O material particulado (MP) atmosférico é associado a vários agravos e doenças, sendo recentemente classificado como carcinogênico para humanos (Grupo 1) pela Agência Internacional de Pesquisa em Câncer (IARC). Embora sua toxicidade, incluindo a genotoxicidade, esteja reconhecidamente ligada ao tamanho das partículas, a contribuição da sua composição química para esses efeitos ainda não está completamente elucidada. O tamanho e a composição das partículas são influenciados por características meteorológicas e climáticas, com destaque para a temperatura e o período de radiação solar. O teste Salmonella/microssoma é o mais utilizado para avaliação da mutagenicidade de amostras de MP, contudo um número reduzido de linhagens é usado. Assim, o objetivo desse estudo foi investigar e comparar a influência das diferentes condições atmosféricas e climáticas das cidades de Limeira (Brasil), Estocolmo (Suécia) e Quioto (Japão) nos perfis de mutagenicidade, utilizando 11 linhagens com diferentes seletividades, e nos perfis de composição química de amostras compostas de partículas totais em suspensão (PTS) coletadas durante o inverno dessas cidades. Para que os resultados pudessem ser diretamente comparados foi adotada a mesma metodologia, incluindo o procedimento de amostragem, o método de preparo de amostra, o protocolo do teste de mutagenicidade e as técnicas de análises químicas para identificação de hidrocarbonetos policíclicos aromáticos (HPA) e de seus derivados alquilados. Limeira apresentou a maior concentração de PTS (99,0 µg/m3), seguida por Quioto (28,0 µg/m3) e Estocolmo (6,2 µg/m3). Apesar da concentração de PTS em Limeira ser 16 vezes maior que em Estocolmo e 3,5 vezes maior que em Quioto, as porcentagens de material orgânico extraído (MOE) obtidas foram 9, 15 e 5%, respectivamente. Os extratos das amostras de PTS coletadas nas três cidades apresentaram atividade mutagênica para todas as linhagens, tanto na ausência quanto na presença de S9, com exceção da TA102 que não detectou a atividade mutagênica em nenhum dos extratos, e para YG7108 na presença de S9, apenas para a amostra de Limeira. Apesar das diferenças nas condições meteorológicas e climáticas dessas cidades, seus perfis de mutagenicidade foram semelhantes. A menor potência mutagênica para a YG7108 na ausência de S9 e a ausência de mutagenicidade na presença de S9 revela a menor contribuição de agentes alquilantes para a mutagenicidade da amostra de Limeira em relação as demais cidades. Considerando a seletividade das linhagens utilizadas, foi observado maior contribuição de compostos que causam danos oxidativo ao DNA e de agentes alquilantes para a mutagenicidade da amostra de Quioto. Porém, de acordo com as respostas das linhagens que possuem atividade aumentada das enzimas nitroredutase (NR) e/ou O-acetiltransferase (OAT), YG1021, YG1024 e YG1041, revelam a maior contribuição de nitroarenos e aminas aromáticas para a mutagenicidade das três cidades, com destaque para aqueles mutágenos que dependem da ativação via OAT. As potências mutagênicas expressadas em função da massa de MOE (rev./µg MOE) foram similares para todas as amostras. Quando expressas por volume de ar (rev./m3), as potências mutagênicas foram proporcionais às concentrações de PTS das três cidades (Limeira > Quioto > Estocolmo). Quando aplicadas as razões diagnósticas foi possível verificar uma mistura de fontes de poluição em Limeira e Estocolmo. As razões diagnósticas dos HPA indicam que a amostra de Limeira é composta por partículas frescas, com um leve predomínio de fontes de combustão. A amostra de Estocolmo apresenta partículas envelhecidas e com predomínio de fontes petrogênicas. Esse resultado foi inesperado, uma vez que as condições atmosféricas de Limeira são mais favoráveis ao envelhecimento das partículas que as de Estocolmo. O estudo do transporte das massas de ar explica, pelo menos em parte, a presença de partículas envelhecidas na amostra de Estocolmo. Sugere também que a redução das concentrações de HPA em Limeira depende do controle das fontes locais, enquanto em Estocolmo o controle das fontes locais não seria eficiente na diminuição desses poluentes. Em paralelo a avaliação das amostras de PTS, foi desenvolvido um novo protocolo miniaturizado do teste Salmonella/microssoma em microssuspensão. O protocolo utilizando microplacas de 12 poços foi validado empregando treze compostos mutagênicos testados com três linhagens de Salmonella selecionadas baseadas em suas diferentes frequências de reversão espontânea (baixa, média e alta). Tanto o teste miniaturizado em microplacas de ágar (MPA) quanto o em microssuspensão apresentaram sensibilidades semelhantes, concluindo que o MPA é uma ferramenta promissora e pode ser particularmente adequado para estudos ambientais como Análise Dirigida pelo Efeito (EDA) ou programas de monitoramento. / Atmospheric particulate matter (PM) is associated with various diseases and has recently been classified as carcinogenic to humans (Group 1) by the International Agency for Research on Cancer (IARC). Although the PM toxicity, including genotoxicity, is known to be related to particle size, the contribution of its chemical composition to the observed effects has not yet been fully elucidated. The size and composition of the particles are influenced by meteorological and climatic characteristics, especially the temperature and the period of solar radiation. The Salmonella/microsome assay is the most used for the evaluate of the mutagenicity of PM samples, however a small number of strains are used. The objective of this study was to investigate and compare the influence of the different atmospheric and climatic conditions of the cities of Limeira (Brazil), Stockholm (Sweden) and Kyoto (Japan) on mutagenicity profiles, using 11 strains with different selectivity, and chemical composition profiles of total particles suspended (TPS) composed samples collected during the winter of these cities. For the results to be directly compared, the same methodology was adopted, including the sampling procedure, the sample preparation protocol, the mutagenicity test protocol, and the chemical analysis techniques for the identification of polycyclic aromatic hydrocarbons (PAH) and their alkylated derivatives. Limeira presented the highest concentration of TPS (99.0 µg/m3), followed by Kyoto (28.0 µg/m3) and Stockholm (6.2 µg/m3). Although the TPS