In this thesis, the adsorption of single-wall carbon nanotubes (SWCNTs) at the liquid/liquid interface, and the subsequent electrochemical investigation of the electrical properties of the adsorbed nanotubes have been studied. Prior to the adsorption of the nanotube, the stability of dispersion of SWCNTs in non-aqueous solvents was assessed by determining the onset of aggregation of the SWCNTs when organic electrolyte was introduced. It was found that electrostatic repulsion between the SWCNTs contributes significantly to the stability of the SWCNTs in non-aqueous solvents. Similar result was also found when the aggregation kinetics of molybdenum disulphide (MoS2) dispersion in non-aqueous media was studied using the same organic electrolyte. The formation of nanomaterial-polymer composites by deliberate electrochemical oxidation of pyrrole and the sonochemical polymerisation of the organic solvent was also studied. Electrolyte addition was shown to be a promising way to separate the 2D material from the sonopolymer.

A proposta do projeto era a imobilização do complexo [RuCl2(PPh3)3] em matriz de nanotubos de carbono pelo ligante 3-piperidinametanol para ser utilizado em reações de ROMP. Para tanto, o trabalho dividiu-se em duas etapas: (1) estudo do complexo [RuCl2 (PPh3)2 (pip-3-MeOH)] e sua atividade na ROMP; (2) imobilização do complexo [RuCl2 (PPh3)3] e estudos de ROMP com o mesmo. Na primeira etapa, o complexo foi caracterizado por análise elementar (CHN), EPR, FT-IR, RMN 31P{1H} e espectroscopia eletrônica na região do UV-vis. Os resultados sugerem um complexo pentacoordenado com os íons cloreto cis-posicionados. A ROMP de norborneno em clorofórmio foi testada na ausência e na presença de diferentes ácidos no meio. Os melhores rendimentos obtidos foram de 93,6% de poliNBE (Mn = 11 x 104 g.mol-1; IPD = 1,8) em reações de 60 min a 50°C, na presença de HCl com razão molar [NBE]/[Ru] = 5000 e 5 μL de EDA. Por MEV, observou-se que os polímeros obtidos não apresentaram poros. Por análise de DSC, obteve-se Tg de aproximadamente 36,5°C. Na segunda etapa do trabalho, o composto obtido foi caracterizado por análise elementar (CHN) e FT-IR. Foram realizados estudos de lixiviação utilizando-se um sistema de Soxhlet seguido de análise por espectroscopia de absorção atômica. A porcentagem de rutênio lixiviada foi de 26,13%. O composto SWNT-Ru foi utilizado em reações de ROMP de NBE. Em reações de 60 min em diclorometano a 50°C com razão molar [NBE]/[Ru] = 5000 e 5 μL de EDA, o rendimento foi de 72,1%. Os polímeros com CNTs foram analisados por MEV e também não apresentaram poros. Já na análise de DSC, observou-se um aumento na Tg, que foi de 42,5°C. Na tentativa de separar o catalisador ancorado do polímero obtido, testou-se a ROMP em tolueno com concentrações de NBE baixa ([NBE]/[Ru] = 300) e alta ([NBE]/[Ru] = 5000), com adição de etil vinil éter para finalizar a reação. Em nenhum dos casos obteve-se sucesso. Um experimento adicional ao trabalho foi a funcionalização de matriz de grafite com complexo de rutênio. O composto obtido foi caracterizado por análise elementar (CHN), FT-IR e espectroscopia eletrônica na região do UV-vis. Os resultados mostraram que o grafite pode ser funcionalizado e é uma alternativa de matriz de baixo custo para imobilização de complexos de rutênio. / The project aimed the complex [RuCl2(PPh3)3] immobilization in carbon nanotubes by the ligand 3-piperidinemethanol to be used in ROMP. So, this work was divided in two parts: study of the complex [RuCl2 (PPh3)2 (pip-3-MeOH)] and its activity in ROMP; (2) complex [RuCl2 (PPh3)3] immobilization and ROMP studies with it. In the first part, the complex was characterized by elemental analysis (CHN), EPR, FT-IR, RMN 31P{1H} and electronic spectroscopy on UV-vis. The results suggest a pentacoordinated complex with cis-positioned chlorides. The ROMP of norbornene in absence and presence of different acids was tested. The best yield was 93,6% ((Mn = 11 x 104 g.mol-1; PDI = 1,8) of poliNBE in reactions of 60 minutes at 50°C in the presence of HCl with a molar ratio [NBE]/[Ru] = 5000 and 5 μL of EDA. By SEM, it was observed that polymers obtained didn\'t showed pores. For DSC analysis, Tg was approximately 36,5°C. In the second part of the work, the obtained compound was characterized by elemental analysis (CHN) and FT-IR. Leaching studies with a Soxhlet system were performed, followed by analysis by atomic absorption spectroscopy. The percentage of leached ruthenium was 26,13%. The SWNT-Ru was used in ROMP of NBE. In 60 minutes reactions in dichloromethane at 50°C with a molar ratio [NBE]/[Ru] = 5000 and 5 μL of EDA, the yield was 72,1%. The polymers with CNTs were analyzed by SEM and also showed no pores. In DSC analysis, an increase in Tg was observed, which was 42,5°C. In attempting to separate the catalyst from the polymer obtained, ROMP in toluene was tested with low (NEB]/[Ru] = 300) and high ([NBE]/[Ru] = 5000) concentrations, with addiction of ethyl vinyl ether to complete the reaction. None of them was successful. An additional experiment was the functionalization of graphite matrix with ruthenium complex. The obtained compound was characterized by elemental analysis (CHN), FT-IR and electronic spectroscopy in the UV-vis region. The results showed that the graphite can be functionalized and is an alternative low-cost matrix for immobilization of ruthenium complexes.

