This work presents the first alkaline redox flow battery (a-RFB) based on the coordination chemistry of cobalt(III/II) and iron(III/II) with amino-alcohol ligands in concentrated NaOH([subscript aq]). The a-RFB was developed by carrying out systematic structural and electrochemical characterizations of various redox-active coordination compounds to find the most suitable candidates for electrochemical energy storage. In the characterization studies, particular attention was given to the redox couple Fe(III/II)- TEA, where TEA = triethanolamine, because of its importance in the fields of supramolecular chemistry, magnetic memory films, and electrochemical energy storage. The structures of Fe(III)-TEA in the solid state and in alkaline solution are reported for the first time. Moreover, experimental evidence is presented for the existence of an EC reaction in the heterogeneous reduction of Fe(III/II)-TEA in concentrated base. Furthermore, experiments were carried out to study the reactivity of Fe(II)-TEA with O2. This is important because O2 reacts spontaneously with Fe(II)-TEA to produce hydrogen peroxide, decreasing the charging-discharging capacity of the a-RFB. The reduction of oxygen by Fe(II)-TEA in concentrated base was studied by UV-Vis spectroscopy and coulometric titrations. Additionally, a new method for the quick identification of redox couples with slow EC reactions, k[subscript f] < 0.1 s-1, is presented. The new method is based on scanning electrochemical microscopy (SECM) and consists of creating a thin-layer cell between the tip and substrate electrode. During analysis of a redox couple, the tip reports a current transient proportional to the decaying concentration of the product of the E reaction, from which an apparent forward rate constant for the C reaction can be determined. This method was designed for the field of RFB research, where the identification of redox couples with no EC reactions is necessary to ensure that a battery can run for thousands of cycles. Lastly, surface oxidation of polycrystalline Ir ultramicroelectrodes was studied by the surface interrogation mode of SECM (SI-SECM), using Fe(II)-TEA as the titrant. This was done to demonstrate the existence of hydrous oxides of Ir(IV) and Ir(V) prior to the onset of oxygen evolution in concentrated base. Numerical simulations were carried out using commercial software and were used to validate the experimental results reported in this work. / text

We consider the problem of synthesizing program inverses for imperative languages. Our primary motivation comes from optimistic parallel discrete event simulation (OPDES). There, a simulator must process events while respecting logical temporal event-ordering constraints; to extract parallelism, an OPDES simulator may speculatively execute events and only rollback execution when event-ordering violations occur. In this context, the ability to perform rollback by running time- and space-efficient reverse programs, rather than saving and restoring large amounts of state, can make OPDES more practical. Synthesizing inverses also appears in numerous other software engineering contexts, such as debugging, synthesizing “undo” code, or even generating decompressors automatically given only lossless compression code. This thesis mainly contains three chapters. In the first chapter, we focus on handling programs with only scalar data and arbitrary control flows. By building a value search graph (VSG) that represents recoverability relationships between variable values, we turn the problem of recovering previous values into a graph search one. Forward and reverse programs are generated according to the search results. For any loop that produces an output state given a particular input state, our method can synthesize an inverse loop that reconstructs the input state given the original loop's output state. The synthesis process consists of two major components: (a) building the inverse loop's body, and (b) building the inverse loop's predicate. Our method works for all natural loops, including those that take early exits (e.g., via breaks, gotos, returns). In the second chapter we extend our method to handling programs containing arrays. Based on Array SSA, we develop a modified Array SSA from which we could easily build equalities between arrays and array elements. Specifically, to represent the equality between two arrays, we employ the array subregion as the constraint. During the search those subregions will be calculated to guarantee that all array elements will be retrieved. We also develop a demand-driven method to retrieve array elements from a loop, in which each time we only try to retrieve an array element from an iteration if that element has not been modified in previous iterations. To ensure the correctness of each retrieval, the boundary conditions are created and checked at the entry and the exit of the loop. In the last chapter, we introduce several techniques of handling high-level constructs of C++ programs, including virtual functions, copying C++ objects, C++ STL containers, C++ source code normalization, inter-procedural function calls, etc. Since C++ is an object-oriented (OO) language, our discussion in this chapter can also be extended to other OO languages like Java.

