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Kohlenstoff 2D-Nanoschichten wie Graphen und Graphenoxid sind vielversprechend, aber schwierig in Bezug auf multivalente Wechselwirkungen zu kontrollieren. Das Verständnis, wie neuartige Funktionalisierungsmethoden die Geometrie, Wechselwirkungen und elektronischen Eigenschaften der Graphenblätter beeinflussen, ist der Schwerpunkt dieser Arbeit. Diese Arbeit untersucht zwei Methoden zur Modifikation von 2D-Graphennanoschichten: "Graft to" und "Graft from" Techniken, unter Verwendung von „[2+1] Nitren-Cycloaddition“ und ringöffnender Polymerisation von Glycerin, zusätzlich zum Wachstum von 2D-Triazin-Kohlenstoffstrukturen. Diese modifizierten Nanoschichten wurden hinsichtlich ihrer Wechselwirkung mit dem Vesikulären Stomatitis-Virus (VSV) und ihrer Zweidimensionalität mittels Rastersondenmikroskopie und Raman-Spektroskopie untersucht. Die Studie zeigt das Potenzial funktionalisierter Graphen in der Virologie und liefert Einblicke für zukünftige Forschungen. Ergebnisse zeigten, dass funktionalisierte 2D-TRGO an VSV-Partikel bindet und flexibel genug bleibt, um auf einer flachen Glimmeroberfläche Falten zu bilden, aber sie können die Virushüllen nicht vollständig umschließen. Dies liegt an den hohen Energiekosten für das Biegen großer lateraler Dimensionen (~1-2 μm) im Vergleich zur 200 nm Länge der VSV-Partikel. Eine optimale laterale Dimension von ~300 nm für funktionalisierte 2D-TRGO-Blätter maximiert virale Wechselwirkungen, Hemmungseffizienz und Anzeichen viraler Umhüllung. Triazin, ein Schlüsselmolekül in der Funktionalisierung, kann zur Herstellung von 2D-Triazin-Strukturen im Gramm-Maßstab verwendet werden. Potenzielle Anwendungen funktionalisierter Graphene umfassen spezialisierte antivirale Therapien und die Verwendung als Plattform für antivirale Medikamente. Zudem zeigten die Ergebnisse minimale Störungen der elektronischen Struktur von Graphen durch Triazin-Funktionalisierung. / Carbon-based 2D nanosheets like graphene and graphene oxide are promising but challenging to control in terms of multivalent interactions. Understanding how novel functionalization methods affect graphene sheets' geometry, interaction specificity and electronic properties is the focus of this thesis, which is crucial for advancing the design of 2D nanomaterials. This thesis examines two novel methods for modifying 2D graphene nanosheets: "graft to" and "graft from" techniques, using [2+1] nitrene cycloaddition reactions and ring-opening multibranch polymerization of glycerol in addition to in plane growth of 2D triazine -carbon based structures. These modified nanosheets were studied for their interaction with vesicular stomatitis virus (VSV) and their two-dimensionality using scanning probe microscopy methods and Raman spectroscopy. The study highlights the potential of functionalized graphene nanosheets in virology and provides insights for future research. Results revealed that functionalized 2D TRGO binds to VSV particles and remains flexible enough to wrinkle on a flat mica interface but they cannot completely wrap the viral envelopes. This is due to the high energy cost of bending large lateral dimensions (~1-2μm) compared to the 200 nm length of VSV particles. An optimum lateral dimension of ~300 nm for functionalized 2D TRGO sheets was found to maximize viral interactions, inhibition efficiency, and signs of viral envelopment. Triazine, a key molecule in functionalization, can also be used to create 2D triazine structures on a gram scale. Functionalized graphene's potential applications include specialized antiviral therapies, such as targeted therapies exploiting multivalent interactions between viruses and cellular receptors, and using functionalized graphene as a delivery platform for antiviral drugs. Additionally, results showed minimal disturbance of graphene electronic structure via Triazine functionalization.

