Carbon nanotubes are molecular-scale tubes of graphitic carbon that possess many unique properties. They have high tensile strength and elastic modulus, are thermally and electrically conductive, and can be structurally modified using well established carbon chemistries. There is global interest in taking advantage of their unique combination of properties and using these interesting materials as components in nanoscale devices and composite materials. The goal of this research was the correlation of the mechanical properties of coiled carbon nanotubes with their chemical structure. Individual nanocoils, grown by chemical vapor deposition, were attached to scanning probe tip using the arc discharge method. Using a scanning probe microscope the nanocoils are repeatedly brought into and out of contact with a chemically-modified substrate. Precise control over the length (or area) of contact with the substrate is achievable through simultaneous monitoring the cantilever deflection resonance, and correlating these with scanner movement. The mechanical response of nanocoils depended upon the extent of their compression. Nonlinear response of the nanocoil was observed consistent with compression, buckling, and slip-stick motion of the nanocoil. The chemical structure of the nanocoil and its orientation on the tip was determined using scanning and transmission electron microscopy. The mechanical stiffness of eighteen different nanocoils was determined in three ways. In the first, the spring constant of each nanocoil was computed from the slope of the linear response region of the force-distance curve. The assumptions upon which this calculation is based are: 1) under compression, the cantilever-nanocoil system can be modeled as two-springs in series, and 2) the nanocoil behaves as an ideal spring as the load from the cantilever is applied. Nanocoil spring constants determined in this fashion ranged from 6.5x10-3 to 5.16 TPa for the CCNTs understudy. In the second, the spring constant of the nanocoil was computed from measuring the critical force required to buckle the nanocoil. The critical force method measured the force at the point where the nanocoil-cantilever system diverges from a linear region in the force curve. Nanocoil spring constants determined in this fashion ranged from 1.3x10-5 to 10.4 TPa for the CCNTs understudy. In the third, the spring constant of each nanocoil was computed from the thermal resonance of the cantilever-nanocoil system. Prior to contact of the nanocoil with the substrate, the effective spring constant of the system is essentially that of the cantilever. At the point of contact and prior to buckling or slip-stick motion, the effective spring constant of the system is modeled as two springs in parallel. Nanocoil spring constants determined in this fashion ranged from 2.7x10-3 to 0.03 TPa for the CCNTs understudy. Using the thermal resonance of the cantilever system a trend was observed relating nanocoil structure to the calculated modulus. Hollow, tube-like nanostructures had a higher measured modulus than solid or fibrous structures by several orders of magnitude. One can conclude that the structure of carbon nanocoils can be determined from using their mechanical properties. This correlation should significantly contribute to the knowledge of the scientific and engineering community. It will enable the integration of carbon nanocoils in microelectromechanical (MEMS) or nanoelectromechanical systems (NEMS) as resonators, vibration dampers, or any other application in which springs are used within complex devices.

Recent carbon allotropes such as carbon nanotubes (CNTs), fullerenes (C60s) and graphene have attracted great interests in both science and engineering due to their unique properties such as excellent electrical and mechanical properties as well as its vast surface area, and have led to many commercial applications. Especially, CNTs have been considered to be one of the promising candidates in the Li ion battery system because of its outstanding properties. However, the experimental results in the pristine CNT system have shown just slight improvement than original graphitic carbon material, which has been attributed to the weak adsorption of Li on CNTs. In this study, we investigated two types of CNT-C60 hybrid system consisting of CNTs and C60s to improve Li adsorption capabilities and predict its performance through quantum mechanical (QM) computations. First, we investigated adsorption energy of lithium (Li) on dilute CNT-C60 hybrid and CNT-C60 nanobud system as well as various electronic properties such as band structure, density of states (DOS), molecular orbital and charge distribution. Then, we expanded our interest to the more realistic condensed structure of CNT-C60 hybrid and nanobud system to examine actual electrochemical characteristics. The study of the condensed structure has been expanded to the very unique CNT-C60 nano-network system and examined mechanical strength as well as electronic properties. Finally, Li adsorption on other carbon allotropes system such as graphene-C60 hybrid and graphene-C60 bud system was investigated in order to provide fundamental understanding of electronic interaction between carbon allotrope and effect of Li adsorption.