A multidisciplinary approach has been applied to the development of sustainable technologies for three industrially relevant projects. Reversible ionic liquids are novel carbon dioxide capture solvents. These non-aqueous silylamines efficiently capture carbon dioxide through chemical and physical absorption and release carbon dioxide with minimal addition of heat. The development of these capture agents aims to eliminate the need for a co-solvent, while minimizing energy loss and achieving solvent recyclability. Also presented is the use of carbon dioxide for amine protection during chemical syntheses. Amine protection is widely used in almost all sectors of chemical and pharmaceutical industries. The use of carbon dioxide as a reversible protecting group reduces solvent waste during protection and deprotection and improves the atom economy of existing processes. Sustainable chemistry has also been applied to the use of reversible ionic liquids as switchable surfactants for nanoparticle synthesis. The reversible ionic liquid system offers two significant advantages toward a more efficient synthesis and deposition of nanoparticles in that an additional surfactant is not required, and due to the reversible nature of the ionic liquids, a facile and waste-reduced deposition method exists.

Digital watermarking of multimedia content has been proposed as a method for different applications such as copyright protection, content authentication, transaction tracking and data hiding. In this thesis, we propose a lossless watermarking approach based on Discrete Cosine Transform (DCT) for a new application of watermarking. A depth map obtained from a stereoscopic image pair is embedded into one of the two images using a reversible watermarking algorithm. Different from existing approaches which hide depth map in spatial domain, the depth information is hidden in the quantized DCT domain of the stereo image in our method. This modification makes the watermarking algorithm compatible with JPEG and MPEG-2 compression. After the investigation of the quantized DCT coefficients distribution of the compressed image and video, The bit-shift operation is utilized to embed the depth map into its associated 2D image reversibly for the purpose of achieving high compression efficiency of the watermarked image and/or video and high visual quality of stereo image and/or video after the depth map is extracted. We implement the proposed method to analyze its performance. The experimental results show that a very high payload of watermark (e.g. depth map) can be embedded into the JPEG compressed image and MPEG-2 video. The compression efficiency is only slightly reduced after the watermark embedding and the quality of the original image or video can be restored completely at the decoder side.

Orientador: Claudio Aguinaldo Buzzi / Banca: Miriam Garcia Manoel / Banca: Angela Maria Sitta / Banca: Parham Salehyan / Banca: Osvaldo Germano do Rocio / Resumo: Neste trabalho apresentamos um estudo dos campos de vetores lineares reversíveis e equivariantes. Tal estudo tem como base a Teoria de Representações de grupos de Lie compactos. Usaremos o fato de que a ascensão de um grupo de Lie compacto pode ser decomposta como soma direta de representações irredutíveis e de acordo com o Lema de Schur tais representações poderão ser de três tipos: R; C ou H. Daremos uma classificação das possíveis estruturas dos sistemas lineares reversíveis equivariantes baseado na teoria de representações citada acima e faremos um estudo dos autovalores para uma classe particular de funções Lreversíveis. Dessa forma temos um cenário bem claro da dinâmica de tais sistemas em cada uma dessas classes. / Abstract: In this work we present a study of the linear equivariant reversible vector fields. This study is based on the Theory of Representation of compact Lie groups. We use the fact that an action of a compact Lie group can be decomposed as a direct sum of irreducible representations, and according to Schur's Lemma these representations can be only of three types: R; C ou H. We give a classification of the possible structures of the linear equivariant reversible systems based on the Theory of Representations mentioned above and we study of the eigenvalues for a particular classes of Lreversible maps. In this way we have a very clear scenario about the dynamics of such systems in each one of these classes. / Mestre

