Orientador: Paulo Roberto Bueno / Coorientador: Flávio Cesar Bedatty Fernandes / Banca: Hideko Yamanaka / Banca: Marina Ribeiro Batistuti / Resumo: Desde a primeira descrição de biossensor reportada por Clark e Lyons em 1962, houve um extenso trabalho no desenvolvimento e aprimoramento de novas técnicas de biossensoriamento para detecção de biomarcadores com relevância médica. Destaca-se nesse processo o estudo de superfície de eletrodos, pois esse influencia diretamente em aspectos como; sensibilidade, estabilidade e qualidade do sinal. Portanto, este projeto consiste em avaliar comparativamente três superfícies de eletrodos baseadas em nanoestruturas contendo nanopartículas de azul da Prússia, funcionando com sonda redox do sistema, e materiais carbonáceos (como óxido de grafeno e nanotubos de carbono) para aplicação em biossensores. Foram avaliados aspectos como composição, características capacitivas redox e estabilidade de sinal. A técnica de análise utilizada é a espectroscopia de capacitância eletroquímica (ECE) que apresenta vantagens como não usar amplificadores de sinal (sondas redox) em solução, configuração esta, importante para métodos de diagnóstico point-of-care. Das superfícies analisadas, a composta por nanopartículas de azul da Prússia e óxido de grafeno (PBNP+GO) apresentou os melhores parâmetros de estabilidade e compatibilidade com os aspectos teóricos da técnica de ECE, sendo então selecionada para realização de testes de biossensoriamento que, através da funcionalização da superfície com anticorpos Anti-IL-6, detectaram seletivamente a presença do biomarcador IL-6. / Abstract: Since the first description of biosensor reported by Clark and Lyons in 1962, numerous works related to the development and enhancement of novel medical biosensing techniques have been published. In that context, it must be highlighted the study of electrode surfaces as it has direct influence in aspects like; sensitivity, stability and signal quality. Therefore, this project aims to evaluate three electrode surfaces based on nanostructures with Prussian blue nanoparticles, as redox probe, and carbonaceous materials (like graphene oxide and carbon nanotubes) and their application in biosensors. It was evaluated aspects like composition, redox capacitive characteristics and signal stability. The electrochemical capacitance spectroscopy technique (ECE) was used as it offers several advantages like no need of signal amplifiers (redox probes) in solution and, then, making this technique more adequate for point-of-care diagnosis. Among the analysed surfaces, the one composed by Prussian blue nanoparticles and graphene oxide (PBNP+GO) was identified as the best surface in terms of stability and compatibility to the theoretical aspects of ECE. Therefore, that structure was selected to further biosensing essays, by functionalizing the surface with Anti-IL-6 antibodies, that indicated the selective detection of the IL-6 biomarker. / Mestre

The aim of this study was to improve electrical properties of conductive polymer composites. For this purpose, various studies were performed using different materials in this dissertation. In order to investigate the effect of alternative composite preparation methods on electrical conductivity, nylon 6/carbon black systems were prepared by both in-situ polymerization and melt-compounding techniques. When compared with melt compounding, in-situ polymerization method provided enhancement in electrical conductivity of nylon 6 composites. Furthermore, it was aimed to improve electrical conductivity of polymer composites by modifying surface chemistry of carbon black. 