Designing Hydrogels that Transform their Shape in Response to Molecular Cues

There has been considerable interest in developing shape-changing soft materials for potential applications in drug delivery, microfluidics and biosensing. These shape- changing materials are inspired by the morphological changes exhibited by plants in nature, such as the Venus flytrap. One specific class of shape-change is that from a flat sheet to a folded structure (e.g., a tube). Such “self-folding” materials are usually composed of polymer hydrogels, and these typically fold in response to external stimuli such as pH and temperature. In order to develop these hydrogels for the previously described applications, it is necessary to expand the range of triggers. The focus of this dissertation is the advancement of shape-changing polymer hydrogels that are sensitive to uncommon cues such as specific biomolecules (enzymes), the substrates for such enzymes, or specific multivalent cations. First, we describe a hybrid gel that responds to the presence of low concentrations of a class of enzymes known as matrix metalloproteinases (MMPs). The hybrid gel was created by utilizing photolithographic techniques to combine two or more gels with distinct chemical composition into the same material. Certain portions of the hybrid gel are composed of a biopolymer derivative with crosslinkable groups. The hybrid gel is flat in water; however, in the presence of MMPs, the regions containing the biopolymer are degraded and the flat sheet folds to form a 3D structure. We demonstrate that hydrogels with different patterns can transform into different 3D structures such as tubes, helices and pancakes. Furthermore, this shape change can be made to occur at physiological concentrations of enzymes. Next, we report a gel with two layers that undergoes a shape change in the presence of glucose. The enzyme glucose oxidase (GOx) is immobilized in one of the layers. GOx catalyzes the conversion of glucose to gluconic acid. The production of gluconic acid decreases the local pH. The decrease in local pH causes one of the layers to swell. As a result, the flat sheet folds to form a tube. The tube unfolds to form a flat sheet when it is transferred to a solution with no glucose present. Therefore, this biomolecule- triggered shape transformation is reversible, meaning the glucose sensing gel is reusable. Furthermore, this shape change only occurs in the presence of glucose and it does not occur in the presence of other small sugars such as fructose. In our final study, we report the shape change of a gel with two layers in the presence of multivalent ions such as Ca2+ and Sr2+. The gel consists of a passive layer and an active layer. The passive layer is composed of dimethylyacrylamide (DMAA), which does not interact with multivalent ions. The active layer consists of DMAA and the biopolymer alginate. In the presence of Ca2+ ions, the alginate chains crosslink and the active layer shrinks. As a result, the gel converts from a flat sheet to a folded tube. What is particularly unusual is the direction of folding. In most cases, when flat rectangular gels fold, they do so about their short-side. However, our gels typically fold about their long-side. We hypothesize that non-homogeneous swelling determines the folding axis.