Fabrication of SWCNT-PMMA and Activated Charcoal- PMMA composites was carried out by the compression moulding technique. Then Mechanical and Electrical properties of the composites were investigated. The morphological studies of composites showed a) good dispersion of fillers and b) good interaction between fillers and matrix. Electrical conductivity of SWCNT-PMMA composites was increased by 9 orders of magnitude (at 0.8 % volume fraction of SWCNT) and that of AC-PMMA composites increased by 16 orders of magnitude (at 17 % volume fraction of AC). The percolation threshold of both composites turned out to be lower compared to the theoretical values. A significant improvement in mechanical properties was obtained ??? particularly in AC-PMMA composites which showed a 400 % improvement in Vickers microhardness ??? raising the polymer matrix abrasion property literally to that of Aluminium alloys (Dobrazanski et al 2006). In conclusion, it is to be noted that Activated Charcoal - PMMA composites have a great potential for cost effective conducting polymer composite production by the use of cheap filler: In addition, the compression moulding technique shows good potential for cost effective fabricating technique for amorphous polymers with high electrical and mechanical properties.

Dans la nature, la réduction du dioxygène est catalysée par des enzymes de la famille des oxydoréductases. A l’heure actuelle, ces protéines spécifiques et efficaces sont envisagés comme biocatalyseurs au sein de biopile enzymatique. Dans ce contexte, l’optimisation de l’orientation et de la connexion d’oxydases multi-cuivre (MCOs) pour la réduction d’O2 sur des matrices de nanotubes carbone (CNTs) fonctionnalisées a été étudiée. Dans un premier temps, le transfert électronique direct de la laccase est optimisé par la fonctionnalisation non covalente de CNTs par divers dérivés hydrophobes. La dynamique moléculaire ainsi que la modélisation électrochimique ont permis la rationalisation des performances des différentes biocathodes développées. Dans une seconde approche, la modification spécifique par des groupements pyrène de la surface de laccases modifiées par mutagénèse a également été envisagée. La fonctionnalisation supramoléculaire de CNTs par des feuillets de graphène fonctionnalisés d’une part, et par des nanoparticules d’or d’autre part, a également permis de favoriser la connexion de laccases. La seconde partie présente l’élaboration d’autres types de biocathodes basées sur la connexion directe de bilirubines oxydases. Plusieurs stratégies de fonctionnalisation covalente et non covalente de CNTs ont été envisagées. Les différentes biocathodes élaborées par l’assemblage supramoléculaire de MCOs et de matériaux nanostructurés délivrent des densités de courant de réduction du dioxygène de plusieurs mA cm-2. Ces nouvelles bioélectrodes combinées à une bioanode qui catalyse l’oxydation du glucose ont permis le développement de biopiles enzymatiques glucose/O2 délivrant des densités maximales de puissances allant de 250 µW cm-2 à 750 µW cm-2 selon les conditions expérimentales. Enfin une bioanode à base d’une hydrogénase hyperthermophile a été développée et associée à une biocathode à base de bilirubine oxydase pour former un nouveau design de biopile H2/O2. Au sein de ce dispositif, la biocathode à diffusion de gaz réduit directement l’oxygène provenant de l’air, ce qui permet de s’affranchir de l’utilisation d’une membrane séparatrice tout en protégeant l’hydrogénase de sa désactivation en présence d’oxygène. Cette nouvelle biopile délivre une densité maximale de puissance de 750 µW cm-2. / The reduction of oxygen is realized in nature by oxidoreductase enzymes. Currently, these highly specific and efficient proteins are considered as biocatalysts for the development of biofuel cells. In this context, optimizing the orientation and the connection of multicopper oxidase (MCOs) for the reduction of O2 on functionalized carbon nanotubes was studied. In the first part of this manuscript, direct electron transfer of laccase is assessed and optimized by the non-covalent functionalization of CNTs by various hydrophobic derivatives. Electrochemical modeling and molecular dynamics enabled the rationalization of the developed biocathodes efficiency. In a second approach, the specific modification by pyrene moieties of laccases surface modified by protein engineered has also been considered. Additionally, supramolecular functionalization of CNTs by modified graphene sheets and gold nanoparticles also helped to promote laccase connection. The second part presents the development of other types of biocathodes based on the direct connection of bilirubin oxidase. Several strategies of covalent and non-covalent CNTs functionalization have been considered. The different biocathodes developed by the supramolecular assembly of nanostructured materials and MCOs delivered current density of several mA cm-2 for oxygen reduction. These new bioelectrodes combined with a bioanode which catalyzes the glucose oxidation have enabled the development of glucose/O2 enzymatic biofuel cells; delivering maximum power densities from 250 µW cm-2 to 750 µW cm-2 depending on the experimental conditions. Finally a hyperthermophilic hydrogenase based bioanode was developed and associated with a bilirubin oxidase-based biocathode to form a new design of H2/O2 biofuel cell. Within this device, the gas diffusion biocathode directly reduces oxygen from the air, which eliminates the use of a separation membrane while protecting the hydrogenase from its deactivation in the presence oxygen. This new biofuel cell delivers a maximum power density of 750 µW cm-2.