The production of cellulose derived hybrid carbon nanofibre (CNF)/carbon nanotubes (CNTs) electrodes for the fabrication of supercapacitors and carbon fibre composites was investigated. The CNTs were grown via a floating catalyst chemical vapor deposition (CVD) method on the top surface of electrospun cellulose derived CNFs. These CNF and CNF/CNTs samples were then used as electrodes to produce liquid electrolyte-based supercapacitors. The growth of CNTs leads to an improvement of electrochemical performance compared to the plain CNFs. This improvement is due to the grown CNTs enlarging the reactive sites through enhanced surface area and porosity, and thereby increasing the conductivity of the system. CNTs have been also grown onto CNFs containing ferrocene and SiC particles. Composites were fabricated by combining the fibres and CNTs grown fibres with model polymers. The stress transfer properties of these materials have been estimated using an in situ Raman spectroscopic method by observing the shift of the Raman band during the tensile deformation of model polymer composites. Using this method, the elastic modulus of CNF/SiC/CNTs fibres has been estimated to be 208 ± 26 GPa. No shifts in the peak positions of bands relating to the carbon structure were obtained for in situ Raman spectroscopic studies of the CNF/CNTs fibres made from the ferrocene embedded fibres. This was thought to be due to the low yield of CNTs on the surface of the fibres. Furthermore, CNF/CNTs electrode-based structural supercapacitors, combining a solid electrolyte with the carbonized fibres, have been produced. These CNF/CNTs electrodes have a better capacitive performance than the plain CNF electrodes. There was a decrease in this performance with increased curing time of the resin, from 2 to 24 h, due to a lack of charge carrier mobility in the latter samples. A Raman spectroscopic study of the deformation of the carbon structures showed that the G-band shift towards a lower wavenumber position for the CNF and CNF/CNTs samples processed at a carbonization temperature of 2000 °C. Moduli of these fibres were estimated to be ~145 GPa and ~271 GPa, respectively, suggesting the growth of CNTs not only enhances the capacitive performance but also the mechanical properties of the structural supercapacitors. No Raman bend shift was found for the CNFs and CNF/CNTs samples processed below a carbonization temperature of 2000 °C, e.g. 900 °C and 1500 °C. This is because the graphitic structures are not well developed at carbonization temperatures below 1500 °C.

