Nanoparticle Platform to Modulate Reaction Mechanism of Phenothiazine Photosensitizers

Herein, we report on the synthesis of photosensitizing nanoparticles in which the generation of different oxidizing species, i.e., singlet oxygen ((1)O(2)) or radicals, was modulated. Sol gel and surface chemistry were used to obtain nanoparticles with specific ratios of dimer to monomer species of phenothiazine photosensitizers (PSs). Due to competition between the reactions involving electron transfer within dimer species and energy transfer from monomer triplets to oxygen, the efficiency of (1)O(2) generation could be controlled. Nanoparticles with an excess of dimer have an (1)O(2) generation efficiency (S(Delta)) of 0.01 while those without dimer have a S, value of 0.4. Furthermore, we demonstrate that the PS properties of the nanoparticles are not subjected to interference from the external medium as is commonly the case for free PSs, i.e., PS ground and triplet states are not reduced by NADH and ascorbate, respectively, and singlet excited states are less suppressed by bromide. The modulated (1)O(2) generation and the PS protection from external interferences make this nanoparticle platform a promising tool to aid in performing mechanistic studies in biological systems. Also, it offers potential application in technological areas in which photo-induced processes take place.

Role of Polyelectrolyte for Layer-by-Layer Compact TiO(2) Films in Efficiency Enhanced Dye-Sensitized Solar Cells

Efficient compact TiO(2) films using different polyeleetrolytes are prepared by the layer-by-layer technique (LbL) and applied as an effective contact and blocking film in dye-sensitized solar cells (DSCs). The polyanion thermal stability plays a major role on the compact layers, which decreases back electron transfer processes and current losses at the FTO/TiO(2) interface. FESEM images show that polyelectrolytes such is sodium sullonated polystyrene (PSS) and sulfonated lignin (SE), in comparison to poly(acrylic acid) (FAA), ensure an adequate morphology for the LbL TiO(2) layer deposited before the mesoporous film, even triter the sintering step at 450 degrees C. The so treated photoanode in DSCs leads to a 30% improvement On the overall conversion efficiency. Electrochemical impedance spectroscopy (EIS) is employed to ascertain the role of die compact films with such polyelectrolytes. The significant increase in V(oc) of the solar cells with adequate polyelectrolytes in the LbL TiO(2) films shows their pivotal role in decreasing the electron recombination at the FTO surface and enhancing the electrical contact of FTO with the mesoporous TiO(2) layer.

Layer-by-layer TiO(2) films as efficient blocking layers in dye-sensitized solar cells

Charge recombination at the conductor substrate/electrolyte interface has been prevented by using efficient blocking layers of TiO(2) compact films in dye-sensitized solar cell photoanodes. Compact blocking layers have been deposited before the mesoporous TiO(2) film by the layer-by-layer technique using titania nanoparticles as cations and sodium sulfonated polystyrene, PSS, as a polyanion. The TiO(2)/PSS blocking layer in a DSC prevents the physical contact of FTO and the electrolyte and leads to a 28% increase in the cell`s overall conversion efficiency, from 5.7% to 7.3%. (C) 2009 Elsevier B.V. All rights reserved.

Using Polycarbonate Membranes as Templates for the Preparation of Au Nanostructures for Surface-Enhanced Raman Scattering

Polycarbonate membranes (PCM) of various pores sizes (400, 200, 100 and 50 nm) were used as templates for gold deposition. The electrodeposition from gold ions resulted in the formation of gold nanotubes when large pores size PCMs (400 and 200 nm) were used. On the other hand, gold nanowires were predominant for the PCMs with smaller pores size (100 and 50 nm). Surface-enhanced Raman scattering (SERS) from the probe molecule 4-mercaptopyridine (4-MPy) was obtained from all these nanostructures. The SERS efficiency of the substrates produced using the PC M templates were compared to two commonly used SERS platforms: a roughened gold electrode and gold nanostructures electrodeposited through organized polystyrene spheres (PSS). The SERS signal of the probe molecule increased as the pore diameter of the PCM template decreased. Moreover, the SERS efficiency from the nanostructures produced using 50 nm PCM templates was four and two times better than the signal from the roughened gold electrode and the PSS template, respectively. The SERS substrates prepared using PCM templates were more homogenous over a larger area (ca. 1 cm(2)), presented better spatial and sample to sample reproducibility than the other substrates. These results show that SERS substrates prepared using PCM templates are promising for the fabrication of planar SERS platforms for analytical/bioanalytical applications.