concentration in Limeira was 16-fold higher than in Stockholm and 3.5-fold higher than in Kyoto, the percentage of extracted organic material (EOM) obtained was 9, 15 and 5%, respectively. The extracts from the TPS samples collected in the three cities presented mutagenic activity for all strains, both in the absence and presence of S9, except for TA102 that did not detect the mutagenic activity in any of the extracts, and for YG7108 in the presence of S9, only for the Limeira sample. Despite the differences in meteorological and climatic conditions of these cities, their mutagenicity profiles were similar. The lower mutagenic potency for YG7108 in the absence of S9 and the non-mutagenicity in the presence of S9 reveals the lower contribution of alkylating agents to the mutagenicity of the Limeira sample in relation to the other cities. Considering the selectivity of the strains used, we can also observe a greater contribution of compounds that cause DNA oxidative damage and of alkylating agents for the mutagenicity of the Kyoto sample. However, according to the responses of the strains that have increased activity of the nitroreductase (NR) and/or O-acetyltransferase (OAT) enzymes, YG1021, YG1024 and YG1041, show the highest contribution of nitroarenes and aromatic amines for the mutagenicity of the three cities, with emphasis on those mutagens that depend on OAT activation. The mutagenic potencies expressed as a function of EOM mass (rev./µg EOM) were similar for all samples. When expressed by air volume (rev./m3), the mutagenic potencies were proportional to TPS concentrations of the three cities (Limeira> Kyoto> Stockholm). When applying the diagnostic ratios, it was possible to verify a mixture of sources of pollution in Limeira and Stockholm. The diagnostic ratios of the PAH indicate that Limeira sample is composed of fresh particles with a slight predominance of combustion sources. The Stockholm sample present aged particles with a predominance of petrogenic sources. This result was unexpected, since Limeira\'s atmospheric conditions are more favorable to particle aging than Stockholm\'s. The study of the transport of air masses explains, at least in part, the presence of aged particles in the Stockholm sample. It also suggests that the reduction of PAH concentrations in Limeira depends on the control of local sources, while in Stockholm control of local sources would not be efficient in reducing these pollutants. In parallel to the evaluation of the TPS samples, a new miniaturized protocol of the Salmonella/microsome assay in microsuspension was also developed. The protocol using 12-well microplates was validated by employing thirteen mutagenic compounds tested with three selected Salmonella strains based on their different spontaneous reversion frequencies (low, medium and high). Both the miniaturized microplate agar (MPA) and the microsuspension assay presented similar sensitivities, concluding that MPA is a promising tool and can be particularly suitable for environmental studies such as effect-directed analysis (EDA) or monitoring programs.

A combinação de célula eletroquímica (EC) com a entrada do equipamento de eletroforese capilar (CE), apesar de recente, tem permitido realizar determinação de ânions radicais; pré-concentração eletroquímica de metais pesados, seguida de redissolução, separação e detecção; bem como monitorar produtos carregados formados por oxidação eletrocatalítica de espécies neutras, como álcoois primários e glicerol. Empregando o sistema EC-CE-C4D desenvolvido pelo grupo, a determinação simultânea de cátions, ânions (no contra fluxo) e espécies neutras (detectadas após derivatização eletroquímica) foi demonstrada pela primeira vez, tendo o antisséptico bucal (Listerine® Tartar Control) como amostra real. Embora constante e reprodutível, a conversão dos álcoois primários nos respectivos carboxilatos apresentou rendimento relativamente baixo, ~16%, nas condições anteriormente adotadas, 1,6 V vs. Ag/AgClKCl 3M empregando eletrodo de platina em meio ácido (HNO3 5 mmol L-1 / HCl 1 mmol L-1). Dessa maneira, avaliou-se a oxidação de álcoois primários de cadeia normal (C2 − C5) sobre diferentes materiais de eletrodo (ouro e platina) em diferentes meios (ácido, neutro e alcalino). Os carboxilatos gerados foram monitorados injetando uma alíquota da amostra derivatizada no capilar (50 µm d.i., 45 cm de comprimento e 20 cm efetivo) aplicando 5 kPa durante 5 s, e durante as separações, 30 kV foi aplicado entre as extremidades do capilar preenchido com Tris 30 mmol L-1 / HCl 10 mmol L-1 usado como BGE. Os resultados obtidos com o sistema EC-CE-C4D apontaram maior conversão dos álcoois nos respectivos ácidos carboxílicos em meio ácido, tanto em ouro quanto em platina. Adicionalmente, em eletrodo de ouro a formação dos carboxilatos apresentou certa seletividade não observada sobre platina, favorecendo a conversão dos álcoois de cadeia menor. Noutra vertente, buscando atender as necessidades atuais por metodologias que possibilitem monitorar a eletrooxidação do glicerol em reatores eletroquímicos, desenvolveu-se um método que permitiu determinar simultaneamente o glicerol e alguns de seus possíveis produtos de oxidação neutros, como gliceraldeído e dihidroxiacetona, explorando a formação de complexo carregado com borato (presente no BGE composto por H3BO3 60 mmol L-1 / LiOH 30 mmol L-1), além dos produtos ionizáveis (ácidos carboxílicos) que são comumente analisados por CE. O equipamento de CE utilizado, munido de dois detectores C4D, também permitiu avaliar a interação de alguns ácidos carboxílicos com os modificadores de EOF, Polybrene® e CTAB, empregando MES 30 mmol L-1 / His 30 mmol L-1 como BGE. Seguindo a atual tendência à miniaturização de sistemas analíticos, avaliou-se a possibilidade de construir um sistema EC-CE-C4D miniaturizado. Para isso, um novo método para fabricação de microdispositivos em vidro, baseado em ablação a laser de CO2 assistida por parafina, como alternativa aos dispendiosos métodos de corrosão por via úmida foi desenvolvido. Os dispositivos obtidos por esse método apresentaram canais de perfil semicircular, e as dimensões puderam ser controladas variando a potência e/ou a velocidade de ablação do laser. Contudo, pelos desafios ainda encontrados para se construir um sistema EC-CE-C4D completo em substrato de vidro por ablação a laser de CO2, optou-se por iniciar