La manipulation de la matière au niveau nanométrique a ouvert depuis une quinzaine d'années de nouveaux champs fondamentaux et applicatifs pour les scientifiques et les industriels. Dans ce nouveau paradigme, la nanoélectronique quantique se propose de fonder une nouvelle électronique basée sur les phénomènes quantiques de la matière et plus particulièrement sur la nature quantique des électrons. Ce projet de thèse s'articule autour d'un système électronique quantique hybride supraconducteur/nanotube de carbone (CNT) dénommé nano-SQUID. Ce dispositif présente une boucle supraconductrice contenant deux jonctions CNT en parallèle. Il couple de façon unique les propriétés d'un interféromètre supraconducteur SQUID avec celles de jonctions Josephson à boîte quantique moléculaire. A travers des expériences de transport réalisées, à des températures de quelques dizaines de milli-Kelvins, dans un cryostat à dilution inversé, nous avons étudié les interactions électroniques entre une boîte quantique nanotube et des électrodes supraconductrices. Nous nous sommes particulièrement focalisés sur l'influence de l'état de spin du nanotube sur le courant supraconducteur, qui peut, dans certaines conditions, conduire à la réalisation d'un jonction-. Par un contrôle électrostatique des paramètres microscopiques du dispositif nous avons ainsi pu définir un diagramme de phase expérimental des transitions 0- d'une jonction Josephson à boîte quantique. La dernière partie de cette thèse a porté sur l'utilisation du nano-SQUID comme magnétomètre. En effet, en couplant un aimant moléculaire au CNT composant le SQUID, il a été montré théoriquement qu'il est possible de détecter le retournement d'aimantation d'un spin unique. Nous avons ainsi couplé au nano-SQUID l'aimant moléculaire Double Decker Holmium et réalisé les premières mesures de détections magnétiques aux résultats prometteurs. / The manipulation of matter at the nano-scale has opened, since fifteen years, new fundamental and application avenues for science and industry. In this new paradigm, quantum nano-electronics propose to start a new electronics based on quantum effects of matter and more particularly on the quantum nature of electrons. This thesis project deals with an electronic hybrid superconductor/carbon nanotube (CNT) system called nano-SQUID. This device has a superconducting loop containing two CNT junctions in parallel. This unique system couples the properties of a superconducting interferometer (SQUID) with those of molecular quantum dot (QD) Josephson junctions (CNT junction). Through transport experiments performed in a reversed dilution cryostat at temperatures of several tens of milli-Kelvin, we studied the electronic interactions between a nanotube quantum dot and superconducting electrodes. We specifically focused on the influence of the magnetic state of the nanotube on the superconducting current flowing through. Depending on the QD spin state, the CNT Josephson junction can behave as a -junction. Finally a complete electrostatic control allowed us to define an experimental 0- phase diagram of a QD Josephson junction.

