Carboxylate anions binding and sensing by a novel tetraazamacrocycle containing ferrocene as receptor

A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl-, PF6-, HSO4-, H2PO4- and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). H-1 NMR titrations in CD3OD indicated that this receptor is not suitable for recognizing HSO4- and H2PO4-, but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3) (CH3)(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the H-1 NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF6-, ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS2 stoichiometry are formed with the first three anions, but RS4 with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H center dot center dot center dot O=C hydrogen bonds for carboxylate anions and N - H center dot center dot center dot F hydrogen bonds for the PF6- anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe center dot center dot center dot Fe intramolecular distances ranging from 10.125(14) to 12.783(15) angstrom.

Modelling fixed plant and algal dynamics in rivers: an application to the River Frome

The development of eutrophication in river systems is poorly understood given the complex relationship between fixed plants, algae, hydrodynamics, water chemistry and solar radiation. However there is a pressing need to understand the relationship between the ecological status of rivers and the controlling environmental factors to help the reasoned implementation of the Water Framework Directive and Catchment Sensitive Farming in the UK. This research aims to create a dynamic, process-based, mathematical in-stream model to simulate the growth and competition of different vegetation types (macrophytes, phytoplankton and benthic algae) in rivers. The model, applied to the River Frome (Dorset, UK), captured well the seasonality of simulated vegetation types (suspended algae, macrophytes, epiphytes, sediment biofilm). Macrophyte results showed that local knowledge is important for explaining unusual changes in biomass. Fixed algae simulations indicated the need for the more detailed representation of various herbivorous grazer groups, however this would increase the model complexity, the number of model parameters and the required observation data to better define the model. The model results also highlighted that simulating only phytoplankton is insufficient in river systems, because the majority of the suspended algae have benthic origin in short retention time rivers. Therefore, there is a need for modelling tools that link the benthic and free-floating habitats.

Modelling sediment supply and transport in the River Lugg: strategies for controlling sediment loads

The River Lugg has particular problems with high sediment loads that have resulted in detrimental impacts on ecology and fisheries. A new dynamic, process-based model of hydrology and sediments (INCA- SED) has been developed and applied to the River Lugg system using an extensive data set from 1995–2008. The model simulates sediment sources and sinks throughout the catchment and gives a good representation of the sediment response at 22 reaches along the River Lugg. A key question considered in using the model is the management of sediment sources so that concentrations and bed loads can be reduced in the river system. Altogether, five sediment management scenarios were selected for testing on the River Lugg, including land use change, contour tillage, hedging and buffer strips. Running the model with parameters altered to simulate these five scenarios produced some interesting results. All scenarios achieved some reduction in sediment levels, with the 40% land use change achieving the best result with a 19% reduction. The other scenarios also achieved significant reductions of between 7% and 9%. Buffer strips produce the best result at close to 9%. The results suggest that if hedge introduction, contour tillage and buffer strips were all applied, sediment reductions would total 24%, considerably improving the current sediment situation. We present a novel cost-effectiveness analysis of our results where we use percentage of land removed from production as our cost function. Given the minimal loss of land associated with contour tillage, hedges and buffer strips, we suggest that these management practices are the most cost-effective combination to reduce sediment loads.

Physics-based modelling for remote sensing of snow

Remote sensing is the only practicable means to observe snow at large scales. Measurements from passive microwave instruments have been used to derive snow climatology since the late 1970’s, but the algorithms used were limited by the computational power of the era. Simplifications such as the assumption of constant snow properties enabled snow mass to be retrieved from the microwave measurements, but large errors arise from those assumptions, which are still used today. A better approach is to perform retrievals within a data assimilation framework, where a physically-based model of the snow properties can be used to produce the best estimate of the snow cover, in conjunction with multi-sensor observations such as the grain size, surface temperature, and microwave radiation. We have developed an existing snow model, SNOBAL, to incorporate mass and energy transfer of the soil, and to simulate the growth of the snow grains. An evaluation of this model is presented and techniques for the development of new retrieval systems are discussed.

Estudo do comportamento mecânico de um solo saprolítico de basalto de Teutônia, RS

Essa dissertação apresenta um estudo experimental, com o objetivo de caracterizar a influência da estrutura no comportamento mecânico do solo saprolítico de basalto da região de Teutônia, RS. São apresentados os resultados de ensaios edométricos, ensaios de compressão isotrópica e ensaios de compressão triaxial não drenados (CIU) em amostras reconstituídas juntamente com ensaios de compressão triaxial drenados (CID) e ensaios de compressão isotrópica em amostras indeformadas. A análise dos resultados obtidos nesta dissertação juntamente com os resultados obtidos por Rigo (2005) mostrou que tanto em compressão confinada como em compressão isotrópica o solo indeformado apresenta um comportamento bem mais rígido que solo reconstituído e consegue sustentar índices de vazios bem maiores para um mesmo valor de tensão. Foi observada uma tensão de plastificação em torno de 350 kPa Nos ensaios triaxiais CID o solo indeformado apresentou um comportamento dependente do nível de tensão confinante. Para tensões confinantes mais elevadas foi observada uma queda brusca na curva tensão-deformação após o pico, associada com a formação de um plano de ruptura polido no corpo de prova. A partir dos resultados dos ensaios de compressão isotrópica e ensaios triaxiais CIU no solo reconstituído foram determinadas uma linha de compressão normal (NCL) e uma linha de estado crítico (CSL) para o solo nesta condição. Foi observado que os resultados dos ensaios triaxiais CID no solo indeformado se ajustaram bem a estas linhas de estado.