In this paper, we propose strain-sensitive thin films based on chemically reduced graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs) without adding any further surfactants. In spite of the insulating properties of the thin-film-based GO due to the presence functional groups such as hydroxyl, epoxy, and carbonyl groups in its atomic structure, a significant enhancement of the film conductivity was reached by chemical reduction with hydro-iodic acid. By optimizing the MWCNT content, a significant improvement of electrical and mechanical thin film sensitivity is realized. The optical properties and the morphology of the prepared thin films were studied using ultraviolet-visible spectroscopy (UV-Vis) and scanning electron microscope (SEM). The UV-Vis spectra showed the ability to tune the band gap of the GO by changing the MWCNT content, whereas the SEM indicated that the MWCNTs were well dissolved and coated by the GO. Investigations of the piezoresistive properties of the hybrid nanocomposite material under mechanical load show a linear trend between the electrical resistance and the applied strain. A relatively high gauge factor of 8.5 is reached compared to the commercial metallic strain gauges. The self-assembled hybrid films exhibit outstanding properties in electric conductivity, mechanical strength, and strain sensitivity, which provide a high potential for use in strain-sensing applications.

A wearable body temperature sensor would allow for early detection of fever or infection, as well as frequent and accurate hassle-free recording. This thesis explores the design of a body-temperature-sensing device inkjet-printed on a flexible substrate. All structures were first modeled by first-principles, theoretical calculations, and then simulated in HFSS. A variety of planar square inductor geometries were studied before selecting an optimal design. The designs were fabricated using multiple techniques and compared to the simulation results. It was determined that inductance must be carefully measured and documented to ensure good functionality. The same is true for parallel-plate and interdigitated capacitors. While inductance remains relatively constant with temperature, the capacitance of the device with a temperature-sensitive dielectric layer will result in a shift in the resonant frequency as environmental or ambient temperature changes. This resonant frequency can be wirelessly detected, with no battery required for the sensing device, from which the temperature can be deduced. From this work, the optimized version of the design comprises of conductive silver in with a temperature-sensitive graphene oxide layer, intended for inkjet-printing on flexible polyimide substrates. Graphene oxide demonstrates a high dielectric permittivity with good sensing capabilities and high accuracy. This work pushes the state-of-the-art in applying these novel materials and techniques to enable flexible body temperature sensors for future biomedical applications.

O objetivo desse trabalho foi desenvolver um compósito cerâmico de zircônia-grafeno para aplicação odontológica. Este estudo avaliou o efeito do pó de partida, concentração de grafeno e da temperatura de sinterização sobre as propriedades mecânicas (dureza e tenacidade à fratura) do compósito desenvolvido. Para isto foram sintetizados os pós de Y-TZP a partir de soluções de óxido-cloreto de zircônio e cloreto de ítrio na proporção desejada de 3mol% através da rota de co-precipitação em solução de hidróxido de amônio seguido por uma série de lavagens em água, etanol e butanol com posterior destilação azeotrópica, secagem, moagem e calcinação. O grafeno foi obtido a partir da exfoliação química de grafite pelo método de Hummers [40] modificado por Marcano [39], o que resultou em um gel acastanhado que foi submetido a lavagem por centrifugação, secagem e desaglomeração em almofariz de ágata, resultando, por fim, no óxido de grafeno. Uma segunda etapa foi o processo de redução química com ácido ascórbico para obtenção de óxido de grafeno reduzido, um pó de coloração escura que foi adicionado à Y-TZP para a obtenção do compósito nas diversas concentrações (em mol%) que foram estudadas: (0,01%, 0,05%, 0,10%, 0,50%, 1,00% e 2,00%). Os pós foram caracterizados por termogravimetria, difração de raios X e espectroscopia (FT-IR). Os espécimes foram confeccionados