Anodised titanium dioxide (titania, TiO2) nanotubes have been widely studied over the last few years, following the discovery in 1999 of nanoporous TiO2 films prepared via anodisation in aqueous solution containing small quantities of hydrofluoric acid. The synthesis of nanotubular titania by anodisation, a relatively simple and low cost technique, represents a motivation for scientists, considering the impact that such a material could have on a variety of applications, including gas-sensing, biomedical, photocatalysis, and photovoltaics. This research project has focused on the optimisation of the growth process of anodic titania nanotubes, both in an aqueous (NaF/Na2SO4) and an organic (Glycerol/NaF) electrolyte containing fluorine ions. Reproducibility and the ability to generate anodic films having a thickness of several micrometers are fundamental steps to be achieved before investigating any possible application of the nanotubes. To characterise the anodic specimens and build upon the general lack of information on the growth mechanism, a comprehensive study of the different stages of the process has been performed, using Scanning and Transmission Electronic Microscopy (SEM and TEM). Among the questions to be addressed in this thesis, is to establish whether the anodic film undergoes a transition from pores to tubes or develops a tubular morphology from the beginning of its growth. Additional characterisation of the anodisation process includes the study of current-time curves, and chemical composition analysis of the anodic layers using X-ray Photo-Electron Spectroscopy (XPS). The thermal stability of the nanotubes and structural/morphological changes as a result of heat treatment at different temperatures were also studied, again using SEM, TEM, XPS and Raman spectroscopy. The final part of the thesis is dedicated to preliminary work on the use of anodised TiO2 nanotubes in Dye Sensitized Solar Cells (DSSCs), along with suggestions for future works and general conclusions.

Thesis (Ph. D.)--University of Nevada, Reno, 2008. / "August 2008." Includes bibliographical references (leaves 126-132). Online version available on the World Wide Web.

No description available.

In nature, cells are not randomly clustered to form tissues. The tissue is a more complicated system with functions that go beyond what any single cell type could accomplish. While studying single-cell mechanics and dynamics is relevant from an investigative point of view, this approach loses, or fail to gather information about the tissue. The tissue investigated in this study is the neurosensory retina which seeing as extension of the brain is a very convenient model for the central nervous system due to its accessibility. The retina is constantly subjected to different mechanical stresses from development to adulthood. Although the majority of the phenomena where mechanical stresses are involved are well-studied, the mechanics behind them is not well understood. However, knowledge about the ability of the retina to adjust to mechanical stresses is essential, for example, for improving retinal surgery. Establishing a method to mechanically probe the retina is a challenge due to the extremely delicate nature of this multilayered neural tissue and to the short-time survival ex vivo. The organotypic tissue culture is a powerful tool because it allows to maintain with high accuracy the complex multicellular anatomy and the microenvironment of the original tissue. One of the limitations of the organotypic culture techniques has been until recently due to the ability to use only post-natal/juvenile tissues for long-term culture. The importance of using adult tissue is incontestable when the investigation focuses on age-related pathologies such as vitreous shrinkage or macula degeneration. In this work, TiO2 nanotube arrays are presented as the innovative substrate for long-term organotypic culture of adult neural tissue. The retinal whole-mount of adult guinea pig and the brain slices of adult mouse were cultures for 14 days without showing any sign of edema or swelling. Furthermore, in order to study the behavior of the retinal tissue under shear stress new set-ups were designed. For the first time, the behavior of the retinal layers were observed showing that the retina does not act as an homogeneous material in response to an applied stress. The methods developed here can be used for future quantitative studies, to provide an exact knowledge of retinal biomechanics which will help retinal surgeons to optimize their methods.