Dans ce manuscrit, nous présentons d'abord le bloc de construction moléculaire ultime pour les dispositifs de spintronique, les aimants à molécule unique (Chapitre 2). En particulier, nous nous concentrerons sur une molecule de TbPc2 et différentes approches pour sonder son aimantation à l'aide de détecteurs a base de nanotubes de carbone et de mécanismes de couplage différents (flux magnétique, couplage électronique et mécanique). Dans le but de construire un detecteur de torque supramoléculaire capable de sonder le moment magnétique d'un aimant moléculaire, nous allons décrire dans le chapitre 3 un candidat très prometteur, un système nanoélectromécanique (NEMS) à base d'un nanotube de carbone. Nous décrirons d'abord les avantages de NEMS à base de carbone par rapport aux résonateurs classiques à base de silicium. Par la suite, nous présenterons l'état de l'art des NEMS à base de nanotubes de carbone, en nous focalisant en particulier sur deux différents mouvements nanomécaniques, un mode de flexion transverse et un mode de compression longitudinal. Dans le chapitre 4, nous présenterons la mise en oeuvre expérimentale d'un detecteur de torque supramoléculaire basé sur NEMS à nanotubes de carbone et des aimants à molécule unique. Nous décrirons d'abord le processus de fabrication ultra propre et les étapes de la caractérisation d'un NEMS à nanotubes de carbone à températures ambiante et cryogénique. Nous allons ensuite démontrer un procédé de greffage d'une molécule aimants de TbPc2 sur un tel NEMS à nanotube de carbone, qui conserve à la fois les propriétés magnétiques de la molécule et les propriétés mécaniques du résonateur. Dans le chapitre 5, nous allons ensuite procéder à une étude systématique du mode de flexion transverse dans un NEMS à nanotube de carbone. Nous montrerons, que la dissipation de ce mode de vibration induit par l'effet tunnel d'électron unique à travers le nanotube de carbone (considére comme point quantique) dépend essentiellement de l'environnement électronique du nanotube, c'est à dire de la capacité, du couplage entre le nanotube de carbone et les electrodes métalliqes, du courant et de la température. Les résultats indiquent que l'on pourrait atteindre des facteurs de qualité de 10^6 ou plus en choisissant un diélectrique de grille appropriées et/ou en améliorant le couplage entre le nanotube de carbone et les electrodes, ce qui permettrait notamment d'augmenter la sensibilité du NEMS nanotubes de carbone par rapport à un torque magnétique générer par le retournement d'un aimant moléculaire. Dans le chapitre 6, nous démontrons la présence d'un mode de vibration longitudinal quantique dans un NEMS à base de nanotube de carbon fonctionnalisé avec des aimants moléculaires de TbPc2. Nous allons en particulier montrer que la nature quantique des deux systèmes, se traduit par un fort couplage entre le mode de compression longitudinal et l'aimantation d'un aimant moléculaire TbPc2 unique greffé sur la parois du nanotube de carbone. Ce fort couplage permet par la suite de détecter les états de spin nucléaire dans la molécule de TbPc2. Enfin, nous présenterons dans la conclusion de ce manuscrit quelques perspectives pour la détection et la manipulation (coherente) d'un seul spin (nucléaire) à l'aide d'un système mécanique quantique. / In this manuscript, we will first present the ultimate molecular building block for spintronic devices, so called single-molecule magnets (Chapter 2). In particular we will focus on a TbPc2 complex and various approaches of probing its magnetization using carbon nanotube detectors and different coupling mechanisms (magnetic flux, electronic and mechanical coupling). With the aim of building a supramolecular torque magnetometer capable of probing the magnetic moment of a molecular magnet, we will describe in Chapter 3 a promising candidate, a carbon nanotube nanoelectromechanical system (NEMS). We will first describe the advantages of carbon based NEMS over classical Si based resonators. Subsequently we will present the state of art of carbon nanotube NEMS and focus in particular on two different nanomechanical motions, a transverse bending mode and a longitudinal stretching mode. In Chapter 4, we present the experimental implementation of a supramolecular torque magnetometer based on carbon nanotube NEMS and single molecule magnets. We first describe the ultraclean bottom-up fabrication process and the extensive characterisation steps of carbon nanotube NEMS at room and cryogenic temperatures. We will finally demonstrate a method of grafting a TbPc2 single molecules magnet on such a carbon nanotube NEMS, that conserves both the magnetic properties of the molecule and the mechanical properties of the resonator. In Chapter 5, we will then perform a systematic study of the transverse bending mode vibration in a carbon nanotube NEMS. We demonstrate for instance, that the dissipation of a carbon nanotube's bending mode vibration to