Investigação do comportamento mecânico de um solo residual de gnaisse da cidade de Porto Alegre

O solo residual de gnaisse ocupa uma grande área da cidade de Porto Alegre. Embora exista histórico de instabilidades de estruturas de contenção executadas neste material, o estudo científico de suas propriedades geotécnicas foi iniciado somente a partir da execução de uma obra de solo grampeado, realizada no ano de 2001. O projeto da obra supracitada foi revisado a partir do início das escavações, através de retro-análises de rupturas induzidas, o que conduziu a parâmetros de resistência ao cisalhamento sensivelmente inferiores aos obtidos inicialmente através de ensaios de campo. Os deslocamentos de crista, medidos nesta estrutura, superaram os valores esperados a partir de dados da literatura. O solo residual de gnaisse estudado apresenta forte anisotropia textural, marcada pelos bandamentos herdados da rocha mãe. Estes bandamentos são formados pela intercalação de bandas micáceas e bandas compostas principalmente por partículas de quartzo e feldspato. Foram realizados ensaios triaxiais com medição local de deformações, ensaios de compressão isotrópica e ensaios de compressão confinada para o estudo da resistência ao cisalhamento e da deformabilidade deste solo residual de gnaisse Os ensaios foram realizados para diferentes ângulos entre o bandamento micáceo e a direção da tensão principal maior a. Diferente dos solos residuais de gnaisse estudados em outras partes do Brasil, o solo residual de gnaisse estudado apresenta clara anisotropia de resistência ao cisalhamento e de deformabilidade, devida à estrutura herdada da rocha mãe. Em um comportamento também diferente dos solos supracitados, o solo residual de gnaisse de Porto Alegre, com base nos ensaios realizados nesta dissertação, não apresenta uma superfície de plastificação dada pela sua estrutura. Realizando-se uma interpretação através dos conceitos da Teoria do Estado Crítico, verificou-se que o solo residual de gnaisse apresenta uma NCL para amostras reconstituídas, mas, devido ao seu caráter anisotrópico, não foi possível determinar a CSL do solo residual de gnaisse, nem definir sobre sua unicidade.

Trendtv : uma arquitetura para mudança automática de canais de TV baseada em redes sociais virtuais com graus de amizade e suporte a múltiplos dispositivos no cenário da TV digital brasileira

Due to the large amount of television content, which emerged from the Digital TV, viewers are facing a new challenge, how to find interesting content intuitively and efficiently. The Personalized Electronic Programming Guides (pEPG) arise as an answer to this complex challenge. We propose TrendTV a layered architecture that allows the formation of social networks among viewers of Interactive Digital TV based on online microblogging. Associated with a pEPG, this social network allows the viewer to perform content filtering on a particular subject from the indications made by other viewers of his network. Allowing the viewer to create his own indications for a particular content when it is displayed, or to analyze the importance of a particular program online, based on these indications. This allows any user to perform filtering on content and generate or exchange information with other users in a flexible and transparent way, using several different devices (TVs, Smartphones, Tablets or PCs). Moreover, this architecture defines a mechanism to perform the automatic exchange of channels based on the best program that is showing at the moment, suggesting new components to be added to the middleware of the Brazilian Digital TV System (Ginga). The result is a constructed and dynamic database containing the classification of several TV programs as well as an application to automatically switch to the best channel of the moment

Aplicação de técnicas de aprendizado de máquina no reconhecimento de classes estruturais de proteínas