Triangular mesh parameterization with trimmed surfaces

Given a 2manifold triangular mesh \(M \subset {\mathbb {R}}^3\), with border, a parameterization of \(M\) is a FACE or trimmed surface \(F=\{S,L_0,\ldots, L_m\}\) -- \(F\) is a connected subset or region of a parametric surface \(S\), bounded by a set of LOOPs \(L_0,\ldots ,L_m\) such that each \(L_i \subset S\) is a closed 1manifold having no intersection with the other \(L_j\) LOOPs -- The parametric surface \(S\) is a statistical fit of the mesh \(M\) -- \(L_0\) is the outermost LOOP bounding \(F\) and \(L_i\) is the LOOP of the ith hole in \(F\) (if any) -- The problem of parameterizing triangular meshes is relevant for reverse engineering, tool path planning, feature detection, redesign, etc -- Stateofart mesh procedures parameterize a rectangular mesh \(M\) -- To improve such procedures, we report here the implementation of an algorithm which parameterizes meshes \(M\) presenting holes and concavities -- We synthesize a parametric surface \(S \subset {\mathbb {R}}^3\) which approximates a superset of the mesh \(M\) -- Then, we compute a set of LOOPs trimming \(S\), and therefore completing the FACE \(F=\ {S,L_0,\ldots ,L_m\}\) -- Our algorithm gives satisfactory results for \(M\) having low Gaussian curvature (i.e., \(M\) being quasi-developable or developable) -- This assumption is a reasonable one, since \(M\) is the product of manifold segmentation preprocessing -- Our algorithm computes: (1) a manifold learning mapping \(\phi : M \rightarrow U \subset {\mathbb {R}}^2\), (2) an inverse mapping \(S: W \subset {\mathbb {R}}^2 \rightarrow {\mathbb {R}}^3\), with \ (W\) being a rectangular grid containing and surpassing \(U\) -- To compute \(\phi\) we test IsoMap, Laplacian Eigenmaps and Hessian local linear embedding (best results with HLLE) -- For the back mapping (NURBS) \(S\) the crucial step is to find a control polyhedron \(P\), which is an extrapolation of \(M\) -- We calculate \(P\) by extrapolating radial basis functions that interpolate points inside \(\phi (M)\) -- We successfully test our implementation with several datasets presenting concavities, holes, and are extremely nondevelopable -- Ongoing work is being devoted to manifold segmentation which facilitates mesh parameterization

Estudo da sinterização de cavacos de aço ferritico

This research studies the sintering of ferritic steel chips from the machining process. Were sintered metal powder obtained from machining process chips for face milling of a ferritic steel. The chip was produced by machining and characterized by SEM and EDS, and underwent a process of high energy mill powder characterized also by SEM and EDS. Were constructed three types of matrixes for uniaxial compression (relation l / d greater than 2.5). The differences in the design of the matrixes were essentially in the direction of load application, which for cylindrical case axial direction, while for the rectangular arrays, the longer side. Two samples were compressed with different geometries, a cylindrical and rectangular with the same compaction pressure of 700 MPa. The samples were sintered in a vacuum resistive furnace, heating rate 20 °C / min., isotherm 1300 °C for 60 minutes, and cooling rate of 25 °C / min to room temperature. The starting material of the rectangular sample was further annealed up to temperature of 800 ° C for 30 min. Sintered samples were characterized by scanning electron microscopy, optical microscopy and EDS. The sample compressed in the cylindrical matrix did not show a regular density reflecting in the sintered microstructure revealed by the irregular geometry of the pores, characterizing that the sintering was not complete, reaching only the second phase. As for the specimen compacted in the rectangular array, the analysis performed by scanning electron microscopy, optical microscopy and EDS indicate a good densification, and homogeneous microstructure in their full extent. Additionally, the EDS analyzes indicate no significant changes in chemical composition in the process steps. Therefore, it is concluded that recycling of chips, from the processed ferritic steel is feasible by the powder metallurgy. It makes possible rationalize raw material and energy by manufacture of known properties components from chips generated by the machining process, being benefits to the environment

Adaptive coatings based on polyaniline for direct 2D observation of diffusion processes in microfluidic systems

[EN] Therefore the understanding and proper evaluation of the flow and mixing behaviour at microscale becomes a very important issue. In this study, the diffusion behaviour of two reacting solutions of HCI and NaOH were directly observed in a glass/polydimethylsiloxane microfluidic device using adaptive coatings based on the conductive polymer polyaniline that are covalently attached to the microchannel walls. The two liquid streams were combined at the junction of a Y-shaped microchannel, and allowed to diffuse into each other and react. The results showed excellent correlation between optical observation of the diffusion process and the numerical results. A numerical model which is based on finite volume method (FVM) discretisation of steady Navier-Stokes (fluid flow) equations and mass transport equations without reactions was used to calculate the flow variables at discrete points in the finite volume mesh element. The high correlation between theory and practical data indicates the potential of such coatings to monitor diffusion processes and mixing behaviour inside microfluidic channels in a dye free environment.