single electron tunneling through the carbon nanotube NEMS-quantum dot critically depends on the dot's electronic environment, i.e. the capacitance, the tunnel coupling to the metal leads, the current and temperature. The findings suggest that one could achieve quality factors of 10^6 or higher by choosing appropriate gate dielectrics and/or by improving the tunnel coupling to the leads, which would notably increase the sensitivity of the carbon nanotube NEMS with respect to a magnetic torque generate by a rotating molecular magnet. In Chapter 6, we demonstrate the presence of a quantized longitudinal stretching mode vibration in a carbon nanotube NEMS functionnalized with TbPc2 single molecule quantum magnets. We will in particular demonstrate that the quantum mechanical nature of both systems, results in a strong coupling between the longitudinal stretching mode and the magnetization of an individual TbPc2 single molecule magnet grafted to the carbon nanotube's sidewall. The strong coupling in fact enables the detection of the nuclear spin states in the TbPc2 molecule. Finally, we present in the conclusion of this manuscript some future prospects for the detection and (coherent) manipulation of a single (nuclear) spin using a mechanical quantum system.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this thesis the behavior of functionalized carbon nanotubes via chemical and physical adsorption and estrural deformation is studied through ab initio calculations based on the DFT formalism, using the SIESTA program. First, we evaluated the behavior of CNTs functionalized with COOH group and it was observed that their position on different sublattices modifies the Carbon nanotube electronic properties, besides the fact that the electronic nature of a semiconductor CNT can be modulated from the concentration of carboxylation. The behavior of armchair CNTs radially deformed was evaluated and it was observed that by the limit of the radial deformation, the electronic character of the nanotubes were keeped as metallic, although the interaction between the walls increases as the deformation increases. The elastic constant values of deformed CNTs with more than one wall indicates the contribution of each individual nanotube constituting the system in its structural and elastic properties. The vibrational frequencies calculated reflect the effect of deformation of the CNTs, as the deformation increases, its frequency decreases. We evaluated the synergistic effect of chemical functionalization of CNTs deformed with the COOH group. For the external functionalization process, more curved region promotes the carboxylation process, whilst for the internal, the COOH group remains confined and does not bind covalently to its wall. Finally, we evaluated the physical adsorption of lithium in deformed CNTs with two layers. Both between the layers, like its exterior, lithium donates charge to the nanotube, not changing its electronic character. The adsorption process of lithium between the walls of deformed CNT is more efficient than on its exterior, in particular for radially deformed configurations. / Nesta tese é estudado o comportamento de nanotubos de carbono funcionalizados via adsorção química e física e deformação estrutural através de cálculos ab initio baseados no formalismo da DFT, utilizando o programa SIESTA. Primeiramente, avaliou-se o comportamento de NTCs funcionalizados com o grupo COOH e observouse que sua posição nas diferentes subredes do nanotubo modifica as propriedades eletrônicas destes, além do fato do caráter eletrônico de um NTC semicondutor poder ser modulado a partir da concentração da carboxilação. O comportamento de NTCs armchair radialmente deformados foi avaliado e observou-se que até o limite da deformação radial, o caráter eletrônico dos nanotubos se mantém metálico, apesar da interação entre as paredes se mostrar cada vez maior à medida que a deformação aumenta. Os valores para a constante elástica de NTCs deformados com mais de uma parede indicam a contribuição individual de cada nanotubo que constitui o sistema em suas propriedades estruturais e elásticas. As frequências vibracionais calculadas refletem o efeito da deformação nos SWNTs, à medida que a deformação aumenta, suas frequências diminuem. Avaliou-se o efeito sinergístico da funcionalização química de NTCs deformados com o grupo COOH. No processo de funcionalização externa, a região mais curva favorece o processo de carboxilação, enquanto que na interna, o grupo COOH se mantém confinado e não se liga covalentemente à sua parede. Por fim, avaliou-se a adsorção física de átomos de lítio em NTCs com duas camadas deformados. Tanto entre as camadas, como em seu exterior, o lítio doa carga para o nanotubo, não mudando seu caráter eletrônico. O processo de adsorção do lítio entre as paredes do NTC deformado se mostrou mais eficiente do que em seu exterior, em especial para as configurações radialmente deformadas.