1 wt. % solutions of 3-Aminopropyltriethoxysilane and formamide were tried as chemical modifier, and treated carbon black was melt mixed with low-density polyethylene (LDPE) and nylon 6. According to electron spectroscopy for chemical analysis (ESCA), chemicals used for surface treatment may have acted as doping agent and improved electrical conductivity of polymer composites more than untreated carbon black did. Formamide was more effective as dopant compared to the silane coupling agent. In order to investigate electromagnetic interference (EMI) shielding effectiveness and dielectric properties of conductive polymer composites, 1, 2 and 3 wt. % solutions of formamide were tried as chemical modifier and treated carbon black was melt mixed with poly(ethylene terephthalate) (PET). Composites containing formamide treated carbon black exhibited enhancement in electrical conductivity, EMI shielding effectiveness and dielectric constant values compared to composites with untreated carbon black. In order to enhance electrical conductivity of polymer composites, the selective localization of conductive particles in multiphase polymeric materials was aimed. For this purpose, carbon nanotubes (CNT) were melt mixed with polypropylene (PP)/PET. Grinding, a type of solid state processing technique, was applied to PP/PET/CNT systems to reduce the average domain size of blend phases and to improve interfacial adhesion between these phases. Grinding technique exhibited improvement in electrical conductivity and mechanical properties of PP/PET/CNT systems at low PET compositions. To investigate application potential of conductive polymer composites, polyaniline (Pani)/carbon nanotubes (CNT) composites were synthesized and electrochemical capacitance performances of these systems, as electrode material in electrochemical capacitors, were studied. Polyaniline/carbon nanotubes composites resulted in a higher specific capacitance than that of the composite constituents. Pseudocapacitance behavior of Pani might contribute to the double layer capacitance behavior of nanotubes. Additionally, as an alternative to Pani/CNT systems, polyaniline films were deposited on treated current collectors and electrochemical capacitance performances of these electrode systems were investigated. The highest specific capacitance of polyaniline/carbon nanotubes composites was 20 F/g and this value increased to 35.5 F/g with polyaniline film deposited on treated current collector.

Orientador: Paulo Roberto Bueno / Coorientador: Flávio Cesar Bedatty Fernandes / Banca: Maria Del Pilar Taboada Sotomayor / Banca: Paulo Inácio da Costa / Resumo: O sucesso no tratamento de muitos tipos doenças passa pela detecção seletiva e sensível de biomarcadores proteicos que permitam um diagnóstico precoce. A dengue é uma doença infecciosa de diagnóstico clínico impreciso e diagnóstico laboratorial demorado e custoso, a qual não possui tratamento ou vacina efetivos. Portanto se requer de ferramentas diagnósticas precisas, baratas e portáveis que permitam o diagnóstico rápido para realizar um tratamento adequado de sintomas e identificar os focos infecciosos para prevenir o espalhamento da doença. Um biomarcador útil na detecção da dengue, é a proteína NS1 que vem sendo utilizada com sucesso em diferentes plataformas de diagnóstico. Porém, nenhuma das plataformas oferecidas a nível comercial, consegue combinar a precisão, portabilidade, baixo custo e facilidade de manuseio. Portanto, o melhoramento de ditas ferramentas é o foco de bastantes pesquisas. Neste trabalho se apresenta uma plataforma que se amostra útil para a detecção de diferentes biomarcadores, incluindo a proteína NS1. Esta plataforma combina o uso de uma técnica eletroquímica como é a Espectroscopia de Capacitância Eletroquímica (ECE), com o uso de peptídeos redox e está baseada na funcionalização de eletrodos de ouro mediante formação de monocamadas auto-organizadas (SAM) confeccionadas com um peptídeo redox (Fc-Glu-Gli-Ser-Gli-Ser-Cys) desenhado para ser ancorado em superfícies metálicas, ao mesmo tempo que tem capacidade de ancorar uma sonda redox e um biorecepto... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Success in the treatment of many kinds of illnesses depends on the selective and sensitive detection of protein biomarkers that allow an early diagnosis. Dengue is and infectious disease of imprecise clinical diagnostic and delayed and expensive laboratorial diagnostic. This disease does not have an effective vaccine or treatment. Therefore, precise, cheap and portable diagnostic tools are necessary to allow a fast diagnostic in order to treat the symptoms, identify focuses of infection, and thus prevent the spreading of the disease. A useful biomarker in the detection of dengue is the protein NS1, which has been successfully