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No. of bitstreams: 1 fabrao_rm_me_arair_par.pdf: 7668439 bytes, checksum: 58607cbddf9360e358535e80f3c03f7c (MD5) Previous issue date: 2016-08-05 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A produção de etanol e açúcar a partir de cana-de-açúcar é um atividade de grande importância no Brasil, mas também fonte de grande preocupação ambiental devido ao grande acúmulo de biomassa na forma de bagaço e vinhaça gerados como rejeitos. A biomassa lignocelulósica é constituída de celulose, com estrutura formada de unidades de glicose polimerizadas, deste modo estudos voltados para a conversão de glicose em compostos químicos com maior valor agregado seria relevante para buscar novas formas de aproveitamento destes rejeitos. O objetivo do presente trabalho é investigar a aplicabilidade da técnica de fotoeletrocatálise para promover a oxidação de glicose em meio aquoso utilizando nanotubos de dióxido de titânio (NT-Ti/TiO2) como fotoanodos com vistas a obtenção de compostos com maior valor agregado. Os eletrodos de nanotubos de dióxido de titânio (NT-Ti/TiO2) foram preparados por oxidação eletroquímica de Ti em solução 1,0 mol L-1 de NaH2PO4 + 0,3% (m/m) HF como eletrólito de suporte sob potencial de 20V por 2 h e calcinado a 450 °C. Um método analitico baseado em cromatografia de troca iônica com detecção amperométrica foi desenvolvido para análise de glicose, acido glicônico, acido glicárico, arabitol e arabinose e curvas analíticas foram construídas em concentrações de 1,00 a 20,0x10-6 mol L-1, r = 0,9995, e o método alcançou limites de detecção e determinação ao redor de LD = 0,03x10-6 mol L-1 e LQ = 0,08x10-6 mol L-1 para a determinação de glicose. O método foi utilizado para monitoramento dos produtos gerados durante oxidação fotoeletrocatalítica de 10,0 mmol L-1 de glicose sob potencial de +1,5 V vs Ag/AgCl e irradiação UV/Vis que alcançou 72% de conversão após 180 min de tratamento. Medidas de remoção de carbono orgânico total mostraram que 28% da glicose foi convertida a CO2 e o restante foi transformado em outro produtos, tais como Arabinose, arabinitol, 4-cetoglicose, glucohexodialdose, glucona-δ-lactona, 6-desoxiglucose e o ácido glicônico, cuja maioria foi confirmada por espectrometria de massas. Os resultados demonstram que a técnica de fotoeletrocatálise pode ser uma alternativa simples, econômica e promissora para promover a conversão da glicose em alguns produtos de interesse econômico. / The production of sugar and ethanol from sugarcane is an activity very important in Brazil, but it is also a source of great environmental concern due to the large accumulation of biomass in form of bagasse and vinasse generated as waste of this process. The lignocellulosic biomass is made up of cellulose, wich structure is made of polymerized glucose units. Thereby studies focused on the conversion of glucose into added value chemical compounds would be relevant to seek new ways to use these waste. This work describes the construction electrodes of titanium dioxide nanotubes (NT-Ti / TiO2) and its application in photoeletrocatalytic oxidation of glucose in aqueous media aimed at converting glucose into compounds with higher added value. The electrodes were prepared by electrochemical oxidation of Ti in solution of 1.0 mol L-1 NaH2PO4 + 0.3% (m/m) HF as supporting electrolyte under a potential of 20V for 2 h and calcined at 450 ° C. An analytical method based on ion exchange chromatography with amperometric detection was developed for glucose, gluconic acid, glucarico acid, arabitol and Arabinose analysis and analytical curves were constructed at concentrations of 1.00 to 20,0x10-5 mol L-1, r = 0.9995, and the method achieved detection limits and determination around 0,03x10-6 mol L-1 and 0,08x10-6 mol L-1 for glucose determination, respectively. The method was used for monitoring the generated products due the oxidation photoeletrocatalytic 10.0 mmol L-1 glucose solution under potential of +1.5 V vs Ag / AgCl and irradiating UV / Vis that achieved 72% conversion after 180 min of treatment. Measurements of total organic carbon removal showed that 28% of the glucose was converted to CO2 and the rest was transformed into other products, such as arabinose, arabinitol, 4- ketoglicose, glucohexodialdose, Glucone-δ-lactone, 6-deoxyglucose and acid gluconic, most of which was confirmed by mass spectrometry. The results demonstrate that photoelectrocatalysis technique may be a simple, economical and attractive alternative to promote glucose conversion into some products of economic interest.