Centralidade espacial : uma nova operacionalização do modelo baseada em um Sistema de Informações Geográficas

Neste trabalho realizou-se a vinculação entre o Modelo de Centralidade e um Sistema de Informações Geográficas. A motivação para a realização dessa tarefa surgiu do reconhecimento de que as principais ferramentas utilizadas atualmente em análises espaciais urbanas – Modelos Urbanos e SIGs – apresentam sérias limitações, e que sua união em uma nova ferramenta pode superar muitas dessas limitações. Propôs-se então uma estrutura básica de Sistemas de Suporte ao Planejamento (PSS) que fosse capaz de oferecer suporte efetivo às diversas etapas do processo de planejamento. Essa estrutura serve como base de apoio para a construção da nova ferramenta, cujo objetivo foi testar duas hipóteses: a) A união de Sistemas de Informação Geográficas e o Modelo de Centralidade pode aumentar a qualidade de análises espaciais urbanas, através de aspectos como visualização e precisão dos resultados, e rapidez, facilidade e flexibilidade na realização das análises. b) Sistemas de Informações Geográficas podem contribuir para operacionalizar novos aportes teóricos no Modelo de Centralidade, principalmente através das capacidades de manipulação de elementos espaciais A ferramenta foi construída através de rotinas de personalização do ArcView (scripts), em conjunto com módulos analíticos externos, em forma de DLL, construídos em Delphi. Os scripts se encarregam de compilar os dados necessários à análise de Centralidade, referentes ao traçado e à quantidade e qualidade das formas edificadas, e alimenta o módulo analítico com as informações necessárias. Este as processa e retorna os resultados aos scripts, que então preenchem as tabelas de atributos referentes às unidades espaciais, deixando-as prontas para serem submetidas aos procedimentos de geração de mapas e cruzamentos de dados usualmente realizadas pelos SIGs “comuns”. Para testar a hipótese “a”, realizou-se um estudo de caso na cidade de Pato Branco (PR) para avaliar o desempenho da ferramenta quando aplicada a uma situação próxima da realidade. O desempenho da ferramenta mostrou-se bastante satisfatório, quando comparado com o método tradicional de análise da Centralidade. A organização dos dados foi beneficiada, assim como o tempo de realização das análises, aumentando a flexibilidade para a realização de testes com diferentes configurações. Para testar a hipótese “b”, propôs-se uma pequena alteração no Modelo de Centralidade, que atribuiu pesos diferenciados às conexões entre elementos espaciais, como forma de tentar superar algumas das limitações das representações utilizadas até o momento. Dessa forma, os ângulos entre os trechos de logradouros passaram a definir custos diferenciados entre trechos, que por sua vez influenciavam na determinação dos caminhos mínimos entre trechos, dado essencial para o conceito de Centralidade Ficou provado então que é possível operacionalizar novos aportes teóricos ao modelo de Centralidade utilizando as capacidades de manipulação de dados espaciais oferecidas pelos SIGs, ainda que a validade do aporte utilizado neste trabalho não tenha sido testada. Outras conclusões do estudo são a adequação da estrutura modular da ferramenta, a necessidade de bases de dados completas e adequadas desde o ponto de vista do modelo de dados, e o reconhecimento de um vasto campo de experimentações a serem feitas como evolução natural das idéias apresentadas aqui.

Projetos de controladores para sistemas de potência utilizando LMI'S

A presente dissertação tem como objetivo estudar e aprimorar métodos de projetos de controladores para sistemas de potência, sendo que esse trabalho trata da estabilidade dinâmica de sistemas de potência e, portanto, do projeto de controladores amortecedores de oscilações eletromecânicas para esses sistemas. A escolha dos métodos aqui estudados foi orientada pelos requisitos que um estabilizador de sistemas de potência (ESP) deve ter, que são robustez, descentralização e coordenação. Sendo que alguns deles tiveram suas características aprimoradas para atender a esses requisitos. A abordagem dos métodos estudados foi restringida à análise no domínio tempo, pois a abordagem temporal facilita a modelagem das incertezas paramétricas, para atender ao requisito da robustez, e também permite a formulação do controle descentralizado de maneira simples. Além disso, a abordagem temporal permite a formulação do problema de projeto utilizando desigualdades matriciais lineares (LMI’s), as quais possuem como vantagem o fato do conjunto solução ser sempre convexo e a existência de algoritmos eficientes para o cálculo de sua solução. De fato, existem diversos pacotes computacionais desenvolvidos no mercado para o cálculo da solução de um problema de inequações matriciais lineares. Por esse motivo, os métodos de projeto para controladores de saída buscam sempre colocar o problema na forma de LMI’s, tendo em vista que ela garante a obtenção de solução, caso essa solução exista.