em matriz metálica cilíndrica e sinterizados em forno tubular em atmosfera inerte. Outros espécimes foram confeccionados em matriz de grafite de alta densidade e sinterizados por Spark Plasma Sintering (SPS). Todas as amostras foram caracterizadas por meio de ensaios de densidade, dureza Vickers, tenacidade à fratura e microscopia eletrônica de varredura. Os maiores valores de densidade relativa foram observados para as amostras sinterizadas em SPS, sendo que se obteve valor de densidade relativa de 98,7 % para a concentração de 0,50% de grafeno e 98,4% para a Y-TZP pura. Por outro lado, o maior valor encontrado em sinterização em atmosfera a 1400°C sem a presença de H2 para Y-TZP pura foi da ordem de 96,76%. Os valores de dureza foram maiores nas amostras sinterizadas em SPS, no entanto a tenacidade à fratura mostrou não se alterar em função do conteúdo de grafeno. As fotomicrografias de MEV mostraram que houve uma variação de tamanho de grão de acordo com a presença do grafeno e do método de sinterização. De acordo com os resultados obtidos neste trabalho foi possível concluir que o processamento desenvolvido permitiu a criação de um compósito cerâmico zircônia-grafeno que pôde ser caracterizado por diversos métodos analíticos. A densidade teórica do compósito desenvolvido não foi alcançada por meio de nenhum dos métodos de sinterização utilizados (Tubular ou SPS) e nem variando-se a temperatura. Para espécimes sinterizados em atmosfera inerte, a maior temperatura de sinterização (1400°C) e a presença do gás H2 não melhorou a densificação. Além disso, esses espécimes tiveram aumento da dureza com o aumento da concentração de grafeno, entretanto, a sua tenacidade à fratura não foi afetada pelo teor de grafeno. Para espécimes sinterizados por meio de SPS, a temperatura de sinterização de 1350°C resultou em melhores valores de densificação. Além disso, para este tipo de sinterização, tanto a dureza como a tenacidade à fratura foram afetadas pelo teor de grafeno. / The objective of this work was to develop a zirconia-graphene ceramic composite for dental application. The study evaluated the effect of the starting powder effect, graphene concentration and sintering temperature on the mechanical properties of the composite. For this, the Y-TZP powders were synthesized from zirconium chloride and yttrium chloride solutions in the desired ratio of 3 mol% through the co-precipitation route in ammonium hydroxide solution followed by a series of washes in water, ethanol and butanol with subsequent azeotropic distillation, drying, grinding and calcination. Graphene was obtained from the chemical exfoliation of graphite by the method of Humans modified by Marcano, which resulted in a brownish gel that was subjected to washing by centrifugation, drying and deagglomeration in agate mortar, resulting finally in the graphene oxide. A second step was the chemical reduction with ascorbic acid to obtain reduced graphene oxide, a dark-colored powder that was added to the Y-TZP to obtain the composite in the various concentrations (in mol%) that were studied (0, 01%, 0.05%, 0.10%, 0.50%, 1.00% and 2.00%). The powders were characterized by thermogravimetry, X-ray diffraction and spectroscopy (FT-IR). The specimens were made in cylindrical metallic matrix and sintered in a tubular oven. Other samples were made in high density graphite matrix and sintered by Spark Plasma Sintering (SPS). All samples were characterized by means of density tests, Vickers hardness, fracture toughness and scanning electron microscopy. The highest values of relative density were observed for the sintered samples in SPS. A relative density of 98.7% was obtained for the 0.50% concentration of graphene and 98.4% for the pure Y-TZP. On the other hand, the highest value found in tubular sintering at 1400 ° C without the presence of H2 for pure Y-TZP was of the order of 96.76%. The hardness values were higher in the sintered samples in SPS, however the fracture toughness showed not to change as a function of the content of graphene. SEM images showed that there was a variation of grain size according to the presence of graphene and the sintering method. According to the results of this study it was concluded that the process developed allowed the creation of a graphene-zirconia ceramic composite which can be characterized by various analytical