In nature, cells are not randomly clustered to form tissues. The tissue is a more complicated system with functions that go beyond what any single cell type could accomplish. While studying single-cell mechanics and dynamics is relevant from an investigative point of view, this approach loses, or fail to gather information about the tissue. The tissue investigated in this study is the neurosensory retina which seeing as extension of the brain is a very convenient model for the central nervous system due to its accessibility. The retina is constantly subjected to different mechanical stresses from development to adulthood. Although the majority of the phenomena where mechanical stresses are involved are well-studied, the mechanics behind them is not well understood. However, knowledge about the ability of the retina to adjust to mechanical stresses is essential, for example, for improving retinal surgery. Establishing a method to mechanically probe the retina is a challenge due to the extremely delicate nature of this multilayered neural tissue and to the short-time survival ex vivo. The organotypic tissue culture is a powerful tool because it allows to maintain with high accuracy the complex multicellular anatomy and the microenvironment of the original tissue. One of the limitations of the organotypic culture techniques has been until recently due to the ability to use only post-natal/juvenile tissues for long-term culture. The importance of using adult tissue is incontestable when the investigation focuses on age-related pathologies such as vitreous shrinkage or macula degeneration. In this work, TiO2 nanotube arrays are presented as the innovative substrate for long-term organotypic culture of adult neural tissue. The retinal whole-mount of adult guinea pig and the brain slices of adult mouse were cultures for 14 days without showing any sign of edema or swelling. Furthermore, in order to study the behavior of the retinal tissue under shear stress new set-ups were designed. For the first time, the behavior of the retinal layers were observed showing that the retina does not act as an homogeneous material in response to an applied stress. The methods developed here can be used for future quantitative studies, to provide an exact knowledge of retinal biomechanics which will help retinal surgeons to optimize their methods.

Объектом исследования являются электроды на основе нанотубулярного диоксида титана, модифицированные различными способами (термическая обработка, создание композитов с углеродными нанотрубками и частицами металлического никеля). Синтезированные образцы исследовались методом растровой электронной микроскопии и различными электрохимическими методами анализа (гальваностатический заряд-разряд, циклическая вольтамперометрия, импедансная спектроскопия). В результате исследования получены электроды: 1) Т/TiO2-НТ; 2) УНТ/TiO2-НТ; 3) Ni/TiO2-НТ представляющие собой: 1) массивы TiO2-НТ толщиной 3,5 мкм, с внутренним диаметром 70-80 нм и толщиной стенок 30-40 нм; 2) массивы TiO2-НТ с углеродными нанотрубками диаметром 10-30 нм и длиной от десятков нм до десятков мкм на поверхности оксидного слоя; 3) массивы TiO2-НТ, декорированные сферическими наночастицами Ni диаметром 70-100 нм с образованием локальных конгломератов частиц до 500 нм. Результаты работы позволили получить информацию об электрохимических характеристиках синтезированных электродов и преимуществах модификации структур TiO2-НТ для использования их в качестве электродов ионистров. / The object of this research is electrodes based on nanotubular titanium dioxide, modified by various methods (thermal treatment, synthesis of composites with carbon nanotubes and metallic nickel particles). The synthesized samples were investigated by scanning electron microscopy and various electrochemical analysis methods (galvanostatic charge-discharge, cyclic voltammetry, impedance spectroscopy). As a result of the study, were obtained: 1) T/TiO2-NT; 2) CNT/TiO2-NT; 3) Ni/TiO2-NT electrodes, which are: 1) arrays of TiO2-NT 3.5 μm thick, with an inner diameter of 70-80 nm and wall thickness 30-40 nm; 2) arrays of TiO2-NT with carbon nanotubes with a diameter of 10-30 nm and a length from tens of nm to tens of microns on the surface of the oxide layer; 3) arrays of TiO2-NT, decorated with spherical Ni nanoparticles with a diameter of 70-100 nm with the formation of local conglomerates of particles up to 500 nm. The results of the work made it possible to obtain information on the electrochemical characteristics of the synthesized electrodes and the advantages of modifying the TiO2-NT structures to use them as supercapacitor electrodes.