Image processing algorithm for the identification of Martian dust devil tracks in MOC and HiRISE images

This paper presents a method for automatic identification of dust devils tracks in MOC NA and HiRISE images of Mars. The method is based on Mathematical Morphology and is able to successfully process those images despite their difference in spatial resolution or size of the scene. A dataset of 200 images from the surface of Mars representative of the diversity of those track features was considered for developing, testing and evaluating our method, confronting the outputs with reference images made manually. Analysis showed a mean accuracy of about 92%. We also give some examples on how to use the results to get information about dust devils, namelly mean width, main direction of movement and coverage per scene. (c) 2012 Elsevier Ltd. All rights reserved.

A layer-by-layer film of chitosan in a taste sensor application

Chitosan is alternated with sulfonated polystyrene (PSS) to build layer-by-layer (LBL) films that are used as sensing units in an electronic tongue. Using impedance spectroscopy as the principle method of detection, an array using chitosan/PSS LBL film and a bare gold electrode as the sensing units was capable of distinguishing the basic tastes - salty, sweet, bitter, and sour - to a concentration below the human threshold. The suitability of chitosan as a sensing material was confirmed by using this sensor to distinguish red wines according to their vintage, vineyard, and brands.

Layer by layer TiO2 thin films and photodegradation of Congo red

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Fabrication and characterization of chemical sensors made from nanostructured films of poly(o-ethoxyaniline) prepared with different doping acids

Chemical sensors made from nanostructured films of poly(o-ethoxyaniline) POEA and poly(sodium 4-styrene sulfonate) PSS are produced and used to detect and distinguish 4 chemicals in solution at 20 mM, including sucrose, NaCl, HCl, and caffeine. These substances are used in order to mimic the 4 basic tastes recognized by humans, namely sweet, salty, sour, and bitter, respectively. The sensors are produced by the deposition of POEA/PSS films at the top of interdigitated microelectrodes via the layer-by-layer technique, using POEA solutions containing different dopant acids. Besides the different characteristics of the POEA/PSS films investigated by UV-Vis and Raman spectroscopies, and by atomic force microscopy.. it is observed that their electrical response to the different chemicals in liquid media is very fast, in the order of seconds, systematical, reproducible, and extremely dependent on the type of acid used for film fabrication. The responses of the as-prepared sensors are reproducible and repetitive after many cycles of operation. Furthermore, the use of an "electronic tongue" composed by an array of these sensors and principal component analysis as pattern recognition tool allows one to reasonably distinguish test solutions according to their chemical composition. (c) 2007 Published by Elsevier B.V.

Pole placement by coordinated tuning of Power System Stabilizers and FACTS-POD stabilizers

This work presents the application of the Decentralized Modal Control method for pole placement in multimachine power systems utilizing FACTS (Flexible AC Transmission Systems), STATCOM (Static Synchronous Compensator) and UPFC (Unified Power Flow Controller) devices. For this, these devices are equipped with supplementary damping controllers, denominated POD ( Power Oscillation Damping), achieving a coordinated project with local controllers (Power System Stabilizers - PSS). Comparative analysis on the function of damping of the FACTS, STATCOM and UPFC is performed using the New England System that has 10 generators, 39 buses and 46 transmission lines. (c) 2011 Elsevier Ltd. All rights reserved.

Diffusion analysis of one photosensitizer in bovine teeth using fluorescence optical imaging

Some photosensitizers (PSs) used for PACT (Antimicrobial Photodynamic Therapy) show an affinity for bacterial walls and can be photo-activated to cause the desired damage. However, on dentine bacterias may be less susceptible to PACT as a result of limited penetration of the PS. The aim of this study was to evaluate the diffusion of one PS based on hematoporphyrin on dentine structures. Twelve bovine incisors were used. Class III cavities (3 x 3 x 1 mm) were prepared on the mesial or distal surfaces using a diamond bur. Photogem (R) solution at 1 mg/mL (10 uL for each cavity) was used. The experimental Groups were divided according to thickness of dentine remaining and etched or no-etched before the PS application. The fluorescence excitation source was a VelScope (R) system. For image capture a scientific CCD color camera PixelFly (R) was coupled to VelScope. For image acquisition and processing, a computational routine was developed at Matlab (R). Fick's Law was used to obtain the average diffusion coefficient of PS. Differences were found between all Groups. The longitudinal temporal diffusion was influenced by the different times, thickness and acid etching.

Numerical exploration of resonant dynamics in the system of Saturnian major satellites

We numerically investigate the long-term dynamics of the Saturnian system by analyzing the Fourier spectra of ensembles of orbits taken around the current orbits of Mimas, Enceladus, Tethys, Rhea and Hyperion. We construct dynamical maps around the current position of these satellites in their respective phase spaces. The maps are the result of a great deal of numerical simulations where we adopt dense sets of initial conditions and different satellite configurations. Several structures associated to the current two-body mean-motion resonances, unstable regions associated to close approaches between the satellites, and three-body mean-motion resonances in the system, are identified in the map. (C) 2010 Elsevier Ltd. All rights reserved.