used in different diagnostic platforms. However, none of the commercially available platforms combines precision, portability, low cost and user friendliness. Consequently, the improvement of such tools is object of ample research. This work, introduces a platform, which is useful for the detection of various biomarkers, including the protein NS1. This platform combines the usage of an electrochemical technique such as Electrochemical Capacitance Spectroscopy (ECS) and the use of redox peptides. It is based in the functionalization of gold electrodes through formation of Self Assembled Monolayers (SAM) formed by a redox peptide (Fc-Glu-Gli-Ser-Gli-Ser-Cys) designed to bind to metallic surfaces as well as to anchor a redox probe and a bioreceptor in the same structure/molecule. It presents the additional advantage of forming anti-fowling SAMs, which is a ... (Complete abstract click electronic access below) / Mestre

Submitted by RAPHAEL MAZZINE BARBOSA DE OLIVEIRA (mazzine.r@gmail.com) on 2018-08-31T12:54:04Z No. of bitstreams: 1 DISSERTACAO_RMAZZINE.pdf: 2481284 bytes, checksum: e17b453dc770c4f6b899c9c0a5de342a (MD5) / Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-09-05T12:38:02Z (GMT) No. of bitstreams: 1 oliveira_rmb_me_araiq_int.pdf: 2195098 bytes, checksum: 013fbe713d5edbed6ff4d629e660b906 (MD5) / Made available in DSpace on 2018-09-05T12:38:02Z (GMT). No. of bitstreams: 1 oliveira_rmb_me_araiq_int.pdf: 2195098 bytes, checksum: 013fbe713d5edbed6ff4d629e660b906 (MD5) Previous issue date: 2018-08-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Desde a primeira descrição de biossensor reportada por Clark e Lyons em 1962, houve um extenso trabalho no desenvolvimento e aprimoramento de novas técnicas de biossensoriamento para detecção de biomarcadores com relevância médica. Destaca-se nesse processo o estudo de superfície de eletrodos, pois esse influencia diretamente em aspectos como; sensibilidade, estabilidade e qualidade do sinal. Portanto, este projeto consiste em avaliar comparativamente três superfícies de eletrodos baseadas em nanoestruturas contendo nanopartículas de azul da Prússia, funcionando com sonda redox do sistema, e materiais carbonáceos (como óxido de grafeno e nanotubos de carbono) para aplicação em biossensores. Foram avaliados aspectos como composição, características capacitivas redox e estabilidade de sinal. A técnica de análise utilizada é a espectroscopia de capacitância eletroquímica (ECE) que apresenta vantagens como não usar amplificadores de sinal (sondas redox) em solução, configuração esta, importante para métodos de diagnóstico point-of-care. Das superfícies analisadas, a composta por nanopartículas de azul da Prússia e óxido de grafeno (PBNP+GO) apresentou os melhores parâmetros de estabilidade e compatibilidade com os aspectos teóricos da técnica de ECE, sendo então selecionada para realização de testes de biossensoriamento que, através da funcionalização da superfície com anticorpos Anti-IL-6, detectaram seletivamente a presença do biomarcador IL-6. / Since the first description of biosensor reported by Clark and Lyons in 1962, numerous works related to the development and enhancement of novel medical biosensing techniques have been published. In that context, it must be highlighted the study of electrode surfaces as it has direct influence in aspects like; sensitivity, stability and signal quality. Therefore, this project aims to evaluate three electrode surfaces based on nanostructures with Prussian blue nanoparticles, as redox probe, and carbonaceous materials (like graphene oxide and carbon nanotubes) and their application in biosensors. It was evaluated aspects like composition, redox capacitive characteristics and signal stability. The electrochemical capacitance spectroscopy technique (ECE) was used as it offers several advantages like no need of signal amplifiers (redox probes) in solution and, then, making this technique more adequate for point-of-care diagnosis. Among the analysed surfaces, the one composed by Prussian blue nanoparticles and graphene oxide (PBNP+GO) was identified as the best surface in terms of stability and compatibility to the theoretical aspects of ECE. Therefore, that structure was selected to further biosensing essays, by functionalizing the surface with Anti-IL-6 antibodies, that indicated the selective detection of the IL-6 biomarker. / 1583843

