso de A. nodosum apresenta enorme potencial de aplicação podendo resultar em preparações cosméticas multifuncionais / The current trend in the cosmetic industry is the development of multifunctional products, or, those with the ability to have different functions, facilitating the results to the consumer. Following this trend, natural actives are interesting alternatives as substitutes for a single active compound, since they are complex matrices and present various components that may have different mechanisms of action and thereby give the product more than one function. For this reason, in recent years the use of natural extracts has grown a lot in this area. With the increased use of natural extracts in cosmetic products, there is also a need for studies to prove its effectiveness and safety. A major function is sought in cosmetic anti-aging action, for instance, the ability of the products act by neutralizing free radicals. In this context, the aim of this study was to evaluate the effectiveness and safety of the extract of Ascophyllum nodosum, and develop a system for incorporation emulsified and verify the effectiveness of this system. The results of cytotoxicity have shown that this extract can be safely used in the proposed concentration (1.2% w/w). Furthermore, it was evaluated by in vitro methods, the antioxidant potential and the potential to inhibit the activity of tyrosinase, and found that the extract of A. nodosum has the ability to act by neutralizing free radicals and inhibiting the enzymatic activity of tyrosinase in the process of melanogenesis. Although additional studies are needed to ensure effectiveness, phytocosmetic developed with aqueous extract of A. nodosum has enormous potential application may result in multifunctional cosmetic preparations

Orientador: Chung Man Chin / Coorientador: Vera Lucia Borges Isaac / Banca: Marcos Antônio Correa / Banca: Helena Margarida Ribeiro / Resumo: A tendência atual na indústria cosmética é o desenvolvimento de produtos multifuncionais, ou seja, aqueles com capacidade de apresentar diferentes funções, possibilitando diferentes resultados para o consumidor. Seguindo esta tendência, ativos naturais são alternativas interessantes como substitutos a um único composto ativo, uma vez que são matrizes complexas e apresentam diversos componentes que podem possuir diferentes mecanismos de ação e, assim, conferir ao produto mais de uma função. Por este motivo, nos últimos anos o uso de extratos naturais tem crescido muito nesta área. Com o aumento da aplicação de extratos naturais em produtos cosméticos, há também a necessidade de estudos que comprovem sua eficácia e segurança. Uma das principais funções buscadas em produtos cosméticos é a ação antienvelhecimento, ou seja, a capacidade dos produtos em atuar neutralizando radicais livres. Neste contexto, o objetivo deste trabalho foi avaliar a eficácia e segurança do extrato de Ascophyllum nodosum, além de desenvolver um sistema emulsionado para sua incorporação e verificar a eficácia deste sistema. Os resultados de citotoxicidade mostraram que este extrato pode ser utilizado com segurança na concentração proposta (1,2% m/m). Além disso, foi avaliado, por metodologias in vitro, o potencial antioxidante e o potencial de inibir a atividade da tirosinase, sendo verificado que o extrato de A. nodosum apresenta a capacidade de atuar neutralizando radicais livres e inibindo a atividade enzimática da tirosinase no processo de melanogênese. Apesar de serem necessários estudos complementares para garantir a eficácia, o fitocosmético desenvolvido com o extrato aquoso de A. nodosum apresenta enorme potencial de aplicação podendo resultar em preparações cosméticas multifuncionais / Abstract: The current trend in the cosmetic industry is the development of multifunctional products, or, those with the ability to have different functions, facilitating the results to the consumer. Following this trend, natural actives are interesting alternatives as substitutes for a single active compound, since they are complex matrices and present various components that may have different mechanisms of action and thereby give the product more than one function. For this reason, in recent years the use of natural extracts has grown a lot in this area. With the increased use of natural extracts in cosmetic products, there is also a need for studies to prove its effectiveness and safety. A major function is sought in cosmetic anti-aging action, for instance, the ability of the products act by neutralizing free radicals. In this context, the aim of this study was to evaluate the effectiveness and safety of the extract of Ascophyllum nodosum, and develop a system for incorporation emulsified and verify the effectiveness of this system. The results of cytotoxicity have shown that this extract can be safely used in the proposed concentration (1.2% w/w). Furthermore, it was evaluated by in vitro methods, the antioxidant potential and the potential to inhibit the activity of tyrosinase, and found that the extract of A. nodosum has the ability to act by neutralizing free radicals and inhibiting the enzymatic activity of tyrosinase in the process of melanogenesis. Although additional studies are needed to ensure effectiveness, phytocosmetic developed with aqueous extract of A. nodosum has enormous potential application may result in multifunctional cosmetic preparations / Mestre

The Earth's atmosphere is a large photochemical reactor consisting primarily of N2 (~78%) and O2 (~21%) with Ar and water vapor being the next most abundant constituents. All of the remaining gases in the atmosphere are referred to as 'trace gases', and they play a critical role in understanding climate change, urban air quality, ozone production and depletion, and in determining the overall 'health' of the atmosphere. These trace components are present in our atmosphere with mixing ratios, i.e., mole fractions, ranging from sub parts per trillion to several hundred parts per million. One class of trace constituents that play a critical role in atmospheric chemistry are free radicals. Free radicals are highly reactive, often initiating the oxidation of natural and anthropogenic atmospheric species, thereby often controlling the fate and lifetimes of these species. The research comprising this dissertation focuses on laboratory studies of the kinetics and mechanisms of free radical (atomic halogen) reactions that can impact the levels