A multi-scale approach to shaping carbon nanotube structures for hollow microneedles

The concept of a carbon nanotube microneedle array is explored in this thesis from multiple perspectives including microneedle fabrication, physical aspects of transdermal delivery, and in vivo transdermal drug delivery experiments. Starting with standard techniques in carbon nanotube (CNT) fabrication, including catalyst patterning and chemical vapor deposition, vertically-aligned carbon nanotubes are utilized as a scaffold to define the shape of the hollow microneedle. Passive, scalable techniques based on capillary action and unique photolithographic methods are utilized to produce a CNT-polymer composite microneedle. Specific examples of CNT-polyimide and CNT-epoxy microneedles are investigated. Further analysis of the transport properties of polymer resins reveals general requirements for applying arbitrary polymers to the fabrication process.

The bottom-up fabrication approach embodied by vertically-aligned carbon nanotubes allows for more direct construction of complex high-aspect ratio features than standard top-down fabrication approaches, making microneedles an ideal application for CNTs. However, current vertically-aligned CNT fabrication techniques only allow for the production of extruded geometries with a constant cross-sectional area, such as cylinders. To rectify this limitation, isotropic oxygen etching is introduced as a novel fabrication technique to create true 3D CNT geometry. Oxygen etching is utilized to create a conical geometry from a cylindrical CNT structure as well as create complex shape transformations in other CNT geometries.

CNT-polymer composite microneedles are anchored onto a common polymer base less than 50 µm thick, which allows for the microneedles to be incorporated into multiple drug delivery platforms, including modified hypodermic syringes and silicone skin patches. Cylindrical microneedles are fabricated with 100 µm outer diameter and height of 200-250 µm with a central cavity, or lumen, diameter of 30 µm to facilitate liquid drug flow. In vitro delivery experiments in swine skin demonstrate the ability of the microneedles to successfully penetrate the skin and deliver aqueous solutions.

An in vivo study was performed to assess the ability of the CNT-polymer microneedles to deliver drugs transdermally. CNT-polymer microneedles are attached to a hand actuated silicone skin patch that holds a liquid reservoir of drugs. Fentanyl, a potent analgesic, was administered to New Zealand White Rabbits through 3 routes of delivery: topical patch, CNT-polymer microneedles, and subcutaneous hypodermic injection. Results demonstrate that the CNT-polymer microneedles have a similar onset of action as the topical patch. CNT-polymer microneedles were also vetted as a painless delivery approach compared to hypodermic injection. Comparative analysis with contemporary microneedle designs demonstrates that the delivery achieved through CNT-polymer microneedles is akin to current hollow microneedle architectures. The inherent advantage of applying a bottom-up fabrication approach alongside similar delivery performance to contemporary microneedle designs demonstrates that the CNT-polymer composite microneedle is a viable architecture in the emerging field of painless transdermal delivery.

Optical properties of excited silicon and germanium at low temperatures

Part I of this thesis deals with 3 topics concerning the luminescence from bound multi-exciton complexes in Si. Part II presents a model for the decay of electron-hole droplets in pure and doped Ge.

Part I.

We present high resolution photoluminescence data for Si doped With Al, Ga, and In. We observe emission lines due to recombination of electron-hole pairs in bound excitons and satellite lines which have been interpreted in terms of complexes of several excitons bound to an impurity. The bound exciton luminescence in Si:Ga and Si:Al consists of three emission lines due to transitions from the ground state and two low lying excited states. In Si:Ga, we observe a second triplet of emission lines which precisely mirror the triplet due to the bound exciton. This second triplet is interpreted as due to decay of a two exciton complex into the bound exciton. The observation of the second complete triplet in Si:Ga conclusively demonstrates that more than one exciton will bind to an impurity. Similar results are found for Si:Al. The energy of the lines show that the second exciton is less tightly bound than the first in Si:Ga. Other lines are observed at lower energies. The assumption of ground state to ground-state transitions for the lower energy lines is shown to produce a complicated dependence of binding energy of the last exciton on the number of excitons in a complex. No line attributable to the decay of a two exciton complex is observed in Si:In.

We present measurements of the bound exciton lifetimes for the four common acceptors in Si and for the first two bound multi-exciton complexes in Si:Ga and Si:Al. These results are shown to be in agreement with a calculation by Osbourn and Smith of Auger transition rates for acceptor bound excitons in Si. Kinetics determine the relative populations of complexes of various sizes and work functions, at temperatures which do not allow them to thermalize with respect to one another. It is shown that kinetic limitations may make it impossible to form two-exciton complexes in Si:In from a gas of free excitons.

We present direct thermodynamic measurements of the work functions of bound multi-exciton complexes in Al, B, P and Li doped Si. We find that in general the work functions are smaller than previously believed. These data remove one obstacle to the bound multi-exciton complex picture which has been the need to explain the very large apparent work functions for the larger complexes obtained by assuming that some of the observed lines are ground-state to ground-state transitions. None of the measured work functions exceed that of the electron-hole liquid.