a miniaturização do sistema EC-CE-C4D com um sistema híbrido em que se aproveita as características mais bem definidas e favoráveis dos tubos capilares de sílica fundida usados em CE convencional. Esse sistema permitiu a determinação quantitativa de metanol na presença de alta concentração de etanol, possibilitando, numa primeira aplicação, realizar o monitoramento da quantidade de metanol e etanol nas frações iniciais coletada durante o processo de destilação fracionada na produção de uísque de milho (moonshine) feito em laboratório. Visto a maior seletividade para conversão dos álcoois de cadeia menor obtidas em eletrodo de ouro e meio ácido, esse foi escolhido para a presente aplicação. As condições que apresentaram melhores resultados no sistema híbrido EC-CE-C4D abrangeram diluição de 100 vezes da amostra em HNO3 2 mmol L-1, eletrooxidação a 1,4 V vs. Ag durante 60 s, injeção eletrocinética no capilar mediante aplicação de 3 kV durante 4 s, e a separação dos carboxilatos realizada aplicando 3 kV entre as extremidades do capilar (50 µm d.i., 15 cm de comprimento com 12 cm efetivo), preenchido com CHES 10 mmol L-1 / NaOH 5 mmol L-1, usado como BGE. A análise das primeiras frações destiladas da \"labmade moonshine\" apresentou um aumento na concentração de etanol (variando de ~80 % a ~100 %) e simultâneo decréscimo da concentração de metanol (variando de 4 % a ~0,1 %). Em suma, avançou-se tanto no leque de aplicações da derivatização eletroquímica hifenizada com a eletroforese capilar como na miniaturização da instrumentação analítica para EC-CE-C4D, favorecendo a disseminação dessa poderosa combinação de três técnicas eletroquímicas. / The direct couple of electrochemical cell (EC) with the inlet of the capillary electrophoresis (CE) equipment, recently demonstrated, has allowed the determination of radical anions; to perform electrochemical preconcentration of traces of heavy metals, followed by stripping, injection, separation and detection; and the generation of charged species by electrochemical oxidation of neutral molecules, e.g. primary alcohols and glycerol. Employing the EC-CE-C4D system developed by our group, the simultaneous determination of cations, anions (in the counter EOF mode) and neutral species (after electrochemical derivatization) was demonstrated for the first time and a mouthwash (Listerine® Tartar Control) was used as a real sample. Although constant and reproducible, the conversion of primary alcohols into carboxylates had a low yield (~16%), under the adopted conditions, 1.6 V vs. Ag/AgClKCl 3M using platinum electrode in acid medium (5 mmol L-1 HNO3 / 1 mmol L-1 HCl). Thus, the yield of carboxylates was studied for the oxidation of alcohols (C2 − C5) on two electrode materials (gold and platinum) in different media (acid, neutral and alkaline). After the electrooxidation step an aliquot of the derivatized sample was automatically injected into the capillary (50 µm i.d., 45 cm in length and 20 cm up to detector) by applying 5 kPa during 5 s. The separation was carried out applying 30 kV between the capillary ends previously filled with 30 mmol L-1 Tris / 10 mmol L-1 HCl BGE. Cyclic voltammograms show higher current density for alcohols oxidation in alkaline medium than in acid one both on gold and platinum electrodes. On the other hand the yields of carboxylic acids were higher in acidic medium. Besides that, only on gold electrode some selectivity for the carboxylate formation was observed favoring the conversion of the short chain alcohols. In order to meet the current needs for methodologies that allow the monitoring of the electrooxidation of glycerol in electrochemical reactors, a method was also developed that allowed the determination of glycerol and some of its possible neutral oxidation products, such as glyceraldehyde and dihydroxyacetone, by exploring the formation of borate complexes (provided in the BGE composed of 60 mmol L-1 H3BO3 / 30 mmol L-1 LiOH), together with ionizable ones like carboxylic acids. The employed CE equipment with two C4D detectors allowed the evaluation of the interaction between some carboxylic acids and the EOF modifiers, Polybrene® and CTAB, using 30 mmol L-1 MES / 30 mmol L-1 His as BGE. Aligned with a current trend of analytical instrumentation, the miniaturized EC-CE-C4D system was attempted. For that, a new method for manufacturing microdevices in glass, based on paraffin-assisted CO2 laser ablation, was developed as an alternative to costly wet-etching methods. The devices obtained by this method presented channels of semicircular profile and the dimensions could be controlled by varying the laser power and/or ablation velocity. Due to remaining challenges in the construction of a complete laser ablated EC-CE-C4D system on glass, a miniaturized system based on a hybrid approach is presented in the thesis, by taking advantage of the more defined and favorable characteristics of the well known fused silica capillary tubes used in CE. This system allowed the quantitative determination of methanol in the presence of high ethanol concentration by taking advantage of the higher yield of short-chain carboxylic acid formation on gold in acidic medium. The first application was the monitoring of the amount of methanol and ethanol in the initial fractions collected during the fractional distillation process in the production of corn whiskey (moonshine) made in the laboratory. The conditions that showed the best results with the hybrid EC-CE-C4D system included a 100-fold dilution of the sample in 2 mmol L-1 HNO3, electrooxidation at 1.4 V vs. Ag for 60 s, electrokinetic injection into the capillary by applying 3 kV for 4 s and separation of the carboxylates carried out under 3 kV between the ends of the capillary (50 µm i.d., 15 cm in length and 12 cm up to detector) previously filled with 10 mmol L-1 CHES / 5 mmol L-1 NaOH, used as BGE. Analysis of the first distilled fractions of labmade moonshine showed an increase in ethanol concentration (ranging from ~ 80% to ~ 100%) and a simultaneous decrease in methanol concentration (ranging from 4% to ~ 0.1%). In short, both the range of applications of electrochemical derivatization hyphenated with capillary electrophoresis as well the miniaturization of analytical instrumentation for EC-CE-C4D were improved, favoring the dissemination of this powerful combination of three electrochemical techniques.