Tanques sépticos seguidos de leitos cultivados com diferentes espécies de macrofitas no tratamento de esgoto

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Agronomia e Medicina Veterinária, Programa de Pós-Graduação em Agronomia, 2016.

Efeito da adição de feldspato e/ou resíduo de caulin em formulações à base de argila ilítica

The red pottery industry in Piauí state is well developed and stands out at the national context for the technical quality of its products. The floor and wall tile industry, however, is little developed since the state has only one company that produces red clay-based ceramic tiles. This thesis aims at using the predominantly illitic basic mass of the above mentioned industry, with the addition of feldspar and/or kaolin residue in order to obtain products of higher technical quality. Kaolin residue consists basically of kaolinite, muscovite mica and quartz; the feldspar used was potassic. In this experiment, basic mass (MB) was used for experimental control and fifteen formulations codified as follows: F2, F4, F8, F16, F32, FR2, FR4, FR8, FR16, FR32, R2, R4, R8, R16 and R32. All raw materials were dry-milled, classified, formulated and then humidified to 10% water. Thereafter, test samples were produced by unixial pressing process in a rectangular steel matrix (60.0 x 20.0 x 5.0) mm3 at (25 MPa). They were fired at four temperatures: 1080°C, 1120°C, 1160°C, with a heating rate of 10°C/min during up to 10 min in an electric oven, and the last one in an industrial oven with a peak of 1140°C, aim ing to confirm the results found in laboratory and, finally, technological tests were performed: MEA, RL, AA, PA, TRF and PF. The results revealed that the residue under study can be considered a raw material with large potential in the industry of red clay-based ceramic tiles, since the results found both in laboratory and in the industry have shown that the test samples produced from the formulations with up to 4% feldspar and those produced with up to 8% feldspar and residue permitted a reduction in the water absorption rate and an increase in the mechanical resistance while those samples produced with up to 4% residue had an increase in the mechanical resistance when compared to those produced from the basic mass and that the formulation with 2% feldspar and residue presented the best technological properties, lowering the sintering temperature down to 1120°C

Desenvolvimento e avaliação de um sistema de cálculo de dose independente para controle de qualidade de IMRT do tipo jaws-only

Dissertação (mestrado)—Universidade de Brasília, Faculdade Gama, Programa de Pós-Graduação em Engenharia Biomédica, 2015.

Exact solutions for the agricultural and the two-dimensional packing problems

Objectives and study method: The objective of this study is to develop exact algorithms that can be used as management tools for the agricultural production planning and to obtain exact solutions for two of the most well known twodimensional packing problems: the strip packing problem and the bin packing problem. For the agricultural production planning problem we propose a new hierarchical scheme of three stages to improve the current agricultural practices. The objective of the first stage is to delineate rectangular and homogeneous management zones into the farmer’s plots considering the physical and chemical soil properties. This is an important task because the soil properties directly affect the agricultural production planning. The methodology for this stage is based on a new method called “Positions and Covering” that first generates all the possible positions in which the plot can be delineated. Then, we use a mathematical model of linear programming to obtain the optimal physical and chemical management zone delineation of the plot. In the second stage the objective is to determine the optimal crop pattern that maximizes the farmer’s profit taken into account the previous management zones delineation. In this case, the crop pattern is affected by both management zones delineation, physical and chemical. A mixed integer linear programming is used to solve this stage. The objective of the last stage is to determine in real-time the amount of water to irrigate in each crop. This stage takes as input the solution of the crop planning stage, the atmospheric conditions (temperature, radiation, etc.), the humidity level in plots, and the physical management zones of plots, just to name a few. This procedure is made in real-time during each irrigation period. A linear programming is used to solve this problem. A breakthrough happen when we realize that we could propose some adaptations of the P&C methodology to obtain optimal solutions for the two-dimensional packing problem and the strip packing. We empirically show that our methodologies are efficient on instances based on real data for both problems: agricultural and two-dimensional packing problems. Contributions and conclusions: The exact algorithms showed in this study can be used in the making-decision support for agricultural planning and twodimensional packing problems. For the agricultural planning problem, we show that the implementation of the new hierarchical approach can improve the farmer profit between 5.27% until 8.21% through the optimization of the natural resources. An important characteristic of this problem is that the soil properties (physical and chemical) and the real-time factors (climate, humidity level, evapotranspiration, etc.) are incorporated. With respect to the two-dimensional packing problems, one of the main contributions of this study is the fact that we have demonstrate that many of the best solutions founded in literature by others approaches (heuristics approaches) are the optimal solutions. This is very important because some of these solutions were up to now not guarantee to be the optimal solutions.