O câncer de pele, no Brasil, é responsavel por 25% de todos os tipos de câncer. Uma alternativa aos tratamentos usuais é a Terapia Fotodinâmica (TFD). Os processos fotodinâmicos em geral dependem da retenção de um composto fotossensível nos tecidos alvos e posterior irradiação com luz visível em comprimento de onda adequado. Após ativação, o fármaco tranfere energia para outras moléculas do meio, podendo gerar espécies como o oxigênio singlete (1O2) , radicais livres (O2,OH) e outras espécies reativas de oxigênio (EROs), essas, são responsáveis pelo processo fotooxidativo e indução da morte celular. Neste trabalho, o fármaco fotossensível NzPc (uma ftalocianina) foi estudado para verificar se suas características fotofísicas e fotoquímicas são adequadas a TFD, e, em seguida, foi associado a nanotubos de carbono de parede múltipla (NTCPM) funcionalizados com o tensoativo Pluronic F-127. Esse sistema de liberação de fármaco desenvolvido, foi caracterizado através de ensaios in vitro nas linhagens de melanoma de rato B16-F10 e carcinoma humano OSCC . O sistema NzPc/NTCPM/PF-127 apresentou atividade fotodinâmica superior ao fármaco na forma livre, possibilitando, maior interiorização do fármaco nas linhagens celulares e maior morte celular após irradiação. / Skin cancer in Brazil are responsible for 25% of all cancers. An alternative to the usual treatments is photodynamic therapy (PDT). Photodynamic processes in general depend on the retention of a photosensitive compound in target tissues and subsequent irradiation with visible light at an appropriate wavelength. After activation, the drug, transfer energy to other molecules of the medium, which can generate species reactivate such as singlet oxygen (1O2), free radicals (O2 , OH) and other reactive oxygen species (ROS), these are responsible for photo-oxidative process and induction of cell death. In this work, NzPc photosensitive drug (a phthalocyanine) was studied to see if their photophysical and photochemical characteristics are suitable for PDT, and then was associated with multi-walled carbon nanotubes (MWCNT) functionalized with surfactant Pluronic F-127. This drug delivery system developed was characterized by in vitro assay on strains of mouse melanoma B16-F10 and carcinoma human OSCC. The system presented NzPc/NTCPM/PF-127 photodynamic activity than the drug in the free form, enabling greater internalization of the drug in cell and increased cell death after irradiation.

Silicon has the highest theoretical capacity of any known anode material, and silicon coated carbon nanotubes (Si-CNTs) have shown promise of dramatically increasing battery capacity. However, capacity fading with cycling and low rate capability prevent widespread use. Here, three studies on differing aspects of these batteries are presented. Here, three studies on differing aspects of these batteries are presented. The first examines the rate capability of these batteries. It compares the cycling of electrodes hundreds of microns thick with and without ten micron access holes to facilitate diffusion. The holes do not improve rate capability, but thinner coatings of silicon do improve rate capability, indicating that the limiting mechanism is the diffusion through the nanoscale bulk silicon. The second attempts to enable stable cycling of anodes heavily loaded with silicon, using a novel monolithic scaffolding formed by coating vertically aligned carbon nanotubes (VACNTs) with nanocrystalline carbon. The structure was only able to stabilize the cycling at loadings of carbon greater than 60% of the electrode by volume. These electrodes have volume capacities of ~1000 mAhr/ml and retained over 725 mAhr/ml by cycle 100. The third studies the use of an encapsulation method to stabilize the solid electrolyte interphase (SEI) and exclude the electrolyte. The method was only able to stabilize cycling at loadings below 5% silicon, but exhibits specific capacities as high as 3000 mAhr/g of silicon after 20 cycles.

Carbon nanotubes (CNTs) are one of the most popular nanomaterials. There has been increasing interest in the development and applications of carbon nanotubes due to their huge potential in industrial and medical applications. Recent applications of carbon nanotubes include development of scaffolds and drug delivery systems. Despite rapidly emerging applications of CNTs, little is known about the impact of CNTs on cellular processes, especially mesenchymal stem cell (MSC)'s differentiation. Also, the effects of nanoparticle exposure under different conditions on cellular responses have not been well characterized yet. To characterize the effects of CNTs on creating nanoscale scaffolds for tissue engineering, we incorporated multi-walled CNTs (MWCNTs) into reconstituted type I collagen, and evaluated proliferation, differentiation, mineralization and inflammatory response of MSC on those scaffolds. MWCNTs were homogeneously distributed in collagen matrix, and strongly entrapped in collagen at the concentrations below 100 ppm. Alkaline phosphatase (AP) activity and mineralized nodules of extracellular matrix (ECM) were monitored as osteogenic differentiation markers. AP activity was significantly increased in 12 days after being replaced by differentiating media. Collagen enhanced AP activity, and MWCNT-collagen scaffolds induced additional increase in AP activity. The MSC released a significantly higher level of AP on MWCNT-collagen scaffolds than the plastic surface did at day 16. An increasing percentage of ECM mineralization was seen at day 16 after being replaced by differentiating media in the presence of MWCNT-collagen scaffolds. This study indicated the possibility of enhancement in MSC differentiation in the MWCNT-collagen scaffolds. The increased level of differentiation markers was due to the increased stiffness of the scaffolds for MSC. Our data indicated that the collagen-MWCNT scaffolds might have the potential application to create nanoscale scaffold materials for tissue engineering. To illustrate the effects of interleukin-8 (IL-8) expression in human alveolar epithelial cells (A549) under various exposure conditions of CNT, we measured the level of IL-8 expression in the presence and absence of serum following exposure of SWCNTs. The results demonstrated that the IL-8 expression was enhanced in the presence of serum. The IL-8 expression kept increasing at low concentration even after removing SWCNTs from the media. Further studies are required to characterize biological functions and toxicological potentials of nanomaterials.