Adolescent (14-17 year-olds) and young adult (18-20 year-olds) women account for a disproportionate 20% of the total number of unintended pregnancies that occur among women of all reproductive ages (14-55 year-olds) each year in the US. Nearly half (41%) of all unintended pregnancies result from the 18% of women who report inconsistent, incorrect, or no use of their contraceptive method. Evidence shows that a large proportion of these young women, especially those who are sexually active, come to the emergency department for their core sexual and reproductive health care needs. By obtaining a better understanding of the sexual and reproductive health needs and preferences of an urban population that is disproportionately low income and ethnically and racially diverse, our hope is to maximize adolescent and young adult accessibility to contraceptive services most feasible in the PED environment such as Nexplanon, in addition to the provision of comprehensive contraceptive counseling and education. OBJECTIVES: The first objective of this subgroup analysis is to determine the percentage of adolescent and young adult females presenting to an urban PED who are familiar with Nexplanon and to describe the demographic, sexual health, and contraceptive use characteristics of these young women. The second main objective of our study is to evaluate the sources of Nexplanon-related information reported by respondents familiar with Nexplanon. In addition to the main objectives, we also determine participant willingness to initiate or switch to Nexplanon® and receptivity to learning about contraceptive methods during a related or nonrelated visit to the PED. METHODS: This is a cross-sectional descriptive study using a paper-based anonymous questionnaire distributed to female patients, ages 16-21 years, presenting to a Boston urban pediatric emergency department (PED). This is a sub-group analysis of a larger study aimed at describing the contraceptive use history of young women who present to the PED. To identify if any statistically significant categorical variables existed between the two assigned groups, univariate analysis was performed using Chi-squared tests. Odds ratios with 95% confidence intervals (CIs) were obtained for the relationship between participants who have heard of Nexplanon and the three statistically significant variables: history of STDs, gravidity, and prior sexual intercourse with a male. Mean and Standard Deviation were used to describe the one continuous variable, age, followed by univariate analysis using independent t-test. Statistical significance was indicated using p-values for the categorical variables and odds ratio with 95% CI for the continuous variable—age. RESULTS: Of the 366 adolescent and young adult females included in our subgroup analysis, 230 (62.8%) indicated they were familiar with Nexplanon. We found that female participants familiar with Nexplanon were 1.3 times more likely to have had a prior STI, twice as likely to have had one or more previous pregnancies, and 3.5 times more likely to have previously engaged in sexual intercourse with a male compared to those female participants unfamiliar with Nexplanon. We also found that most (42.2%) female participants familiar with Nexplanon obtained their contraceptive information from their family and friends only, while about a third obtained their contraceptive information from medical professionals only. Among our total population of respondents, 6% (22/366) of our sub-group participants identified the contraceptive implant as their current method of contraception. Lastly, approximately 21% of female participants familiar with Nexplanon indicated current use of a long-acting reversible contraceptive method at the time of the survey. CONCLUSION: Overall, our study findings are supportive of and consistent with the provision and education of Nexplanon in the PED. This would be a crucial opportunity to provide comprehensive contraceptive counseling and convenient access to the most effective method of contraception among a population that disproportionately affected by unintended pregnancy. This can be made possible by enabling PED health care providers with the proper access to and training in Nexplanon. By adapting these patient-centered practices and techniques, the PED setting can contribute to the notable reduction in teen pregnancy seen in a variety of similar clinic-based interventions. The PED atmosphere has enormous potential to serve young women as an additional venue for contraception education and access.

abstract: Solar energy is leading in renewable energy sources and the aspects surrounding the efforts to harvest light are gaining importance. One such aspect is increasing the light absorption, where heliotropism comes into play. Heliotropism, the ability to track the sun across the sky, can be integrated with solar cells for more efficient photon collection and other optoelectronic systems. Inspired by plants, which optimize incident sunlight in nature, several researchers have made artificial heliotropic and phototropic systems. This project aims to design, synthesize and characterize a material system and evaluate its application in a phototropic system. A gold nanoparticle (Au NP) incorporated poly(N-isopropylacrylamide) (PNIPAAm) hydrogel was synthesized as a photo-thermo-responsive material in our phototropic system. The Au NPs generate heat from the incident via plasmonic resonance to induce a volume phase change of the thermo-responsive hydrogel PNIPAAm. PNIPAAm shrinks or swells at temperature above or below 32°C. Upon irradiation, the Au NP-PNIPAAm micropillar actuates, specifically bending toward the incident light and precisely following the varying incident angle. Swelling ratio tests, bending angle tests with a static incident light and bending tests with varying angles were carried out on hydrogel samples with varying Au NP concentrations. Swelling ratios ranging from 1.45 to 2.9 were recorded for pure hydrogel samples and samples with very low Au NP concentrations. Swelling ratios of 2.41 and 3.37 were calculated for samples with low and high concentrations of Au NPs, respectively. A bending of up to 88° was observed in Au NP-hydrogel pillars with a low Au NP concentration with a 90° incident angle. The light tracking performance was assessed by the slope of the pillar Bending angle (response angle) vs. Incident light angle plot. A slope of 1 indicates ideal tracking with top of the pillar being normal to the incident light, maximizing the photon absorption. Slopes of 0.82 and 0.56 were observed for the low and high Au NP concentration samples. The rapid and precise incident light tracking of our system has shown the promise in phototropic applications. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2016