A combinação de célula eletroquímica (EC) com a entrada do equipamento de eletroforese capilar (CE), apesar de recente, tem permitido realizar determinação de ânions radicais; pré-concentração eletroquímica de metais pesados, seguida de redissolução, separação e detecção; bem como monitorar produtos carregados formados por oxidação eletrocatalítica de espécies neutras, como álcoois primários e glicerol. Empregando o sistema EC-CE-C4D desenvolvido pelo grupo, a determinação simultânea de cátions, ânions (no contra fluxo) e espécies neutras (detectadas após derivatização eletroquímica) foi demonstrada pela primeira vez, tendo o antisséptico bucal (Listerine® Tartar Control) como amostra real. Embora constante e reprodutível, a conversão dos álcoois primários nos respectivos carboxilatos apresentou rendimento relativamente baixo, ~16%, nas condições anteriormente adotadas, 1,6 V vs. Ag/AgClKCl 3M empregando eletrodo de platina em meio ácido (HNO3 5 mmol L-1 / HCl 1 mmol L-1). Dessa maneira, avaliou-se a oxidação de álcoois primários de cadeia normal (C2 − C5) sobre diferentes materiais de eletrodo (ouro e platina) em diferentes meios (ácido, neutro e alcalino). Os carboxilatos gerados foram monitorados injetando uma alíquota da amostra derivatizada no capilar (50 µm d.i., 45 cm de comprimento e 20 cm efetivo) aplicando 5 kPa durante 5 s, e durante as separações, 30 kV foi aplicado entre as extremidades do capilar preenchido com Tris 30 mmol L-1 / HCl 10 mmol L-1 usado como BGE. Os resultados obtidos com o sistema EC-CE-C4D apontaram maior conversão dos álcoois nos respectivos ácidos carboxílicos em meio ácido, tanto em ouro quanto em platina. Adicionalmente, em eletrodo de ouro a formação dos carboxilatos apresentou certa seletividade não observada sobre platina, favorecendo a conversão dos álcoois de cadeia menor. Noutra vertente, buscando atender as necessidades atuais por metodologias que possibilitem monitorar a eletrooxidação do glicerol em reatores eletroquímicos, desenvolveu-se um método que permitiu determinar simultaneamente o glicerol e alguns de seus possíveis produtos de oxidação neutros, como gliceraldeído e dihidroxiacetona, explorando a formação de complexo carregado com borato (presente no BGE composto por H3BO3 60 mmol L-1 / LiOH 30 mmol L-1), além dos produtos ionizáveis (ácidos carboxílicos) que são comumente analisados por CE. O equipamento de CE utilizado, munido de dois detectores C4D, também permitiu avaliar a interação de alguns ácidos carboxílicos com os modificadores de EOF, Polybrene® e CTAB, empregando MES 30 mmol L-1 / His 30 mmol L-1 como BGE. Seguindo a atual tendência à miniaturização de sistemas analíticos, avaliou-se a possibilidade de construir um sistema EC-CE-C4D miniaturizado. Para isso, um novo método para fabricação de microdispositivos em vidro, baseado em ablação a laser de CO2 assistida por parafina, como alternativa aos dispendiosos métodos de corrosão por via úmida foi desenvolvido. Os dispositivos obtidos por esse método apresentaram canais de perfil semicircular, e as dimensões puderam ser controladas variando a potência e/ou a velocidade de ablação do laser. Contudo, pelos desafios ainda encontrados para se construir um sistema EC-CE-C4D completo em substrato de vidro por ablação a laser de CO2, optou-se por iniciar a miniaturização do sistema EC-CE-C4D com um sistema híbrido em que se aproveita as características mais bem definidas e favoráveis dos tubos capilares de sílica fundida usados em CE convencional. Esse sistema permitiu a determinação quantitativa de metanol na presença de alta concentração de etanol, possibilitando, numa primeira aplicação, realizar o monitoramento da quantidade de metanol e etanol nas frações iniciais coletada durante o processo de destilação fracionada na produção de uísque de milho (moonshine) feito em laboratório. Visto a maior seletividade para conversão dos álcoois de cadeia menor obtidas em eletrodo de ouro e meio ácido, esse foi escolhido para a presente aplicação. As condições que apresentaram melhores resultados no sistema híbrido EC-CE-C4D abrangeram diluição de 100 vezes da amostra em HNO3 2 mmol L-1, eletrooxidação a 1,4 V vs. Ag durante 60 s, injeção eletrocinética no capilar mediante aplicação de 3 kV durante 4 s, e a separação dos carboxilatos realizada aplicando 3 kV entre as extremidades do capilar (50 µm d.i., 15 cm de comprimento com 12 cm efetivo), preenchido com CHES 10 mmol L-1 / NaOH 5 mmol L-1, usado como BGE. A análise das primeiras frações destiladas da \"labmade moonshine\" apresentou um aumento na concentração de etanol (variando de ~80 % a ~100 %) e simultâneo decréscimo da concentração de metanol (variando de 4 % a ~0,1 %). Em suma, avançou-se tanto no leque de aplicações da derivatização eletroquímica hifenizada com a eletroforese capilar como na miniaturização da instrumentação analítica para EC-CE-C4D, favorecendo a disseminação dessa poderosa combinação de três técnicas eletroquímicas. / The direct couple of electrochemical cell (EC) with the inlet of the capillary electrophoresis (CE) equipment, recently demonstrated, has allowed the determination of radical anions; to perform electrochemical preconcentration of traces of heavy metals, followed by stripping, injection, separation and detection; and the generation of charged species by electrochemical oxidation of neutral molecules, e.g. primary alcohols and glycerol. Employing the EC-CE-C4D system developed by our group, the simultaneous determination of cations, anions (in the counter EOF mode) and neutral species (after electrochemical derivatization) was demonstrated for the first time and a mouthwash (Listerine® Tartar Control) was used as a real sample. Although constant and reproducible, the conversion of primary alcohols into carboxylates had a low yield (~16%), under the adopted conditions, 1.6 V vs. Ag/AgClKCl 3M using platinum electrode in acid medium (5 mmol L-1 HNO3 / 1 mmol L-1 HCl). Thus, the yield of carboxylates was studied for the oxidation of alcohols (C2 − C5) on two electrode materials (gold and platinum) in different media (acid, neutral and alkaline). After the electrooxidation step an aliquot of the derivatized sample was automatically injected into the capillary (50 µm i.d., 45 cm in length and 20 cm up to detector) by applying 5 kPa during 5 s. The separation was carried out applying 30 kV between the capillary ends previously filled with 30 mmol L-1 Tris / 10 mmol L-1 HCl BGE. Cyclic voltammograms show higher current density for alcohols oxidation in alkaline medium than in acid one both on gold and platinum electrodes. On the other hand the yields of carboxylic acids were higher in acidic medium. Besides that, only on gold electrode some selectivity for the carboxylate formation was observed favoring the conversion of the short chain alcohols. In order to meet the current needs for methodologies that allow the monitoring of the electrooxidation of glycerol in electrochemical reactors, a method was also developed that allowed the determination of glycerol and some of its possible neutral oxidation products, such as glyceraldehyde and dihydroxyacetone, by exploring the formation of borate complexes (provided in the BGE composed of 60 mmol L-1 H3BO3 / 30 mmol L-1 LiOH), together with ionizable ones like carboxylic acids. The employed CE equipment with two C4D detectors allowed the evaluation of the interaction between some carboxylic acids and the EOF modifiers, Polybrene® and CTAB, using 30 mmol L-1 MES / 30 mmol L-1 His as BGE. Aligned with a current trend of analytical instrumentation, the miniaturized EC-CE-C4D system was attempted. For that, a new method for manufacturing microdevices in glass, based on paraffin-assisted CO2 laser ablation, was developed as an alternative to costly wet-etching methods. The devices obtained by this method presented channels of semicircular profile and the dimensions could be controlled by varying the laser power and/or ablation velocity. Due to remaining challenges in the construction of a complete laser ablated EC-CE-C4D system on glass, a miniaturized system based on a hybrid approach is presented in the thesis, by taking advantage of the more defined and favorable characteristics of the well known fused silica capillary tubes used in CE. This system allowed the quantitative determination of methanol in the presence of high ethanol concentration by taking advantage of the higher yield of short-chain carboxylic acid formation on gold in acidic medium. The first application was the monitoring of the amount of methanol and ethanol in the initial fractions collected during the fractional distillation process in the production of corn whiskey (moonshine) made in the laboratory. The conditions that showed the best results with the hybrid EC-CE-C4D system included a 100-fold dilution of the sample in 2 mmol L-1 HNO3, electrooxidation at 1.4 V vs. Ag for 60 s, electrokinetic injection into the capillary by applying 3 kV for 4 s and separation of the carboxylates carried out under 3 kV between the ends of the capillary (50 µm i.d., 15 cm in length and 12 cm up to detector) previously filled with 10 mmol L-1 CHES / 5 mmol L-1 NaOH, used as BGE. Analysis of the first distilled fractions of labmade moonshine showed an increase in ethanol concentration (ranging from ~ 80% to ~ 100%) and a simultaneous decrease in methanol concentration (ranging from 4% to ~ 0.1%). In short, both the range of applications of electrochemical derivatization hyphenated with capillary electrophoresis as well the miniaturization of analytical instrumentation for EC-CE-C4D were improved, favoring the dissemination of this powerful combination of three electrochemical techniques.