methods. The theoretical density of the composite developed was not achieved by any of the sintering methods used (tubular or SPS) nor by varying the temperature. For tubular sintered specimens, the higher sintering temperature (1400 ° C) and the presence of H2 gas did not improve densification. In addition, these specimens had increased hardness with increasing graphene concentration, however, their fracture toughness was not affected by graphene content. For sintered specimens by SPS, the sintering temperature of 1350 ° C resulted in better densification values. In addition, for this type of sintering, both hardness and fracture toughness were affected by the content of graphene

Nos últimos anos, materiais baseados em grafeno têm atraído grande interesse na área eletroquímica devido às suas excelentes propriedades eletrônicas. Neste trabalho, apresentamos a obtenção de óxido de grafeno reduzido utilizando métodos eletroquímicos. A redução eletroquímica do óxido de grafeno (OG) foi realizada na superfície de um eletrodo de carbono vítreo (ECV) utilizando voltametria cíclica. O óxido de grafeno reduzido eletroquimicamente (OG-RE) foi caracterizado utilizando espectroscopia Raman, microscopia eletrônica de varredura (MEV), microscopia de força atômica (MFA), espectroscopia de fotoelétrons excitados por raios-X (XPS) e espectroscopia de impedância eletroquímica. A relação ID/IG obtida através dos espectros Raman do OG e do OG-RE foram de 0,98 e 1,15, respectivamente, indicando que o processo de redução resultou em uma maior desorganização estrutural. A espectroscopia de fotoelétrons de raios-X mostrou que a proporção entre C e O no OG foi de 45,7% e, que após a redução eletroquímica essa relação diminuiu para 38,5%. O eletrodo modificado com OG-RE foi empregado para quantificação de furosemida (FUR) em amostras farmacêuticas utilizando voltametria de pulso diferencial e análise por injeção em fluxo com detecção amperométrica. Os limites de detecção e quantificação calculados para o método proposto foram de 0,35 e 1,18 µmol L-1, respectivamente. Visando à aplicação em amostras de interesse clínico, fabricou-se um sensor descartável e de baixo custo para a detecção de FUR utilizando papel sulfite pintado com lápis de desenho e ativado por laser de CO2. Os estudos voltamétricos utilizando o [Ru(NH3)6]Cl3 mostraram que o transporte de massa neste dispositivo foi governado por difusão e que o tratamento com laser diminui a resistência a transferência de carga, assim como resultou em um menor problema relacionado ao envenenamento da superfície do eletrodo / In recent years, graphene-based materials have attracted great interest in the area of electrochemistry due to its excellent electronic properties. In this work, we present the production of reduced graphene oxide using electrochemical methods. The electrochemical reduction of graphene oxide (GO) was carried out on the surface of a glassy carbon electrode (GCE) using the cyclic voltammetry technique. Electrochemically reduced graphene oxide (ER-GO) was characterized using Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), Xray excited photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). ID / IG ratio obtained through Raman spectra of GO and ER-GO were 0.98 and 1.15, respectively, indicating that the reduction process resulted in greater structural disorganization. XPS showed that the ratio between C and O in the GO was 45.7% and that after electrochemical reduction this ratio decreased to 38.5%. The ER-GO modified electrode was used as a sensor for furosemide (FUR) in pharmaceutical samples using the techniques of differential pulse voltammetry and flow injection analysis with amperometric detection. The limits of detection and quantification for the proposed method were 0.35 and 1.18 µmol L-1, respectively. Aiming to the application in clinical samples a disposable, low-cost paper-based sensor for the detection of FUR was fabricated using office paper painted with drawing pencil and activated by CO2 laser. Voltammetric studies using [Ru(NH3)6]Cl3 have shown that mass transport in this device was controlled by diffusion and the laser decreases resistance to charge transfer, as well as, avoided the problem with electrode surface poisoning