Submitted by Lucas Custodio Recco null (recco_natacao@yahoo.com.br) on 2016-11-16T18:05:08Z No. of bitstreams: 1 Dissertação tese final 1.pdf: 2637411 bytes, checksum: a84a13ce10364272026f9558f59c65df (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-11-23T12:35:19Z (GMT) No. of bitstreams: 1 recco_lc_me_bot.pdf: 2637411 bytes, checksum: a84a13ce10364272026f9558f59c65df (MD5) / Made available in DSpace on 2016-11-23T12:35:20Z (GMT). No. of bitstreams: 1 recco_lc_me_bot.pdf: 2637411 bytes, checksum: a84a13ce10364272026f9558f59c65df (MD5) Previous issue date: 2016-09-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho foram estudadas síntese e caracterização de filmes finos híbrido de polímeros escovas constituídos de polieletrolíticos reforçados com nanotubos de carbono sobre o substrato de óxido de índio e estanho (ITO). Para a caracterização das superfícies dos filmes foram utilizadas as técnicas de microscopia eletrônica de varredura (MEV), energia dispersiva de raio-x (EDX) e espectroscopia Raman. Foram avaliadas diferentes propriedades estímulo-responsivas dos polímeros escovas que levam a modificações estruturais dos filmes como a influência de pH e da força iônica. Os polímeros escolhidos como modelos foram os polímeros Poli (Vinil Imidazol)-(PVI) e Poli (Àcido Acrilíco)-(PAA). Os ensaios eletroquímicos evidenciaram uma dependência da conformação dos polímeros escovas com a variação de pH e da força iônica e também revelaram o aumento da capacitância desses polímeros quando reforçados com os nanotubos de carbono, sendo que, o PVI obteve melhor resposta quando exposto a pH ácido, uma vez que suas cadeias poliméricas estavam estendidas e carregadas positivamente, permitindo a difusão da espécie redox carregada negativamente até a superfície do eletrodo. O PAA também obteve melhor resposta em meio ácido. Nesse caso as cadeias colapsadas aproximam os tubos do transdutor (ITO), facilitando a troca do par redox. Após a caracterização dos referidos polímeros, os mesmos foram testados como sensores para o monitoramento de hormônios e neurotransmissores que desempenham funções importantes no nosso organismo. / This study describes the synthesis and characterization of hybrid polyelectrolyte based on polymer brush reinforced multi-layer type carbon nanotubes. The characterization of the thin films we used the scanning electron microscopy techniques (SEM), energy dispersive x-ray (EDX) and Raman spectroscopy . The influence of pH and ionic strength were evaluated by electrochemical technique. The polymers Poly (vinyl imidazole) - (PVI) and poly (acrylic acid) - (PAA) were used as matrix brush for anchoring the nanotubes. Electrochemical tests showed a dependence of the conformation of the brush polymers with pH change and ionic strength, and also showed the increase in capacitance of these polymers when reinforced with carbon nanotubes, and the PVI obtained a better response when exposed to acidic pH since its polymer chains were extended and positively charged, allowing the diffusion of negatively charged redox species to the electrode surface. The PAA also obtained better response in acid. In this case the collapsed chains near the transducer tubes (ITO) facilitate the electrons transference. The made electrodes were applied to monitor hormones and neurotransmitters that play important functions in our body.