Une antenne auto-complémentaire possède des caractéristiques radioélectriques très intéressantes en ce qui concerne l’élargissement de sa bande passante. Basée sur le principe de Babinet, l’auto-complémentarité permet en effet de maximiser la largeur de bande de par la complémentarité air-métal dans la structure de l’antenne. L’objectif de cette thèse est d’étudier quels pouvaient être les apports de l’auto-complémentarité dans le cas d’antennes à fortes contraintes d’intégration telles que celles utilisées pour les terminaux mobiles. Pour tester les limites de notre étude, nous avons choisi d’appliquer nos résultats à l’intégration d’antennes auto-complémentaires dans un objet communicant de type Smartphone multi-standards. Les antennes dites AC doivent par conséquent satisfaire de nombreux critères de performances tout en montrant leur capacité d’intégration. Celle-ci est rendue d’autant plus délicate, que la miniaturisation implique à son tour des phénomènes physiques limitant certaines performances, notamment en basse fréquence avec la nouvelle bande LTE. Dans une première étude, nous avons considéré différentes antennes et opté pour les antennes IFA-AC sur un plan de masse fini afin de couvrir initialement les bandes hautes DCS/PCS/UMTS et WLAN/LTE2600. Dans une seconde étude, nous avons amélioré leurs performances à l’aide d’éléments structurels nouveaux et interdépendants (éléments rayonnants de type double IFA), qui nous ont permis d’obtenir des résultats probants relatifs notamment à la couverture des bandes LTE800 et GSM. Enfin, nous avons complété notre projet en optimisant le lien radio par l’intégration de plusieurs éléments rayonnants AC sur un même PCB. / In this thesis we present the design and optimization of self-complementary antennas to be integrated into a Smartphone. A self-complementary antenna is known as a radio antenna with very interesting bandwidth characteristics. Self-complementarity is based on the Babinet’s principle which aims to maximize bandwidth by considering the complementarity of the air and metal in the construction of an antenna. To achieve an objective, the antennas must satisfy a number of criteria, both in terms of performance and also for the design methods and integration. Miniaturization is very sensitive and it is more difficult to implement an antenna because of the physical phenomena limiting performance, especially at low frequency with the new 4G band. In this study we considered initially the self-complementary-IFA on a finite ground plane size: 120x60mm² in order to cover the high frequencies: DCS/PCS/UMTS and WLAN/LTE2600. In the second part, we focused on the possibility of using some improvement techniques by adding structural element (capacitive elements and radiating elements). Various geometrical modifications applied to antenna structures have also been used to obtain results satisfying all criteria, including coverage of LTE800 bands and GSM bands. Several prototypes were used to compare the theoretical results and validate the concept of self-complementarity. We completed the project by developing a way to improve the radio link in natural environments. We have implemented several radiating self-complementary miniature multiband/broadband elements on the same PCB in order to implement the principles of diversity or MIMO.

O material particulado (MP) atmosférico é associado a vários agravos e doenças, sendo recentemente classificado como carcinogênico para humanos (Grupo 1) pela Agência Internacional de Pesquisa em Câncer (IARC). Embora sua toxicidade, incluindo a genotoxicidade, esteja reconhecidamente ligada ao tamanho das partículas, a contribuição da sua composição química para esses efeitos ainda não está completamente elucidada. O tamanho e a composição das partículas são influenciados por características meteorológicas e climáticas, com destaque para a temperatura e o período de radiação solar. O teste Salmonella/microssoma é o mais utilizado para avaliação da mutagenicidade de amostras de MP, contudo um número reduzido de linhagens é usado. Assim, o objetivo desse estudo foi investigar e comparar a influência das diferentes condições atmosféricas e climáticas das cidades de Limeira (Brasil), Estocolmo (Suécia) e Quioto (Japão) nos perfis de mutagenicidade, utilizando 11 linhagens com diferentes seletividades, e nos perfis de composição química de amostras compostas de partículas totais em suspensão (PTS) coletadas durante o inverno dessas cidades. Para que os resultados pudessem ser diretamente comparados foi adotada a mesma metodologia, incluindo o procedimento de amostragem, o método de preparo de amostra, o protocolo do teste de mutagenicidade e as técnicas de análises químicas para identificação de hidrocarbonetos policíclicos aromáticos (HPA) e de seus derivados alquilados. Limeira apresentou a maior concentração de PTS (99,0 µg/m3), seguida por Quioto (28,0 µg/m3) e Estocolmo (6,2 µg/m3). Apesar da concentração de PTS em Limeira ser 16 vezes maior que em Estocolmo e 3,5 vezes maior que em Quioto, as porcentagens de material orgânico extraído (MOE) obtidas foram 9, 15 e 5%, respectivamente. Os extratos das amostras de PTS coletadas nas três cidades apresentaram atividade mutagênica para todas as linhagens, tanto na ausência quanto na presença de S9, com exceção da TA102 que não detectou a atividade mutagênica em nenhum dos extratos, e para YG7108 na presença de S9, apenas para a amostra de Limeira. Apesar das diferenças nas condições meteorológicas e climáticas dessas cidades, seus perfis de mutagenicidade foram semelhantes. A menor potência mutagênica para a YG7108 na ausência de S9 e a ausência de mutagenicidade na presença de S9 revela a menor contribuição de agentes alquilantes para a mutagenicidade da amostra de Limeira em relação as demais cidades. Considerando a seletividade das linhagens utilizadas, foi observado maior contribuição de compostos que causam danos oxidativo ao DNA e de agentes alquilantes para a mutagenicidade da amostra de Quioto. Porém, de acordo com as respostas das linhagens que possuem atividade aumentada das enzimas nitroredutase (NR) e/ou O-acetiltransferase (OAT), YG1021, YG1024 e YG1041, revelam a maior contribuição de nitroarenos e aminas aromáticas para a mutagenicidade das três cidades, com destaque para aqueles mutágenos que dependem da ativação via OAT. As potências mutagênicas expressadas em função da massa