Les travaux réalisés dans cette thèse ont porté sur la synthèse d’oxydes de manganèse et leur association dans des composites avec des matériaux carbonés (NTC, Graphène), pour une utilisation comme matériaux d’électrodes de supercondensateurs fonctionnant en milieux aqueux. Les caractérisations physico-chimiques et électrochimiques ont été menées sur ces matériaux afin d’évaluer leurs performances et étudier l’effet de la nanostructuration. Il s’est avéré que la réalisation de nanocomposites MnO2/ nanotubes de carbone ou MnO2/ oxydes de graphène réduits contribue à l’amélioration des performances électrochimiques. Plusieurs compositions Mn/C ont été étudiées afin de réaliser un matériau d’électrode de supercondensateur optimisé. Des dispositifs asymétriques en milieux aqueux ont été assemblés associant les meilleurs nanocomposites avec une électrode négative de graphène. De nettes améliorations en termes de densités d’énergie et de puissance ont été obtenues sur ces systèmes asymétriques fonctionnant sur 2 volts en milieux aqueux. / The work realized in this thesis focused on the synthesis of manganese oxides and their assembly in composites with carbon materials (CNT, graphene) for supercapacitor applications in aqueous media. Physico-chemical and electrochemical characterizations were conducted to evaluate the effect of the nanostruturation. It was found that nanocomposites MnO2/CNT and MnO2/ reduced graphene oxide contributed to improve the electrochemical performances in aqueous media. Several compositions Mn/C were tested to estimate the best ratio for optimized electrode materials. In order to maximize the energy of the devices, asymmetric devices in aqueous media were assembled using graphene as negative electrode and nanocomposites for positive. Clear improvements in term of energy and power densities were obtained with these systems working at 2 volts in aqueous media.

Nos últimos anos, materiais baseados em grafeno têm atraído grande interesse na área eletroquímica devido às suas excelentes propriedades eletrônicas. Neste trabalho, apresentamos a obtenção de óxido de grafeno reduzido utilizando métodos eletroquímicos. A redução eletroquímica do óxido de grafeno (OG) foi realizada na superfície de um eletrodo de carbono vítreo (ECV) utilizando voltametria cíclica. O óxido de grafeno reduzido eletroquimicamente (OG-RE) foi caracterizado utilizando espectroscopia Raman, microscopia eletrônica de varredura (MEV), microscopia de força atômica (MFA), espectroscopia de fotoelétrons excitados por raios-X (XPS) e espectroscopia de impedância eletroquímica. A relação ID/IG obtida através dos espectros Raman do OG e do OG-RE foram de 0,98 e 1,15, respectivamente, indicando que o processo de redução resultou em uma maior desorganização estrutural. A espectroscopia de fotoelétrons de raios-X mostrou que a proporção entre C e O no OG foi de 45,7% e, que após a redução eletroquímica essa relação diminuiu para 38,5%. O eletrodo modificado com OG-RE foi empregado para quantificação de furosemida (FUR) em amostras farmacêuticas utilizando voltametria de pulso diferencial e análise por injeção em fluxo com detecção amperométrica. Os limites de detecção e quantificação calculados para o método proposto foram de 0,35 e 1,18 µmol L-1, respectivamente. Visando à aplicação em amostras de interesse clínico, fabricou-se um sensor descartável e de baixo custo para a detecção de FUR utilizando papel sulfite pintado com lápis de desenho e ativado por laser de CO2. Os estudos voltamétricos utilizando o [Ru(NH3)6]Cl3 mostraram que o transporte de massa neste dispositivo foi governado por difusão e que o tratamento com laser diminui a resistência a transferência de carga, assim como resultou em um menor problema relacionado ao envenenamento da superfície do eletrodo / In recent years, graphene-based materials have attracted great interest in the area of electrochemistry due to its excellent electronic properties. In this work, we present the production of reduced graphene oxide using electrochemical methods. The electrochemical reduction of graphene oxide (GO) was carried out on the surface of a glassy carbon electrode (GCE) using the cyclic voltammetry technique. Electrochemically reduced graphene oxide (ER-GO) was characterized using Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), Xray excited photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). ID / IG ratio obtained through Raman spectra of GO and ER-GO were 0.98 and 