Otimização evolucionária para problemas de transferência de calor em PCI usando MEC

Dissertação (mestrado)—Universidade de Brasília, Faculdade UnB Gama, Programa de Pós-graduação em Integridade de Materiais da Engenharia, 2015.

2 D game ediror on-line : A edição de videojogos em contexto web

Descreve-se, no presente trabalho, os esforços envidados no sentido de criar uma solução informática generalista, para os problemas mais recorrentes do processo de produção de videojogos 20, baseados em sprites, a correr em plataformas móveis. O sistema desenvolvido é uma aplicação web que está inserida no paradigma cloud­computing, usufruindo, portanto, de todas as vantagens em termos de acessibilidade, segurança da informação e manutenção que este paradigma oferece actualmente. Além das questões funcionais, a aplicação é ainda explorada do ponto de vista da arquitetura da implementação, com vista a garantir um sistema com implementação escalável, adaptável e de fácil manutenção. Propõe-se ainda um algoritmo que foi desenvolvido para resolver o problema de obter uma distribuição espacial otimizada de várias áreas retangulares, sem sobreposições nem restrições a nível das dimensões, quer do arranjo final, quer das áreas arranjadas. ABSTRACT: This document describes the efforts taken to create a generic computing solution for the most recurrent problems found in the production of two dimensional, sprite­based videogames, running on mobile platforms. The developed system is a web application that fits within the scope of the recent cloud-computing paradigm and, therefore, enjoys all of its advantages in terms of data safety, accessibility and application maintainability. In addition, to the functional issues, the system is also studied in terms of its internal software architecture, since it was planned and implemented in the perspective of attaining an easy to maintain application, that is both scalable and adaptable. Furthermore, it is also proposed an algorithm that aims to find an optimized solution to the space distribution problem of several rectangular areas, with no overlapping and no dimensinal restrictions, neither on the final arrangement nor on the arranged areas.

A aprendizagem da multiplicação perspetiva através através da resolução da sequência de problemas

Este estudo tem como objetivo compreender de que forma os alunos desenvolvem a aprendizagem da multiplicação através da resolução de uma sequência de problemas. Mais concretamente, pretende Identificar e analisar as estratégias e procedimentos de cálculo utilizados pelos alunos quando resolvem problemas de multiplicação e o contributo da sequência de problemas na aprendizagem desta operação. O quadro teórico integra duas secções que discutem as seguintes temáticas: a resolução de problemas e o ensino e aprendizagem da multiplicação. A metodologia deste estudo segue uma abordagem qualitativa, na vertente de investigação-ação. Nele participaram 20 alunos de uma turma do 2.º ano de escolaridade. A recolha de dados foi realizada com recurso à observação participante, à recolha documental, a conversas informais e à entrevista. Os resultados deste estudo sobre as estratégias e procedimentos de cálculo usados pelos alunos quando resolvem problemas de multiplicação revelam que: (i) recorrem a alguma diversidade de estratégias e procedimentos de cálculo na resolução de problemas de multiplicação, (ii) há alunos que, numa fase inicial, recorrem a várias estratégias e procedimentos para resolver um mesmo problema, (iii) por vezes, os alunos regridem na estratégia utilizada comparando com a que usou no problema anterior da sequência e (iv) associada a cada uma das estratégias há procedimentos de cálculo mais frequentes do que outros. Estes resultados mostram, ainda, no que se refere ao contributo da sequência de problemas na aprendizagem da multiplicação que: (i) problemas com contextos associados ao modelo de disposição retangular contribuem para o uso de estratégias multiplicativas, desde que os números envolvidos sejam adequados, (ii) os números de referência e do conhecimento dos alunos facilitam os cálculos efetuados pelos mesmos e (iii) a articulação entre os problemas da sequência contribui para a progressão das estratégias utilizadas pelos alunos.