Thesis (MSc. (Chemistry)) -- University of Limpopo, 2013 / Drinkable water is water that is safe enough to be consumed by humans or used with low risk of immediate or long term harm. World-wide, insufficient access to portable water and use of sources contaminated with disease vectors, pathogens, and unacceptable levels of toxins is a huge problem. The use of such water for drinking and food preparation leads to the widespread of acute and chronic illnesses. This is a major cause of death and misery in many undeveloped countries. Reduction of waterborne diseases is a major public health goal in developing countries. Nanotechnology offers the possibility of an efficient removal of pollutants and microorganisms from water. Essentially, three classes of nanoscale materials were investigated as functional materials for water purification in this study. Silver nanoparticles, carbon nanotubes and beta ()-cyclodextrin polymers were synthesised and characterised specifically for purification of water samples. β-cyclodextrin is soluble in both water and other aqueous media. In order to render cyclodextrins insoluble, they were converted into highly cross-linked polymers, by polymerisation with a bifunctional linker, hexamethylene diisocyanate. Cyclodextrins were functionalised and synthesised with either the allyl or the benzoyl group. Characterisation with fourier transform infrared (FTIR) spectrophotometer confirmed the functionalisation process. Thereafter the scanning electron microscopy (SEM) analysis confirmed the polymers’ morphology to be spongy, and capable of absorbing contaminants. Multi-walled carbon nanotubes (MWCNTs) were treated with a mixture of sulphuric and nitric acid in order to introduce the carboxyl and hydroxyl groups. These were characterised by SEM, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR spectroscopy to confirm the functionalisation process. Silver nanoparticles were synthesised from sodium citrate and silver nitrate, using sodium dodecyl sulphate as a surfactant. Their characterisation was done by SEM, energy dispersive X ray (EDX) spectroscopy, TEM, UV/Vis spectroscopy and XRD to confirm a face centred cubic structure with an estimated crystallite size ranging from 50 to 100 nm.β-cyclodextrin polymers, functionalised multi-walled carbon nanotubes and silver nanoparticle-doped MWCNTs/cyclodextrin composites were characterised by SEM, TEM, XRD, Brunauer-Emmet-Teller (BET) and EDX. Analysis of the phenolic compound, 4-hydroxynitrobenzene in water, using these nanocomposites, demonstrated good capabilities of removing organic contaminants from water samples as indicated by their high absorption efficiencies of the contaminants. The synthesised metal-organic composites were tested for their effectiveness in removing organic contaminants as well as for eliminating Escherichia coli bacteria from water. The synthesised composites presented up to 97% absorption efficiency of organic contaminants and up to 100% inactivation of the bacteria. There was complete destruction of bacteria from the water analysed at various times and varying concentrations. After a long exposure of the nanocomposites to E. coli, pits were noticeable on the external morphology of the bacteria, thus suggesting that the nanocomposites are bactericidal. The bacterial activity increased with temperature,when studied between 10 oC and 30 oC.