Nowadays, classifying proteins in structural classes, which concerns the inference of patterns in their 3D conformation, is one of the most important open problems in Molecular Biology. The main reason for this is that the function of a protein is intrinsically related to its spatial conformation. However, such conformations are very difficult to be obtained experimentally in laboratory. Thus, this problem has drawn the attention of many researchers in Bioinformatics. Considering the great difference between the number of protein sequences already known and the number of three-dimensional structures determined experimentally, the demand of automated techniques for structural classification of proteins is very high. In this context, computational tools, especially Machine Learning (ML) techniques, have become essential to deal with this problem. In this work, ML techniques are used in the recognition of protein structural classes: Decision Trees, k-Nearest Neighbor, Naive Bayes, Support Vector Machine and Neural Networks. These methods have been chosen because they represent different paradigms of learning and have been widely used in the Bioinfornmatics literature. Aiming to obtain an improvment in the performance of these techniques (individual classifiers), homogeneous (Bagging and Boosting) and heterogeneous (Voting, Stacking and StackingC) multiclassification systems are used. Moreover, since the protein database used in this work presents the problem of imbalanced classes, artificial techniques for class balance (Undersampling Random, Tomek Links, CNN, NCL and OSS) are used to minimize such a problem. In order to evaluate the ML methods, a cross-validation procedure is applied, where the accuracy of the classifiers is measured using the mean of classification error rate, on independent test sets. These means are compared, two by two, by the hypothesis test aiming to evaluate if there is, statistically, a significant difference between them. With respect to the results obtained with the individual classifiers, Support Vector Machine presented the best accuracy. In terms of the multi-classification systems (homogeneous and heterogeneous), they showed, in general, a superior or similar performance when compared to the one achieved by the individual classifiers used - especially Boosting with Decision Tree and the StackingC with Linear Regression as meta classifier. The Voting method, despite of its simplicity, has shown to be adequate for solving the problem presented in this work. The techniques for class balance, on the other hand, have not produced a significant improvement in the global classification error. Nevertheless, the use of such techniques did improve the classification error for the minority class. In this context, the NCL technique has shown to be more appropriated

Uma estratégia dirigida a modelos e baseada em linguagem de descrição arquitetural para linhas de produtos de software

Model-oriented strategies have been used to facilitate products customization in the software products lines (SPL) context and to generate the source code of these derived products through variability management. Most of these strategies use an UML (Unified Modeling Language)-based model specification. Despite its wide application, the UML-based model specification has some limitations such as the fact that it is essentially graphic, presents deficiencies regarding the precise description of the system architecture semantic representation, and generates a large model, thus hampering the visualization and comprehension of the system elements. In contrast, architecture description languages (ADLs) provide graphic and textual support for the structural representation of architectural elements, their constraints and interactions. This thesis introduces ArchSPL-MDD, a model-driven strategy in which models are specified and configured by using the LightPL-ACME ADL. Such strategy is associated to a generic process with systematic activities that enable to automatically generate customized source code from the product model. ArchSPLMDD strategy integrates aspect-oriented software development (AOSD), modeldriven development (MDD) and SPL, thus enabling the explicit modeling as well as the modularization of variabilities and crosscutting concerns. The process is instantiated by the ArchSPL-MDD tool, which supports the specification of domain models (the focus of the development) in LightPL-ACME. The ArchSPL-MDD uses the Ginga Digital TV middleware as case study. In order to evaluate the efficiency, applicability, expressiveness, and complexity of the ArchSPL-MDD strategy, a controlled experiment was carried out in order to evaluate and compare the ArchSPL-MDD tool with the GingaForAll tool, which instantiates the process that is part of the GingaForAll UML-based strategy. Both tools were used for configuring the products of Ginga SPL and generating the product source code

MyPersonal-EPG: um EPG personalizável e com suportes a recomendações para o SBTVD

In this work we present the architecture and implementation of MyPersonal-EPG, a personal EPG with support to recommendations, built on top of the Ginga middleware, that fulfill the following requirements: (i) to allow users to build their own personal programming grids, based on programming guides from several broadcasters; (ii) to offer a mechanism to tune the desired channels on the moment the selected programs are about to begin; (iii) to allow users to select the desired programs categories; (iv) to offer programs recommendations, in both synchronous and asynchronous way, based on the categories previously selected by users; (v) to allow users to modify the current configuration options; (vi) to allow the creation of several users accounts, so that each user can store its own information. The application‟s usability test is also presented and its results are discussed and analyzed

Dos requisitos à arquitetura em linhas de produtos de software: uma estratégia de transformações entre modelos

The tracking between models of the requirements and architecture activities is a strategy that aims to prevent loss of information, reducing the gap between these two initial activities of the software life cycle. In the context of Software Product Lines (SPL), it is important to have this support, which allows the correspondence between this two activities, with management of variability. In order to address this issue, this paper presents a process of bidirectional mapping, defining transformation rules between elements of a goaloriented requirements model (described in PL-AOVgraph) and elements of an architectural description (defined in PL-AspectualACME). These mapping rules are evaluated using a case study: the GingaForAll LPS. To automate this transformation, we developed the MaRiPLA tool (Mapping Requirements to Product Line Architecture), through MDD techniques (Modeldriven Development), including Atlas Transformation Language (ATL) with specification of Ecore metamodels jointly with Xtext , a DSL definition framework, and Acceleo, a code generation tool, in Eclipse environment. Finally, the generated models are evaluated based on quality attributes such as variability, derivability, reusability, correctness, traceability, completeness, evolvability and maintainability, extracted from the CAFÉ Quality Model

Conteúdo educativo para a televisão digital interativa

Pós-graduação em Televisão Digital: Informação e Conhecimento - FAAC

Televisão digital interativa: alternativa de design e usabilidade para o aplicativo som e prosa

Pós-graduação em Televisão Digital: Informação e Conhecimento - FAAC