Simulação de fluxo de fluidos em meios porosos desordenados uma análise de efeito de escala na estimativa da permeabilidade e do coeficiente de arrasto

The present study provides a methodology that gives a predictive character the computer simulations based on detailed models of the geometry of a porous medium. We using the software FLUENT to investigate the flow of a viscous Newtonian fluid through a random fractal medium which simplifies a two-dimensional disordered porous medium representing a petroleum reservoir. This fractal model is formed by obstacles of various sizes, whose size distribution function follows a power law where exponent is defined as the fractal dimension of fractionation Dff of the model characterizing the process of fragmentation these obstacles. They are randomly disposed in a rectangular channel. The modeling process incorporates modern concepts, scaling laws, to analyze the influence of heterogeneity found in the fields of the porosity and of the permeability in such a way as to characterize the medium in terms of their fractal properties. This procedure allows numerically analyze the measurements of permeability k and the drag coefficient Cd proposed relationships, like power law, for these properties on various modeling schemes. The purpose of this research is to study the variability provided by these heterogeneities where the velocity field and other details of viscous fluid dynamics are obtained by solving numerically the continuity and Navier-Stokes equations at pore level and observe how the fractal dimension of fractionation of the model can affect their hydrodynamic properties. This study were considered two classes of models, models with constant porosity, MPC, and models with varying porosity, MPV. The results have allowed us to find numerical relationship between the permeability, drag coefficient and the fractal dimension of fractionation of the medium. Based on these numerical results we have proposed scaling relations and algebraic expressions involving the relevant parameters of the phenomenon. In this study analytical equations were determined for Dff depending on the geometrical parameters of the models. We also found a relation between the permeability and the drag coefficient which is inversely proportional to one another. As for the difference in behavior it is most striking in the classes of models MPV. That is, the fact that the porosity vary in these models is an additional factor that plays a significant role in flow analysis. Finally, the results proved satisfactory and consistent, which demonstrates the effectiveness of the referred methodology for all applications analyzed in this study.

Les cultes domestiques dans la Grèce antique : catalogue raisonné d’autels domestiques

Si la religion grecque a fait l’objet de nombreuses études, les informations concernant les rites domestiques se font plus discrètes. Nous avons donc tenté de présenter les traces archéologiques de ses cultes domestiques en nous concentrant sur un élément bien précis, les autels. Nous vous proposons donc dans ce mémoire de présenter un catalogue raisonné des autels domestiques de la Grèce antique. Celui-ci répertorie 140 autels domestiques, qu’ils soient de types fixes (construits) ou portatifs (arulae). Une analyse quantitative et qualitative des informations colligées dans le catalogue fait suite à ce dernier. Nous pouvons tirer quelques conclusions partielles suite à l’analyse de notre catalogue. Il est possible d’affirmer qu’il existe beaucoup plus d’autels portatifs que d’autels fixes. Les arulae n’ont pour la plupart pas été trouvés in situ, contrairement aux autels construits. La grande majorité des autels se trouvent dans la cour de la demeure ou contre un mur extérieur de la maison. Les autels portatifs, eux se retrouvent aussi dans diverses pièces de la maison, dont la pastas. La majorité des autels portatifs sont faits de terre-cuite, alors que les fixes sont tous faits de différentes pierres. Peu importe le type, la majorité des autels sont rectangulaires plutôt que circulaires. Très peu d’autels sont dédiés spécifiquement à un dieu et ceux attribués à Zeus Herkeios le sont seulement par leur position dans la cour de la demeure et non à cause d’un décor ou d’objets affiliés. Les autels autant portatifs que fixes peuvent porter un décor, allant d’une simple moulure à un riche décor rappelant les grands autels monumentaux des sanctuaires. Certains sont par contre nus et ont même des faces non travaillées. Nous détaillons dans la dernière section le cas de Zeus Ktésios et Zeus Kataibatès, comme nous possédons beaucoup d’informations pertinentes sur ces deux divinités et nous pouvons donc nous attarder sur leur culte. Il est par contre difficile de recréer des rites domestiques complets. Pour ce faire, il faudrait avoir accès aux catalogues complets des artéfacts retrouvés sur chaque site. Nous pourrions ainsi créer des assemblages et mettre en liens ces objets et les autels et tenter d’interpréter et de reconstituer ces différents rites domestiques.