Submitted by Veronica Neshmi Salaues Mendoza (neshmi_salaues@hotmail.com) on 2018-04-18T15:18:38Z No. of bitstreams: 1 Salaues_M_Dissert_Araraiq.pdf: 2461056 bytes, checksum: b0790442c72a5c574565c09b578075df (MD5) / Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-04-18T19:43:41Z (GMT) No. of bitstreams: 1 mendonza_vns_me_araiq_int.pdf: 2392917 bytes, checksum: 3697fdc59d96b5ae59f7207b7abe76e6 (MD5) / Made available in DSpace on 2018-04-18T19:43:41Z (GMT). No. of bitstreams: 1 mendonza_vns_me_araiq_int.pdf: 2392917 bytes, checksum: 3697fdc59d96b5ae59f7207b7abe76e6 (MD5) Previous issue date: 2018-03-13 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O sucesso no tratamento de muitos tipos doenças passa pela detecção seletiva e sensível de biomarcadores proteicos que permitam um diagnóstico precoce. A dengue é uma doença infecciosa de diagnóstico clínico impreciso e diagnóstico laboratorial demorado e custoso, a qual não possui tratamento ou vacina efetivos. Portanto se requer de ferramentas diagnósticas precisas, baratas e portáveis que permitam o diagnóstico rápido para realizar um tratamento adequado de sintomas e identificar os focos infecciosos para prevenir o espalhamento da doença. Um biomarcador útil na detecção da dengue, é a proteína NS1 que vem sendo utilizada com sucesso em diferentes plataformas de diagnóstico. Porém, nenhuma das plataformas oferecidas a nível comercial, consegue combinar a precisão, portabilidade, baixo custo e facilidade de manuseio. Portanto, o melhoramento de ditas ferramentas é o foco de bastantes pesquisas. Neste trabalho se apresenta uma plataforma que se amostra útil para a detecção de diferentes biomarcadores, incluindo a proteína NS1. Esta plataforma combina o uso de uma técnica eletroquímica como é a Espectroscopia de Capacitância Eletroquímica (ECE), com o uso de peptídeos redox e está baseada na funcionalização de eletrodos de ouro mediante formação de monocamadas auto-organizadas (SAM) confeccionadas com um peptídeo redox (Fc-Glu-Gli-Ser-Gli-Ser-Cys) desenhado para ser ancorado em superfícies metálicas, ao mesmo tempo que tem capacidade de ancorar uma sonda redox e um bioreceptor na mesma estrutura/molécula, com a vantagem adicional que a SAM obtida tem propriedades anti-incrustantes desejáveis em biossensoriamento. Ensaios realizados com a proteína NS1 permitiram a detecção de esta proteína em concentrações de 2 µg/ml. / Success in the treatment of many kinds of illnesses depends on the selective and sensitive detection of protein biomarkers that allow an early diagnosis. Dengue is and infectious disease of imprecise clinical diagnostic and delayed and expensive laboratorial diagnostic. This disease does not have an effective vaccine or treatment. Therefore, precise, cheap and portable diagnostic tools are necessary to allow a fast diagnostic in order to treat the symptoms, identify focuses of infection, and thus prevent the spreading of the disease. A useful biomarker in the detection of dengue is the protein NS1, which has been successfully used in different diagnostic platforms. However, none of the commercially available platforms combines precision, portability, low cost and user friendliness. Consequently, the improvement of such tools is object of ample research. This work, introduces a platform, which is useful for the detection of various biomarkers, including the protein NS1. This platform combines the usage of an electrochemical technique such as Electrochemical Capacitance Spectroscopy (ECS) and the use of redox peptides. It is based in the functionalization of gold electrodes through formation of Self Assembled Monolayers (SAM) formed by a redox peptide (Fc-Glu-Gli-Ser-Gli-Ser-Cys) designed to bind to metallic surfaces as well as to anchor a redox probe and a bioreceptor in the same structure/molecule. It presents the additional advantage of forming anti-fowling SAMs, which is a highly desirable property for biosensing. Tests made with NS1 protein allowed the detection of this protein in concentrations as low as 2 µg/ml. / 190233/2015-0