Made available in DSpace on 2016-12-08T17:19:26Z (GMT). No. of bitstreams: 1 Iury.pdf: 24951 bytes, checksum: 2940126ad384e071aa040115b3667855 (MD5) Previous issue date: 2015-02-19 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / O estado de dispersão das nanopartículas na matriz está diretamente ligado às propriedades físicas dos nanocompósitos. Assim técnicas que visam um estado de dispersão mais homogêneo das nanopartículas na matriz são constantemente estudadas. Funcionalização não covalente, ou física, é uma técnica que utiliza-se de interações Coulombianas e/ou barreira estérica com o objetivo de estabilizar a interação entre nanopartícula/matriz e consequentemente obter um estado de dispersão homogêneo. Utilizando copolímero em bloco BYK- 9077® como agente funcionalizante não covalentemente, este trabalho teve como objetivo produzir nanocompósitos de matriz epoxídica Novolac® reforçados com nanoplateletes de grafeno ou nanotubos de carbono funcionalizados não covalentemente. Foram analisadas a influência da adição do copolímero em bloco nas propriedades mecânicas, térmicas e morfológicas dos nanocompósitos produzidos. Utilizou-se frações volumétricas de nanopartículas nos valores de 0,15%, 0,50% e 1,50%. A partir destes valores foi adicionado copolímero em bloco nas quantidades de 1, 5 e 10 vezes a quantidade em massa das nanopartículas. Foram realizadas espectroscopia Raman para caracterização das nanopartículas, verificando o grau de pureza das mesmas, assim como o número de plateletes empilhados. Analisando os resultados, estado de dispersão das nanopartículas na matriz sem a adição de copolímero em bloco não foi homogêneo, assim foram encontrados aglomerados de nanopartículas em Microscopia Eletrônica de Transmissão. Também os valores de Tg s não variaram significativamente em comparação com a resina pura, indicando dispersão não homogênea. Já ao adicionar copolímero em bloco, em quantidades baixas, 1x, foi possível observar aumentos de 8% no módulo de elasticidade, indicativo de que a adição de copolímero em bloco nesta quantidade tornou a dispersão das nanopartículas mais homogênea na matriz. Esta afirmação foi verificada em Microscopia Eletrônica de transmissão. Em contrapartida, conforme foi aumentado a quantidade de copolímero em bloco, 5 e 10x, foram observadas formação de uma segunda fase, que por consequência diminuiu o módulo de elasticidade, tensão de ruptura e Tg.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-08-31T14:13:50Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese doutorado Bárbara V M Silva.pdf: 8451335 bytes, checksum: 8f05c2e3a44caad45cfbe00e5b36c3eb (MD5) / Made available in DSpace on 2016-08-31T14:13:50Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese doutorado Bárbara V M Silva.pdf: 8451335 bytes, checksum: 8f05c2e3a44caad45cfbe00e5b36c3eb (MD5) Previous issue date: 2016-02-24 / CAPEs / A presente tese descreve o desenvolvimento de sensores eletroquímicos para imunoensaios empregando a tecnologia de eletrodos impressos com a finalidade de detectar a troponina T cardíaca, o marcador mais específico, atualmente, do infarto agudo do miocárdio. Um dos desafios na confecção de sensores eletroquímicos para imunoensaios é alcançar baixos limites de detecção. Nanomateriais de carbono são, recentemente, considerados excelentes estratégias no preparo de superfícies sensoras devido às suas excelentes propriedades, tais como rápida transferência elétrica e atividade catalítica, aumento da relação superfície/volume e, consequentemente, maior quantidade de biomoléculas imobilizadas. Nesta tese, nanotubos de carbono e grafeno foram utilizados sob diferentes abordagens para modificação de superfícies eletródicas. Um imunossensor baseado em eletrodos serigrafados obtidos pela impressão de filmes de nanotubos de carbono amino funcionalizados incorporados em tinta de carbono foi desenvolvido para detecção “livre de marcação”. Os grupos amino dos nanotubos expostos na interface sensora impressa foram utilizados para imobilização orientada dos anticorpos monoclonais anti-troponina T. Os nanofilmes impressos apresentaram uma excelente estabilidade e reprodutibilidade, exibindo um desvio padrão relativo (DP) menor que ~2% (n = 8), comparado com controle (DP ~9%, n = 8). A resposta