Part II.

A new model for the decay of electron-hole-droplets in Ge is presented. The model is based on the existence of a cloud of droplets within the crystal and incorporates exciton flow among the drops in the cloud and the diffusion of excitons away from the cloud. It is able to fit the experimental luminescence decays for pure Ge at different temperatures and pump powers while retaining physically reasonable parameters for the drops. It predicts the shrinkage of the cloud at higher temperatures which has been verified by spatially and temporally resolved infrared absorption experiments. The model also accounts for the nearly exponential decay of electron-hole-droplets in lightly doped Ge at higher temperatures.

Estudo de eventos amparado em métricas contábeis: detectando performance operacional anormal em firmas brasileiras

O estudo de eventos amparado em métricas contábeis pode ser considerado como aquele que investiga se os retornos anormais no mercado acionário possuem uma contrapartida no lado real, ou seja, se a performance operacional da firma sofreu modificação decorrente de um determinado evento econômico. O presente estudo tem como foco as escolhas que um pesquisador deve fazer na hora da modelagem de um estudo de evento amparado em métricas contábeis, tais como: que medida de performance utilizar, que modelo de expectativa de performance operacional servirá como benchmark, e que teste estatístico poderia detectar com mais eficiência as anormalidades. Um exemplo de estudo que testa empiricamente, nos EUA, o efeito das escolhas acima nas especificações e poder dos testes estatísticos é o de Barber e Lyon (1996). O presente trabalho pretende testar empiricamente os modelos, analisados por esses autores, nas empresas brasileiras. Para tal, foram extraídas da base de dados da Economática todas as empresas listadas na Bolsa de Valores de São Paulo BOVESPA, com dados contábeis disponíveis para os anos de 2004 a 2010, sendo que foram objeto de análise os anos de 2005 a 2010. Obtiveram-se dados para 605 empresas, e uma média de 1606 observações por métrica contábil. Foram testadas 6 medidas contábeis de performance operacional e 13 modelos de expectativa de desempenho. Para atingir o objetivo, a pesquisa foi dividida em três fases. Fase I Elaboração dos Modelos de Expectativa e formação dos Grupos de Controle; Fase II Teste do Poder explicativo dos Modelos de Expectativa; Fase III Testes para Detectar Performance Operacional Anormal. Para o caso brasileiro, pode-se dizer que a melhor medida para detectar performances operacionais anormais é o ROA2 (Ebitda/Ativo Total), já que foi a que apresentou mais modelos que atenderam a todos os testes estabelecidos, em todas as fases da pesquisa. Quanto ao benchmark, o melhor apontado pelos resultados foi o filtro indústria, classificação Economática. O modelo de desempenho defasado da firma, também apresentou resultados satisfatórios. Por fim, o teste estatístico mais apropriado para detectar performances operacionais anormais é o de Wilcoxon.

Da contemplação à imersão e subjetividade: estéticas dos museus de arte contemporânea e centros culturais

O estudo desenvolvido nesta Tese de Doutorado trata da análise crítica da estética dos conceitos: forma, tectônica, funcionalidade, semiótica e afetuosidade, no âmbito da arquitetura, no programa de museus de arte contemporânea e centros culturais. Os museus de arte contemporânea e centros culturais, estudos de caso, selecionados para nossa Tese de Doutorado foram inaugurados na década de 1990. Como segue: Centro Cultural Jean-Marie Tijibaou (Nova Caledônia, França), de Renzo Piano; Museu de Arte Contemporânea de Naoshima (Japão), de Tadao Ando; Museu Guggenheim Bilbao (Espanha), de Frank O. Gehry; Museu de Arte Contemporânea Fundação Serralves (Portugal), de Álvaro Siza Vieira; Museu de Arte Contemporânea de Niterói (Brasil), de Oscar Niemeyer; Fundació Museu d'Art Contemporani de Barcelona (Espanha), de Richard Meier; Museu de Arte Contemporânea Carré d'Art de Nimes (França), de Norman Foster; Museu de Arte Contemporânea de Lyon (França), de Renzo Piano; Centro Cultural Consonni (Espanha), ausência de um arquiteto autor do projeto. Tanto os estudos de caso como os arquitetos, autores dos projetos, são considerados de destaque no panorama da arquitetura internacional erudita contemporânea. Os teóricos que forneceram a fundamentação conceitual deste estudo multidisciplinar são, em primeiro lugar, o Professor Catedrático Luiz Felipe Baêta Neves Flores (Transdisciplinaridade) além da Professora Catedrática Maria Luisa Amigo Fernández de Arroyabe (Ócio Estético) e ainda, os também importantes, Manuel Cuenca Cabeza (Ócio Humanista), Charles Jencks e Gonçalo Miguel Furtado Cardoso Lopes (Crítica de Arquitetura), Jesús Pedro Lorente, Chris van Uffelen e Roberto Segre (Museus de Arte Contemporânea).