de MOE (rev./µg MOE) foram similares para todas as amostras. Quando expressas por volume de ar (rev./m3), as potências mutagênicas foram proporcionais às concentrações de PTS das três cidades (Limeira > Quioto > Estocolmo). Quando aplicadas as razões diagnósticas foi possível verificar uma mistura de fontes de poluição em Limeira e Estocolmo. As razões diagnósticas dos HPA indicam que a amostra de Limeira é composta por partículas frescas, com um leve predomínio de fontes de combustão. A amostra de Estocolmo apresenta partículas envelhecidas e com predomínio de fontes petrogênicas. Esse resultado foi inesperado, uma vez que as condições atmosféricas de Limeira são mais favoráveis ao envelhecimento das partículas que as de Estocolmo. O estudo do transporte das massas de ar explica, pelo menos em parte, a presença de partículas envelhecidas na amostra de Estocolmo. Sugere também que a redução das concentrações de HPA em Limeira depende do controle das fontes locais, enquanto em Estocolmo o controle das fontes locais não seria eficiente na diminuição desses poluentes. Em paralelo a avaliação das amostras de PTS, foi desenvolvido um novo protocolo miniaturizado do teste Salmonella/microssoma em microssuspensão. O protocolo utilizando microplacas de 12 poços foi validado empregando treze compostos mutagênicos testados com três linhagens de Salmonella selecionadas baseadas em suas diferentes frequências de reversão espontânea (baixa, média e alta). Tanto o teste miniaturizado em microplacas de ágar (MPA) quanto o em microssuspensão apresentaram sensibilidades semelhantes, concluindo que o MPA é uma ferramenta promissora e pode ser particularmente adequado para estudos ambientais como Análise Dirigida pelo Efeito (EDA) ou programas de monitoramento. / Atmospheric particulate matter (PM) is associated with various diseases and has recently been classified as carcinogenic to humans (Group 1) by the International Agency for Research on Cancer (IARC). Although the PM toxicity, including genotoxicity, is known to be related to particle size, the contribution of its chemical composition to the observed effects has not yet been fully elucidated. The size and composition of the particles are influenced by meteorological and climatic characteristics, especially the temperature and the period of solar radiation. The Salmonella/microsome assay is the most used for the evaluate of the mutagenicity of PM samples, however a small number of strains are used. The objective of this study was to investigate and compare the influence of the different atmospheric and climatic conditions of the cities of Limeira (Brazil), Stockholm (Sweden) and Kyoto (Japan) on mutagenicity profiles, using 11 strains with different selectivity, and chemical composition profiles of total particles suspended (TPS) composed samples collected during the winter of these cities. For the results to be directly compared, the same methodology was adopted, including the sampling procedure, the sample preparation protocol, the mutagenicity test protocol, and the chemical analysis techniques for the identification of polycyclic aromatic hydrocarbons (PAH) and their alkylated derivatives. Limeira presented the highest concentration of TPS (99.0 µg/m3), followed by Kyoto (28.0 µg/m3) and Stockholm (6.2 µg/m3). Although the TPS concentration in Limeira was 16-fold higher than in Stockholm and 3.5-fold higher than in Kyoto, the percentage of extracted organic material (EOM) obtained was 9, 15 and 5%, respectively. The extracts from the TPS samples collected in the three cities presented mutagenic activity for all strains, both in the absence and presence of S9, except for TA102 that did not detect the mutagenic activity in any of the extracts, and for YG7108 in the presence of S9, only for the Limeira sample. Despite the differences in meteorological and climatic conditions of these cities, their mutagenicity profiles were similar. The lower mutagenic potency for YG7108 in the absence of S9 and the non-mutagenicity in the presence of S9 reveals the lower contribution of alkylating agents to the mutagenicity of the Limeira sample in relation to the other cities. Considering the selectivity of the strains used, we can also observe a greater contribution of compounds that cause DNA oxidative damage and of alkylating agents for the mutagenicity of the Kyoto sample. However, according to the responses of the strains that have increased activity of the nitroreductase (NR) and/or O-acetyltransferase (OAT) enzymes, YG1021, YG1024 and YG1041, show the highest contribution of nitroarenes and aromatic amines for the mutagenicity of the three cities, with emphasis on those mutagens that depend on OAT activation. The mutagenic potencies expressed as a function of EOM mass (rev./µg EOM) were similar for all samples. When expressed by air volume (rev./m3), the mutagenic potencies were proportional to TPS concentrations of the three cities (Limeira> Kyoto> Stockholm). When applying the diagnostic ratios, it was possible to verify a mixture of sources of pollution in Limeira and Stockholm. The diagnostic ratios of the PAH indicate that Limeira sample is composed of fresh particles with a slight predominance of combustion sources. The Stockholm sample present aged particles with a predominance of petrogenic sources. This result was unexpected, since Limeira\'s atmospheric conditions are more favorable to particle aging than Stockholm\'s. The study of the transport of air masses explains, at least in part, the presence of aged particles in the Stockholm sample. It also suggests that the reduction of PAH concentrations in Limeira depends on the control of local sources, while in Stockholm control of local sources would not be efficient in reducing these pollutants. In parallel to the evaluation of the TPS samples, a new miniaturized protocol of the Salmonella/microsome assay in microsuspension was also developed. The protocol using 12-well microplates was validated by employing thirteen mutagenic compounds tested with three selected Salmonella strains based on their different spontaneous reversion frequencies (low, medium and high). Both the miniaturized microplate agar (MPA) and the microsuspension assay presented similar sensitivities, concluding that MPA is a promising tool and can be particularly suitable for environmental studies such as effect-directed analysis (EDA) or monitoring programs.