analítica do sensor, obtida por voltametria de pulso diferencial, apresentou uma faixa linear entre 0,0025 e 0,5 ng/mL de troponina T (r = 0,995; p<0,0001; n=7), combinado a um baixo erro relativo (<<1%) e limite de detecção de 0,0035 ng/mL. Com o propósito de substituir os anticorpos anti-troponina T, visto que estes constituem parte onerosa do dispositivo, um sensor biomimético foi desenvolvido a partir de uma superfície nanoestruturada de grafeno e polipirrol. A técnica de impressão biomimética em superfície (“surface imprinting”) foi utilizada como estratégia para simplificar e reduzir em uma única etapa a produção das cavidades biomiméticas. Estas foram obtidas através da eletropolimerização do polipirrol e derivados copoliméricos orgânicos mimetizando grupos proteicos amino-reativos. As respostas analíticas do sensor foram geradas por voltametria de pulso diferencial, exibindo uma faixa linear de resposta variando de 0,01 a 0,1 ng/mL de troponina T (r = 0,9953; p<0,0001; n=5) e um limite de detecção de 0,006 ng/mL, mostrando um ótimo desempenho do sensor biomimético. As cavidades biomiméticas apresentaram uma constante de dissociação (KD) de 7,3 10- 13 mol/L, indicando boa afinidade à troponina quando comparadas com o sensor controle (sem troponina T), KD igual a 11,6 10-13 mol/L. Em conclusão, ambas as plataformas sensoras mostram potencial para detecção da troponina T em níveis de importância clínica no diagnóstico do infarto agudo, constituindo testes de pronto atendimento para emergências cardiológicas. / This thesis describes the development of electrochemical sensors for immunoassay by using a screen-printed electrodes technology in order to detect the human cardiac troponin T, the most important marker currently of the acute myocardial infarction. One of the challenges in the manufacturing of electrochemical sensors for immunoassays is to reach low limits of detection. Carbon nanomaterials are recently considered excellent strategies in preparing sensing surfaces due to theirs excellent properties, such as rapid electrical transfer and catalytic activity, increase surface / volume ratio and, consequently, offering higher amount of immobilized biomolecules. In this thesis, carbon nanotubes and graphene were used under different approaches in order to modify the sensors surfaces. An immunosensor based on screen printed electrode obtained by printing of amino functionalized carbon nanotubes films incorporated into carbon ink has been developed for "label-free" detection. The amino groups exposed on the imprinted sensor interface were utilized for oriented immobilization of the monoclonal antibody anti-troponin T. The imprinted nanofilms showed an excellent stability and reproducibility, exhibiting a relative standard deviation (RSD) less than ~2% (n = 8) compared to control (RSD ~9%, n = 8). The analytical response of the sensor, obtained by differential pulse voltammetry, showed a linear range between 0.0025 and 0.5 ng/mL (r = 0.995; p <0.0001, n = 7), combined with a low relative error (<< 1 %) and a calculated limit of detection of 0.0035 ng/mL. In order to replace the anti-troponin T antibody, since these are costly part of the device, a biomimetic sensor was developed from a nanostructured surface of graphene and polypyrrole. The biomimetic technique of surface imprinting was used as a strategy for simplify and reduce in a one-step production of the biomimetic cavities. These were obtained by electropolymerization of the pyrrole and its organic copolymers mimicking amino reactive protein groups. The analytical responses of the sensor were obtained by differential pulse voltammetry, exhibiting a linear range response in 0.01 and 0.1 ng/mL of troponin T (r = 0.9953; p <0.0001, n = 5) and a limit of detection of 0.006 ng/mL, showing a good performance of the biomimetic sensor. The biomimetic sites exhibited a dissociation constant (KD) of 7.3 10-13 mol/L, indicating a good affinity to troponin when compared to its control (without troponin T), KD equal to 11.6 10-13 mol/L. In conclusion, both sensor platform the sensor platforms showed a potential for troponin T detection in levels of clinical important for acute myocardial infarction diagnostic, constituting point-of-care testing for cardiac emergency departments.