Les capteurs sont des dispositifs ayant montré une utilisation répandue, allant de la détection des molécules en phase gazeuse au suivi de signaux chimiques dans les cellules biologiques. En général, un capteur est réalisé à partir d’un élément actif de détection et d’un signal transducteur produisant un signal de sortie qui peut être électrique, optique, thermique ou magnétique. Les électrodes à base de nanotubes de carbone à simple paroi et les électrodes à base de graphène se sont révélées être un matériau excellent pour le développement des biocapteurs électrochimiques, puisqu’ils montrent des propriétés électroniques remarquables et la capacité de se comporter en tant que nano-électrodes individuelles, un excellent transport de porteur de charge à faible dimension, et permettent de l’électrocatalyse de surface. Le travail présenté vise à la préparation et à l’étude d’électrodes de nanotubes de carbone à simple paroi et d’électrodes de graphène modifiées par voie électrochimique pour des applications dans le domaine des biocapteurs. Nous avons d’abord étudié les films de nanotubes de carbone à simple paroi et nous nous sommes intéressés à leur topographie, à leur composition de surface, et leurs propriétés électriques et optiques. Nous montrons que ces films sont homogènes avec une conductivité d’environ 200-300 Ω/□, et une transparence d’environ 40%. En parallèle aux nanotubes de carbone à simple paroi, des films de graphène ont été étudiés. Des valeurs de résistance plus élevées en comparaison avec les films de nanotubes ont été obtenues. La modification de surface par voie électrochimique des deux types d'électrodes a été étudiée en suivant deux voies, (i) l’électro-greffage de sels d’aryl diazonium, et (ii) l’addition électrophile de 1, 3- benzodithiolilyumtetrafluoroborate (BDYT). Les caractéristiques qualitatives et quantitatives de la surface modifiée des électrodes ont été étudiées, comme le degré de fonctionnalisation et la composition de surface. La combinaison de spectroscopie Raman, et de photoelectrons X- (XPS) de microscopie à force atomique (AFM),d'électrochimie et d’autres techniques, a montré que des précurseurs particuliers peuvent être ancrés de façon covalente à la surface des électrodes de nanotubes etde graphène, grâce à la formation de nouvelles liaisons carbone-carbone. Dans le premier cas (i), leur post-modification par des réactions de « clickchemistry» mène finalement à l’immobilisation sur la surface de l’électrode des groupes fonctionnels souhaités, comme des sondes/shuttles redox (e.g., un groupeferrocenyl) ou des groupements catalytiques (e.g., une enzyme). L'enzyme HRP(horse-radish peroxidase) a été, par exemple, immobilisée sur des surfaces de nanotubes de carbones à simple paroi modifiées par un groupe aryl, et l'étude voltammétrique a montré une réponse catalytique avec l’augmentation de la concentration de peroxyde d’hydrogène en solution, en suivant le « shuttle » redoxhydroquinone/benzoquinone à la surface de l’électrode. Dans le second cas (ii), l’addition électrophile de radicaux BDYT électro-générés a été étudiée pour la première fois sur des électrodes de nanotubes de carbone à simple paroi ou sur les électrodes de graphène. La combinaison de différentes techniques complémentaires a montré l’attachement covalent de BDYT aux électrodes de nanotubes de carbone à paroi simple. Une telle modification mène à la formation de rubans torsadés qui ont pu être observés et analysés par AFM et parmicroscopie électronique à balayage. Aucune preuve de la formation de rubans torsadés n’a pu être mise en évidence pour les électrodes modifiées à base de graphène. / Sensors are devices that have shown wide spread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. In general, a sensor is made of an active sensing element and a signal transducer producing an electrical,optical, thermal or magnetic output signal. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. We show that these films are homogeneous with thickness around 6̴ 0-70 nm, resistance values around 2̴ 00-300Ω/□, and transparency around 4̴ 0%. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films.The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation. In route (i), their post-modification by click-chemistry reactions finally leads to the immobilization at the electrode surface of desired functional groups, such as redoxprobes/shuttles (e.g., a ferrocenyl group) or catalytic moieties (e.g., an enzyme).HRP has been for instance immobilized on SWCNT-aryl-modified surfaces, and its voltammetric study showed catalytic response with the increasing concentration of hydrogen peroxide in solution upon monitoring the redox shuttlehydroquinone/benzoquinone at the electrode surface. In route (ii), the electrophylic addition of electrogenerated BDYT radicals was investigated for the first time at either SWCNT- or graphene-based electrodes. The combination of different techniques has demonstrated the covalent attachment of BDYT to SWCNT-based electrodes. Such modification leads to the formation of twisted ropes observed and analyzed by AFM and scanning electron microscopy. No evidence of twisted ropes formation was instead observed for modified graphene based electrodes.

Thesis (M.S.)--University of Nevada, Reno, 2005. / "May, 2005." Includes bibliographical references (leaves100-103). Online version available on the World Wide Web.

Highly ordered nanoparticle arrays have been successfully fabricated by our group recently using ultra-thin porous alumina membranes as masks in the evaporation process. The sizes of the nanoparticles can be adjusted from 5-10 nm to 200 nm while the spacing between adjacent particles can also be adjusted from several nanometers to about twice the size of a nanoparticle. The configuration of the nanoparticles can be adjusted by changing the height of the alumina masks and the evaporation direction. Due to the high pore regularity and good controllability of the particle size and spacing, this method is useful for the ordered growth of nanocrystals. Different kinds of nanoparticle arrays have been prepared on silicon wafer including semiconductors (e.g., germanium) and metals (e.g., nickel). The germanium nanoparticle arrays have potential applications in memory devices while the nickel catalyst nanoparticle arrays can be used for the growth of ordered carbon nanotubes. / Singapore-MIT Alliance (SMA)