Les antennes présentes dans la plupart des systèmes communicants comme les véhicules automobiles, les avions et les trains se multiplient et sont soumises à une contrainte d’intégration de plus en plus sévère. De nombreuses techniques de miniaturisation d’antennes existent et passent toutes par un compromis entre la taille et les performances (bande passante et/ou rendement de rayonnement). Pour les systèmes cités ci-dessus, les antennes sont souvent placées devant ou à proximité d’un réflecteur métallique (toit de véhicule, carlingue d’aéronef). Dans ce cas, l’épaisseur de système antennaire est une contrainte majeure et les métamatériaux de type Conducteur Magnétique Artificiel (CMA) ouvrent des perspectives intéressantes grâce à leurs propriétés électromagnétiques non conventionnelles. Cependant, pour les applications sub-GHz (RFID, LTE, PMR…), les CMA sont limités par les dimensions des cellules unitaires nécessaires à leur mise en œuvre (λg/4) ainsi que leur bande réduite de fonctionnement. Réduire leurs dimensions permet de rendre leur utilisation compatible avec le contexte des antennes miniatures intégrées. Ajouter l’agilité fréquentielle permet de palier le problème de la bande passante réduite dans le cas des antennes et des CMA miniaturisés en ajustant le fonctionnement du système antennaire sur une large bande passante. Cette thèse de doctorat propose d’étudier et de développer un nouveau système antennaire à faible profil composé d’une antenne miniature associée à une métasurface compacte reconfigurable en fréquence et compatible avec le standard NB-IoT dans la bande basse LTE (700 MHz – 960 MHz). / Antennas are now very integrated in several connected systems like cars, airplanes and trains. Many antenna miniaturization techniques exist and all go through a compromise between size and performance (bandwidth and/or radiation efficiency). For the systems mentioned above, the antennas are often placed near a metallic reflector (vehicle roof, aircraft cabin). Within this context, Artificial Magnetic Conductors (AMC) present an attractive reflector for low profile antennas which can take advantage of intrinsic zero reflection phase response to boost antenna performance without the need for thick quarter wave backplane. However, for sub-GHz applications (RFID, LTE, PMR ...), AMC are limited by the size of the unit cells necessary for their implementation (λg/4) as well as their reduced operating bandwidth. AMC miniaturization makes their use compatible with small antennas. Adding tunability restores the possibility of adjusting the operating frequency over a large bandwidth. This PhD thesis proposes to study and develop a new electrically small, low-profile antenna based on miniaturized and tunable AMC for the NB-IoT standard in low LTE band (700 MHz – 960 MHz).

Les progrès rapides de la microélectronique sont liées à la miniaturisation du transistor MOS. Pour limiter les courants de fuite, SiO2 a déjà été remplacé par HfO2.mais de nouveaux diélectriques de grande constante diélectrique (high-k) devront être intégrés pour poursuivre cette progression. Le microscope à force atomique (AFM) en mode Conductive-AFM (C-AFM) est aujourd'hui un outil incontournable pour la caractérisation électrique des diélectriques en couche mince à l'échelle nanométrique. Dans nos travaux, nous avons cherché à étudier les limites du C-AM. Le C-AFM consiste à utiliser une pointe AFM comme électrode supérieure afin de faire des mesures de type I(V) ou des cartographies de courant. Nous avons cherché à identifier le phénomène qui conduit à la dégradation de la couche diélectrique par l'application d'une tension de pointe positive, matérialisée par la déformation de la surface. Nous avons montré qu'il s'agissait d'un effet thermique due à la forte densité de courant, ne s'apparentant pas à la DBIE observée sur dispositif, et pouvant aller jusqu'à la détérioration du substrat à l'interface. Ce phénomène, sans en être la conséquence, est largement favorisé par la présence d'eau. Ceci confirme qu'il est préférable de réaliser les caractérisations électriques sous ultra-vide malgré les contraintes expérimentales. Les études du diélectriques sont ainsi compromises puisque le mode de dégradation est en partie propre à la technique AFM et ne permet pas aisément d'extrapoler le comportement du matériau intégré dans un dispositif. De plus, l'étude statistique la dégradation de la couche (Weibull), couramment utilisée, est affectée par un biais d'interdépendance. De la même façon, la modélisation de la conduction à travers la couche doit être utilisée avec précaution, car la surface du contact électrique pointe-diélectrique demeure un paramètre incertain. La technique de pompage de charges permet de caractériser les pièges à l'interface oxyde/semi- conducteur en les sollicitant par l'application d'une tension de grille périodique. Elle permet d'extraire la densité d'état Dit(E) les sections efficaces de capture (σ(E)), mais ne donne pas d'information sur leur répartition spatiale. Nous avons donc adapté cette technique à la microscopie champ proche, la pointe AFM conductrice faisant office de grille. Sur des transistors dépourvus de grille spécialement préparés pour l’occasion, nous avons pu montrer la faisabilité de la technique, en accord satisfaisant avec les mesures macroscopiques. Nous mesurons un signal que nous associons à un courant pompé. Cependant, le signal est déformé comparativement aux mesures macroscopiques. Un modèle physique reste à développer puisque dans notre cas, les charges minoritaires doivent traverser depuis la source et le drain un espace non polarisé par la grille. Par la suite, un dispositif de cartographie des défauts d'interface, éventuellement résolue en énergie, pourra être développé. / The rapid progress of the microelectronic is obtained by the strong reduction of the dimensions of the MOS transistor. In order to reduce the leakage currents SiO2 is nox replaced by HfO2, but new dielectrics with a high permittivity (high-k) will have to be integrated in the future so that the progession continues. The atomic force microscope (AFM) in Conductive-AFM (C-AFM) mode is an ideal tools for the electrical characterization of thin oxide films at the nanometric scale. In our work, we have tried to study the limits of the C-AFM. C-AFM consists in using an AFM tip as a top electrode in order to perform Intensity-Current (I-V) curves or mapping the current. We have tried and identify the phenomenon which lead to the degradation of the dielectric layer during the application of the positive voltage bias on the tip, which results in a deformation of the surface under study. We have shown that it is a thermal effect due to a large density of current, which is different from dielectric induced breakdown epitaxy (DBIE) observed on the devices, and which may even lead to the degradation of the susbstrate at the interface. This phenomon is favored by the presence of water on the surface although it is not its consequence. This confirms that such electrical measurements should be performed in ultra-high vacuum in spite of the consequences in terms of complexity of the measurement setup. As a consequence, the study of the dielectric material are questionned since the degradation process is partly due to the AFM technique itself and does not allow to extrapolate easily the behaviour of the integrated device. Moreover, the statistical study of the degradation of the layer (Weibull), commonly used, is affected by a bias (measurements are interdependent). In the same way, the modeling of the conduction through the layer must be questionned because the surface of the electrical contact between the tip and the dielectric layer remains a very variable parameter. The charge pumping technique, which consists in caracterizing the traps at the semiconductor / dielectric interface by filling/emptying them with the application of an alternating gate voltage. It allows to extract the states density (Dit(E) and the capture cross section (σ(E)) but does not provide any information about their repartition on the interface. So, we have adapted this technique to the scanning probe microscopy with the conducting AFM probe as a gate. Using gate-less transistors fabricated in the frame of this work, we have demonstrated the feasability of this technique with a satisfying agreement with macroscopic measurements. We are able to measure a signal that can be related to charge pumping. However, the signal is distorted compared to macroscopic measurements. Modeling is needed because in our case, minority carriers must travel from source to drain via a non polarised area. As a perspective, an energetically resolved method to map the interfacial defects might be developed.