Orientador: Celia Marisa Rizzatti Barbosa / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-02T19:46:49Z (GMT). No. of bitstreams: 1 Silva-Concilio_LaisRegianeda_M.pdf: 2601283 bytes, checksum: e3d20b72a9e5b76acb85ff36d0a4bd45 (MD5) Previous issue date: 2002 / Resumo: O objetivo deste trabalho foi avaliar a alteração linear de modelos refratários obtidos a partir de moldes de hidrocolóide reversível (HR) de duas marcas comerciais (DUPLlCADOR VIPI® -Dental VIPI Ltda. e DUPLlCADOR K27® - Knebel Produtos Dentários Ltda.), submetidos a 15 ciclos de reutilização. Para isto, foi utilizado um modelo metálico com 4 marcações (A, B, C e D) que quando unidas, admitiam a mensuração linear das distâncias AB, BC, CD, DA, BD e AC. A partir deste modelo, foram confeccionados 10 modelos em gesso tipo IV, divididos aleatoriamente, para cada marca comercial de HR, em dois grupos com 5 modelos cada um (Grupo Controle). O HR foi fluidificado em forno de microondas de acordo com as instruções dos fabricantes e vertido no interior da mufla que continha o modelo de gesso. O molde era preenchido com revestimento de silicato de etila (REFRADEN® - Knebel Produtos Dentários Ltda.), e deste eram obtido os seus modelos refratários, respectivos a cada marca comercial. Esta metodologia foi repetida nos 15 ciclos de reutilização de cada HR. Os modelos refratários gerados pela 1a fluidificação, 5a, 10a e 15a reutilizações dos HRs, totalizando 40 modelos, foram mensurados em um microscópio mensurador (Mesuring Microscope STM - Olympus®). As médias foram submetidas à análise estatística pelos testes de Análise de Variância, Tukey e Dunnett, ao nível de 5% de significância. Os resultados evidenciaram que os modelos refratários obtidos pelo HR da marca VIPI® apresentaram alterações lineares em relação ao Grupo Controle, nas distâncias AB (1a fuidificação= -1,25% e 5a reutilização= -1,20%); AD (1a fluidificação=0,76%, 10a =0,65% e 15a =0,52% reutilizações); BD (1a fluidificação=0,58%). De acordo com os resultados obtidos, foi possível concluir que, mesmo havendo diferença significativa até 15 ciclos de reutilizações do HR, este fator não comprometeu à finalidade protética que se propõe o HR, gerando modelos de revestimento aceitáveis para ambas marcas comerciais investigadas / Abstract: The aim of this study was to evaluate linear alterations of refractories models obtained by 15 several cycles of heating using two reversible hydrocolloides (HR) (DUPLlCADOR VIPI® and DUPLlCADOR K27®).It was used a metallic master model with four defined points (A, B, C and D) which were linked to permit the measurement of the distances AB, BC, CD, DA, DB and AC. From this model, 10 stone models were obtained and separated in two groups randomized, according to the HR. After this, each model was duplicated with the same HR, according to the manufacturer. The mold was poured with ethyla silicate investment (REFRADEN® and so, the refractories models were obtained. By this methodology, each HR was used for 15 cycles. The respective refractories models obtained at the 1sth, 5th, 10th and 15thfluidification-geleification cycles were measured 3 times at a linear microscope (Mesuring Microscope STM - Olympus®. The averages of the distances were analyzed by ANOVA, Tukey and Dunnett testes (p<0.05).The results showed that the refractories models obtained by VIPI® HR had linear alterations when compared to stone models (control group) in distances AB (1st cycle= - 1.25% and 5th cycle=-1.20%); AD (1st cycle=0.76%, 10th=0.65% and 15th=0.52% cycles); BD (1st cycle=0.58%). According to the results, it can be concluded that although there is a significative difference after using HR for 15 cycles, it is irrelevant due to prosthetic use of HR when making investment model with both commercial types studied. / Mestrado / Protese Dental / Mestre em Clínica Odontológica