1.15, respectively, indicating that the reduction process resulted in greater structural disorganization. XPS showed that the ratio between C and O in the GO was 45.7% and that after electrochemical reduction this ratio decreased to 38.5%. The ER-GO modified electrode was used as a sensor for furosemide (FUR) in pharmaceutical samples using the techniques of differential pulse voltammetry and flow injection analysis with amperometric detection. The limits of detection and quantification for the proposed method were 0.35 and 1.18 µmol L-1, respectively. Aiming to the application in clinical samples a disposable, low-cost paper-based sensor for the detection of FUR was fabricated using office paper painted with drawing pencil and activated by CO2 laser. Voltammetric studies using [Ru(NH3)6]Cl3 have shown that mass transport in this device was controlled by diffusion and the laser decreases resistance to charge transfer, as well as, avoided the problem with electrode surface poisoning

Chapter I: This chapter briefly gives an introduction about microorganisms, their varieties, growth, reproduction etc. In particular, about bacterial function. A sincere attempt is made to review this briefly, including an account of the studies already reported in the literature. Chapter II deals with the antimicrobial activity of Ag/agar film on Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Candida albicans (C. albicans). In particular, films were repeatedly cycled for its antimicrobial activity. The antimicrobial activity of Ag/agar film was found to be in the order, C. albicans > E. coli > S. aureus. Chapter III describes the synthesis of Ag@AgI NPs in agarose matrix. A detailed antibacterial studies including repetitive cycles are carried out on E. coli and S. aureus bacteria. EPR and TEM studies are carried out on the Ag@AgI/Agarose and the bacteria, respectively, to elucidate a possible mechanism for killing of the bacteria. The hybrid could be recycled for the antibacterial activity many times and is found to be non toxic towards human cervical cancer cell (HeLa cells). Chapter IV reports the antibacterial efficacy of silver nanoparticles (Ag NPs) deposited alternatively layer by layer (LBL) on chitosan polymer in the form of a thin film over a quartz plate and stainless steel strip against E. coli. AFM studies are carried out on the microbe to know the morphological changes affected by the hybrid film. The hybrid films on aging (3 months) are found to be as bioactive as before. Cytotoxicity experiments indicated good biocompatibility. Chapter V describes the fabrication of carbon foam porous electrode modified with reduced graphene oxide-Ag nanocomposites. The device can perform sterilization by killing pathogenic microbes with the aid of just one 1.5V battery with very little power consumption. Chapter VI Here we have studied in particular a property say the influence of surface defect in the production of ROS by ZnO NPs and in turn the bactericide activity. Secondly, a homogeneous ZnO and ZnO/Ag nanohybrid has been synthesized by employing chitosan as mediator. The synergistic antibacterial effect of ZnO/Ag nanohybrid on bacteria is found to be more effective, compared to the individual components (ZnO and Ag). A possible mechanism has been proposed for the death of bacteria by ZnO/Ag nanohybrid, based on EPR studies and TEM studies.

This thesis deals with the research work carried out on the properties and applications such as GaN nanoparticles, Graphene etc. Chapter 1 of the thesis gives introduction to nanomaterials and various aspects of the thesis. Chapter 2 of the thesis describes the synthesis of GaN nanocrystals and their use as white light sources and as room temperature gas sensors. It also discusses negative differential resistance above room temperature exhibited by GaN. Electroluminescence from GaN-polymer heterojunction forms the last section of this chapter. Chapter 3 demonstrates the role of defect concentration on the photodetecting properties of ZnO nanorods with different defects prepared at different temperatures. Chapter 4 presents remarkable infrared and ultraviolet photodetector properties of reduced graphene oxide and graphene nanoribbons. Chapter 5 presents the infrared detecting properties of graphene-like few-layer MoS2. The summary of the thesis is given at the end of the thesis.