Determing the Effect of Thermal Treatment Timing on Ultra-High Performance Concrete Beams

The loss of prestressing force over time influences the long-term deflection of the prestressed concrete element. Prestress losses are inherently complex due to the interaction of concrete creep, concrete shrinkage, and steel relaxation. Implementing advanced materials such as ultra-high performance concrete (UHPC) further complicates the estimation of prestress losses because of the changes in material models dependent on curing regime. Past research shows compressive creep is "locked in" when UHPC cylinders are subjected to thermal treatment before being loaded in compression. However, the current precasting manufacturing process would typically load the element (through prestressing strand release from the prestressing bed) before the element would be taken to the curing facility. Members of many ages are stored until curing could be applied to all of them at once. This research was conducted to determine the impact of variable curing times for UHPC on the prestress losses, and hence deflections. Three UHPC beams, a rectangular section, a modified bulb tee section, and a pi-girder, were assessed for losses and deflections using an incremental time step approach and material models specific to UHPC based on compressive creep and shrinkage testing. Results show that although it is important for prestressed UHPC beams to be thermally treated, to "lock in" material properties, the timing of thermal treatment leads to negligible differences in long-term deflections. Results also show that for UHPC elements that are thermally treated, changes in deflection are caused only by external loads because prestress losses are "locked-in" following thermal treatment.

NEW MICROFLUIDIC SYSTEM TO INCREASE ROBUSTNESS OF ELECTRODE PERFORMANCE AND DEVELOP POINT-OF-CARE HEMATOCRIT DEVICE

The present dissertation aimed to develop a new microfluidic system for a point-of-care hematocrit device. Stabilization of microfluidic systems via surfactant additives and integration of semipermeable SnakeSkin® membranes was investigated. Both methods stabilized the microfluidic systems by controlling electrolysis bubbles. Surfactant additives, Triton X-100 and SDS stabilized promoted faster bubble detachment at electrode surfaces by lowering surface tension and decreased gas bubble formation by increasing gas solubility. The SnakeSkin® membranes blocked bubbles from entering the microchannel and thus less disturbance to the electric field by bubbles occurred in the microchannel. Platinum electrode performance was improved by carbonizing electrode surface using red blood cells. Irreversibly adsorbed RBCs lysed on platinum electrode surfaces and formed porous carbon layers while current response measurements. The formed carbon layers increase the platinum electrode surface area and thus electrode performance was improved by 140 %. The microfluidic system was simplified by employing DC field to use as a platform for a point-of-care hematocrit device. Feasibility of the microfluidic system for hematocrit determination was shown via current response measurements of red blood cell suspensions in phosphate buffered saline and plasma media. The linear trendline of current responses over red blood cell concentration was obtained in both phosphate buffered saline and plasma media. This research suggested that a new and simple microfluidic system could be a promising solution to develop an inexpensive and reliable point-of-care hematocrit device.