Le développement croissant de systèmes de stockages connectés au réseau électrique se voit stimulé par les problématiques de gestion de réseau liés entre autres à l'intégration croissante de technologies de production renouvelables. L'accumulation hydropneumatique d'énergie apparait comme une solution propre et économiquement intéressante dans le panel des technologies existantes. Cette étude analyse une configuration d'accumulation air-eau sans séparation, en cycle fermé et utilisant une pompe/turbine rotodynamique. Les principales problématiques en relation à ces choix techniques sont : les phénomènes de transfert de masse et de chaleur à l'interface air-eau, les caractéristiques de fonctionnement d'une machine hydraulique rotodynamique en régime d'opération variable et le rendement d'accumulation du système. Ces aspects sont traités ici par des approches locales dans certains cas, puis globales afin de pouvoir proposer un modèle de comportement dynamique du système de stockage pouvant faire l'objet de simulations rapides. Les aspects de modélisation ont été élaborés en parallèle au développement d'un banc d'essais de 45 kW réalisé dans le cadre de ce travail. Les observations expérimentales obtenues sur ce banc sont comparées aux résultats du modèle qui rend bien compte de la dynamique et de l'état énergétique du système. Des études d'amélioration du système sont engagées à la fin du document. Elles concernent d'une part la question de la flexibilité de fourniture de puissance et d'autre part le rendement d'accumulation du réservoir de stockage. / The present increasing development of storage systems connected to electrical network is stimulated by network management issues related to recent energetic landscape evolutions such as the increasing integration of renewable production sources. The hydro-pneumatic system seems to offer a clean and cheap energy storage solution among the set of existing storage technics. The present study analyses an air-water direct contact accumulation configuration, in closed cycle and using a rotodynamic pump/turbine. The main points of interest related to these technical choices are: the air-water interface mass and heat phenomena, variable operating point performances of a rotodynamic hydraulic machine and the overall efficiency of the storage device. These aspects are studied by, in some cases, a local approach, and then a global one in order to propose a dynamic behaviour model of the storage system suitable for rapid simulations. The modelling aspects were treated in parallel to the development of a 45 kW test rig built during this project. The experimental observations made on this test rig are compared to the modelling results that represent correctly the dynamics and energetic state of the system. At the end of this document, some studies for the improving of the power delivery flexibility and efficiency increasing of the accumulation element are engaged.

Digital watermarking of multimedia content has been proposed as a method for different applications such as copyright protection, content authentication, transaction tracking and data hiding. In this thesis, we propose a lossless watermarking approach based on Discrete Cosine Transform (DCT) for a new application of watermarking. A depth map obtained from a stereoscopic image pair is embedded into one of the two images using a reversible watermarking algorithm. Different from existing approaches which hide depth map in spatial domain, the depth information is hidden in the quantized DCT domain of the stereo image in our method. This modification makes the watermarking algorithm compatible with JPEG and MPEG-2 compression. After the investigation of the quantized DCT coefficients distribution of the compressed image and video, The bit-shift operation is utilized to embed the depth map into its associated 2D image reversibly for the purpose of achieving high compression efficiency of the watermarked image and/or video and high visual quality of stereo image and/or video after the depth map is extracted. We implement the proposed method to analyze its performance. The experimental results show that a very high payload of watermark (e.g. depth map) can be embedded into the JPEG compressed image and MPEG-2 video. The compression efficiency is only slightly reduced after the watermark embedding and the quality of the original image or video can be restored completely at the decoder side.