of important trace atmospheric species. In the studies reported herein, laser flash photolysis (LFP) was coupled with time resolved atomic resonance fluorescence (RF) spectroscopic detection of Cl or Br atoms to investigate halogen atom chemistry. The research addresses three groups of reactions: Cl atom reactions with alkyl bromides, Cl and Br-initiated oxidations of small (C2-C6) alkenes, and Cl reactions with CH3SCH3 (DMS, dimethylsulfide) and CH3SeCH3 (DMSe, dimethylselenide). The alkyl bromide reactions were experimentally unique in that we were able to deduce kinetics of the Cl atom reaction with bromoethane, n-bromopropane, and 1,2-dibromoethane by monitoring the appearance of the Br product by LFP-RF. The Br is formed via elimination that occurs essentially instantaneously following β-H abstraction by the Cl atom. All three of the bromoalkanes investigated are emitted into the atmosphere primarily from anthropogenic sources and all three have been identified by the World Meteorological Organization (WMO) as very short-lived (lifetime less than 6 months) source gases with significant ozone depletion potentials (ODPs). Additionally, the bromoalkanes mentioned above have been of interest as model compounds for larger partially halogenated organics found in the atmosphere, and they have been considered as potential replacement compounds for chlorofluorocarbons (CFCs) that have been banned as a result of the Montreal Protocol. Brominated very short-lived compounds are thought to contribute 20-25% of total stratospheric bromine. Thus, there is considerable interest in understanding the atmospheric chemistry of even the most short-lived organic bromine compounds. Temporal profiles of Br atoms provided important kinetic and mechanistic insight for the reactions over a wide range of temperature and pressure. Temperature-dependent rate coefficients are determined for the alkyl bromides of interest for the first time, and the potential importance of the Cl reaction as an atmospheric degradation pathway for each alkyl bromide is qualitatively assessed. The studies of halogen atom reactions with alkenes focused on formation of weakly-bound adducts where kinetics of adduct formation and dissociation as well as non-adduct forming channels were evaluated. The elementary steps in the Br initiated oxidation of the alkenes 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-2-butene (tetramethylethylene, TME), and 1,3-butadiene have been investigated. The experimental kinetic database for these reactions is quite sparse. The kinetic results reported herein, suggests that Br reaction with the above olefins is much faster than previously thought. Analysis of the temperature dependence of the "approach to equilibrium" kinetic data in conjunction with electronic structure calculations allows for determination of enthalpy and entropy changes associated with each addition reaction. Where possible, both forward addition and reverse dissociation channels as well as H-abstraction pathways were characterized. The enthalpy change associated with the addition reaction to give the Br−isoprene and Br−1,3-butadiene adducts has been determined for the first time and the bond dissociation enthalpy obtained for the Br−TME adduct is in reasonable agreement with the only other previously reported value. It should be noted that in the case of isoprene and 1,3-butadiene, there are multiple possible adducts that could be formed. In order to help clarify which adducts are more or less likely to be formed, we rely on electronic structure calculations (see Chapter 5) to aid in our overall understanding of the adduct forming channels. Furthermore, for the Br reactions with the three alkenes above, atomic Br kinetics have been monitored directly both in the absence and in the presence of O2 which allowed, for the first time, determination of rate coefficients for the elementary steps in the overall complex mechanism including determination of the Br−olefin + O2 rate coefficient. Also included in this group of reactions is the chlorine reaction with isoprene. In addition to the well-known fact that isoprene is emitted into the atmosphere from vegetation, a potentially significant marine source of isoprene has received considerable attention. Chlorine has long been thought to exist primarily in marine environments, however, recent findings also suggest a significant Cl production rate in the middle of the continental United States. There are numerous room temperature kinetic studies for the Cl + isoprene reaction in the literature, however, there is only one temperature dependent study reported. Current recommended 298 K rate coefficients for isoprene reactions suggest the Cl reaction is ~ 4x faster than the analogous OH reaction. If indeed this is the case, the Cl reaction could play a non-neglibible role in isoprene oxidation in atmospheric locales where Cl concentrations are relatively high. In addition, the C−Cl bond strength in Cl−C5H8 is obtained from direct measurements of the forward and reversible addition rate coefficients. Our results are compared with the literature data, and the potential importance of Cl-initiated oxidation as an atmospheric sink for isoprene is assessed. The final group of reactions investigated involves reactions of Cl with DMS and DMSe. DMS and DMSe are the most prevalent sulfur and selenium compounds emitted to the atmosphere from the oceans. The oxidation of DMS has been studied extensively due to the interest in the possible role of DMS oxidation in the formation of sulfate aerosols, however, DMSe oxidation processes have hardly been studied at all. And, DMSe oxidation products are likely to be less volatile than the analogous DMS species. Selenium is an essential nutrient for many plants and animals; however, there is a fine line between enough and excess selenium which can be toxic. Most studies suggest that atmospheric deposition is an important source of Se contamination, and it is therefore critical to evaluate the source emissions and fate of Se in the atmosphere. Since the majority of atmospheric Se exists in the form of DMSe, determination of the kinetics and oxidation mechanisms of DMSe will go a long way towards understanding the global biogeochemical cycle of Se. Both reversible addition and H-abstraction pathways have been characterized, and the first experimental determination of bond strength of the gas-phase DMS−Cl and DMSe−Cl adducts have been obtained.