<p>This thesis explores bodily representations in Late Iron Age Scandinavia (400–1050 AD). Non-human bodies, such as gold foil figures, and human bodies are analysed. The work starts with an examination and deconstruction of the sex/gender categories to the effect that they are considered to be of minor value for the purposes of the thesis. Three analytical concepts – masks, miniature, and metaphor – are deployed in order to interpret how and why the chosen bodies worked within their prehistoric contexts.</p><p>The manipulations the figures sometimes have undergone are referred to as masking practices, discussed in Part One. It is shown that masks work and are powerful by being paradoxical; that they are vehicles for communication; and that they are, in effect, transitional objects bridging gaps that arise in continuity as a result of events such as symbolic or actual deaths.</p><p>In Part Two miniaturization is discussed. Miniaturization contributes to making worlds intelligible, negotiable and communicative. Bodies in miniatures in comparison to other miniature objects are particularly potent. Taking gold foil figures under special scrutiny, it is claimed that gold, its allusions as well as its inherent properties conveyed numinosity. Consequently gold foil figures, regardless of the context, must be understood as extremely forceful agents.</p><p>Part Three examines metaphorical thinking and how human and animal body parts were used in pro-creational acts, resulting in the birth of persons. However, these need not have been human, but could have been the outcomes of turning a deceased into an ancestor, iron into a steel sword, or clay into a ceramic urn, hence expanding and transforming the members of the family/household. Thus, bone in certain contexts acted as a transitional object or as a generative substance.</p><p>It is concluded that the bodies of research are connected to transitions, and that the theme of transformation was one fundamental characteristic of the societies of study.</p>

Artificial magnetic materials (AMMs) are a type of metamaterials which are engineered to exhibit desirable magnetic properties not found in nature. AMMs are realized by embedding electrically small metallic resonators aligned in parallel planes in a host dielectric medium. In the presence of a magnetic field, an electric current is induced on the inclusions leading to the emergence of an enhanced magnetic response inside the medium at the resonance frequency of the inclusions. AMMs with negative permeability are used to develop single negative, or double negative metamaterials. AMMs with enhanced positive permeability are used to provide magneto-dielectric materials at microwave or optical frequencies where the natural magnetic materials fail to work efficiently. Artificial magnetic materials have proliferating applications in microwave and optical frequency region. Such applications include inversely refracting the light beam, invisibility cloaking, ultra miniaturizing and frequency bandwidth enhancing low profile antennas, planar superlensing, super-sensitive sensing, decoupling proximal high profile antennas, and enhancing solar cells efficiency, among others. AMMs have unique enabling features that allow for these important applications. Fundamental limitations on the performance of artificial magnetic materials have been derived. The first limitation which depends on the generic model of permeability functions expresses that the frequency dispersion in an AMM is limited by the desired operational bandwidth. The other constraints are derived based on the geometrical limitations of inclusions. These limitations are calculated based on a circuit model. Therefore, a formulation for permeability and magnetic susceptibility of the media based on a circuit model is developed. The formulation is in terms of a geometrical parameter that represents the geometrical characteristics of the inclusions such as area, perimeter and curvature, and a physical parameter that represents the physical, structural and fabrication characteristics of the medium. The effect of the newly introduced parameters on the effective permeability of the medium and the magnetic loss tangent are studied. In addition, the constraints and relations are used to methodically design artificial magnetic material meeting specific operational requirements. A novel design methodology based on an introduced analytical formulation for artificial magnetic material with desired properties is implemented. The synthesis methodology is performed in an iterative four-step algorithm. In the first step, the feasibility of the design is tested to meet the fundamental constraints. In consecutive steps, the geometrical and physical factors which are attributed to the area and perimeter of the inclusion are synthesized and calculated. An updated range of the inclusion's area and perimeter is obtained through consecutive iterations. Finally, the outcome of the iterative procedure is checked for geometrical realizability. The strategy behind the design methodology is generic and can be applied to any adopted circuit based model for AMMs. Several generic geometries are introduced to realize any combination of geometrically realizable area and perimeter (s,l) pairs. A realizable geometry is referred to a contour that satisfies Dido's inequality. The generic geometries introduced here can be used to fabricate feasible AMMs. The novel generic geometries not only can be used to enhance magnetic properties, but also they can be configured to provide specific permeability with desired dispersion function over a certain frequency bandwidth with a maximum magnetic loss tangent. The proposed generic geometries are parametric contours with uncorrelated perimeter and area function. Geometries are configured by tuning parameters in order to possess specified perimeter and surface area. The produced contour is considered as the inclusion's shape. The inclusions are accordingly termed Rose curve resonators (RCRs), Corrugated rectangular resonators (CRRs) and Sine oval resonators (SORs). Moreover, the detailed characteristics of the RCR are studied. The RCRs are used as complementary resonators in design of the ground plane in a microstrip stop-band filter, and as the substrate in design of a miniaturized patch antenna. The performance of new designs is compared with the counterpart devices, and the advantages are discussed.

Wireless communications have been an indispensable aspect of everyday life, and there is an increasing consumer demand for accessing several wireless communication technologies from a single, compact, mobile device. System-on-package (SOP) technology is an advanced packaging technology that has been proven to realize the convergence of multiple functions into miniaturized, high-performance systems to meet this demand. With the advancements in the SOP technology, the miniaturization of the front-end module has been achieved using embedded passives in multilayer packages. However, the integration of the antenna directly on the module package is still the barrier to achieve a fully-integrated, high-performance RF SOP system. The main reason for this missing link is that integrating the antenna on the package requires miniaturizing the antenna, which is a difficult task. The focus of this dissertation is to design high-performance antennas along with developing techniques for miniaturization and system-on-package (SOP) integration of these antennas to achieve fully-integrated SOP systems using advanced multilayer organic substrates and thin-film magneto-dielectric materials. The targeted spectrum for the antenna designs are 2.4/5 GHz WLAN/WiMAX and 60 GHz WPAN bands. Several novel antenna designs and configurations to integrate the antenna on the package along with the module are discussed in this dissertation. The advanced polymers used in this research are Liquid Crystalline Polymer (LCP), RXP, and thin-film magneto-dielectrics.