Chapter 1: The unique chemical and biological properties of porphyrins have led to increased interest in the development of porphyrin-based materials. Metal organic frameworks (MOFs) can act as a scaffold for the immobilization of porphyrins in desired arrangements. The crystalline nature of MOFs allows for control over spatial arrangement of porphyrins and the local environment of the porphyrin molecules. This opens up the possibility of conducting systematic studies aimed at exploring structure-property relationships. Several strategies for the design and synthesis of porphyrin-based frameworks have been developed over the last two decades, such as, the pillared-layer strategy, construction of nanoscopic metal-organic polyhedrals (MOPs), post-synthetic modification, etc. These strategies provide an opportunity to engineer porphyrin-based MOFs that can target a specific application or serve as multi-functional assemblies. Porphyrin-based MOFs provide a tunable platform to perform a wide variety of functions ranging from gas adsorption, catalysis and light harvesting. The versatile nature of these frameworks can be exploited by incorporating them in multi-functional assemblies that mimic biological and enzymatic systems. Nano-thin film fabrication of porphyrin-based MOFs broadens their application range, making it possible to use them in the construction of photovoltaic and electronic devices. Chapter 2: The reaction of zirconium salts with meso-tetracarboxyphenylporphyrin (TCPP) in the presence of different modulators results in the formation of a diverse set of metal-organic frameworks (MOFs), each displaying distinct crystalline topologies. However, synthesis of phase-pure crystalline frameworks is challenging due to the concurrent formation of polymorphs. The acidity and concentration of modulator greatly influence the outcome of the MOF synthesis. By systematically varying these two parameters, selective framework formation can be achieved. In the present study, we aimed to elucidate the effect of modulator on the synthesis of zirconium-based TCPP MOFs. With the help of powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM), modulator candidates and the optimal synthetic conditions yielding phase-pure PCN-222, PCN-223 and MOF-525 were identified. 1H NMR analysis, TGA and N2 gas adsorption measurements were performed on select MOFs to gain insight into the relationship between their defectivity and modulator properties. Chapter 3: Singlet-singlet energy transfer in PCN-223(free-base), a highly stable Zr-MOF based on meso-tetrakis(4-carboxyphenyl)porphyrin was investigated, using diffuse reflectance spectroscopy, steady-state emission spectroscopy, time-correlated single photon counting (TCSPC) spectroscopy and nanosecond transient absorption spectroscopy. The effects of the surrounding media and temperature on the excited-state properties of PCN-223(fb) were explored to understand the mechanistic aspects of energy transfer. Stern-Volmer photoluminescence quenching of PCN-223(fb) suspensions was performed to extract quenching rate constants and gain insight into the efficiency of energy transfer. Chapter 4: The fourth chapter of this thesis is adapted from chapter 14 of the book "Elaboration and Applications of Metal-Organic Frameworks" authored by Jie Zhu, Shaunak Shaikh, Nicholas J Mayhall and Amanda J Morris. This chapter summarizes the fundamental principles of energy transfer in MOFs and provides an overview of energy transfer in lanthanide-Based luminescent MOFs, Ru/Os-Based MOFs, porphyrin- and metalloporphyrin-based MOF materials, and nonporphyrinic, organic chromophore-based MOFs. / Master of Science / Metal Organic frameworks (MOFs) composed of Zirconium-oxo clusters connected through meso-tetra(4-carboxyphenyl)porphyrin (TCPP) linker molecules have emerged as promising solid-state materials because of their unique structural features and diverse applications. Although these MOFs have demonstrated great potential over the years, synthesizing them in phase-pure form has proven to be very challenging as they are susceptible to polymorphism. Syntheses of these frameworks often result in phase mixtures and have poor reproducibility. To address, this issue, we conducted a systematic exploration of the synthetic parameter landscape to identify reaction conditions for the synthesis of phase-pure Zirconium-based porphyrin MOFs, and to gain deeper insights into the factors governing the formation of these MOFs. We also investigated the defectivity of pristine Zr-TCPP MOFs using a variety of techniques, including 1H NMR spectroscopy, thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry (ICP-MS), and Nitrogen gas adsorption/desorption measurements. The long-term goal of this project is to use phase-pure Zr-based porphyrin MOFs as model systems to study energy transfer in three dimensional structures. To achieve this goal, we characterized the photophysical properties of PCN-223(fb) (a Zr-based porphyrin MOF) using a variety of techniques including steady-state photoluminescence spectroscopy, time-resolved photoluminescence spectroscopy, nanosecond transient absorption spectroscopy and femtosecond transient absorption spectroscopy. Understanding the mechanistic aspects of energy transfer in PCN-223(fb) can pave the way for the design of a new generation of solar energy conversion devices.

Metastable β titanium alloys stand out as prominent candidates for structure materials in aerospace industries due to their light weight and exceptional high strength. This dissertation systematically investigates the microstructural evolutions in the metastable β Ti-5Al-5Mo-5V-3Cr (wt. %, Ti5553) alloy induced by various defects including grain boundary, twin boundary, and dual-phase interface using advanced characterization techniques such as transmission Kikuchi diffraction (TKD), 3D FIB-SEM tomography, and 4D STEM. Firstly, the morphology of grain boundary α precipitates was characterized using quantitative 3D FIB-SEM tomography combined with 3D phase field simulation. Our findings highlighted the critical role of the inclination angle between habit plane of α and grain boundary plane in determining the morphology of grain boundary α precipitates. Secondly, the nanoscale substructures of a novel high-indexed {10 9 3} twin and its influence on the formation of hierarchical α microstructure were studied, employing conventional TEM and aberration-corrected STEM. Thirdly, the early stage α nucleation in Ti-5553 was studied utilizing interrupted heat treatments and ex-situ characterizations via TEM and aberrationcorrected STEM. Our findings indicated that the preformed β/ω interface can act as nucleation sites for α precipitates. Lastly, the microstructure and defects in the direct energy deposited (DEDed) Ti-5553 alloy were investigated. The results demonstrate that the addition of stainless steel 316L can significantly refine the grain size while also introducing different defects.

Suspensões coloidais de microesferas de poliestireno carregadas proporcionam um sistema experimental excelente para estudar muitos problemas em física da matéria condensada. Sob condições apropriadas as partículas nessas suspensões podem se auto-organizar em um cristal com ordem de longo alcance, o chamado cristal coloidal. Neste trabalho apresentamos resultados de simulações por Dinâmica Molecular relacionados a defeitos pontuais, vacâncias e interstícios, em um cristal coloidal 2D. Calculamos a energia de formação e a interação destes defeitos pontuais, mostrando que um interstício é mais provável de ser criado do que uma vacância e que a interação entre os defeitos (vacância-vacância e interstício-interstício) é atrativa. Em conjunto esses resultados apontaram que os defeitos pontuais podem afetar o mecanismo de fusão do cristal coloidal 2D. Com relação à dinâmica dos defeitos, o foco foi sobre as vacâncias. Calculamos as entalpias de migração deste defeito de uma forma original, baseada na troca de topologias. Concluímos que a vacância não difunde de acordo com um único mecanismo, mas sim um misto de dois comportamentos, são eles: relação de Arrhenius corrigida e relação de potência com a temperatura. Calculamos também as entalpias e entropias relativas de formação das topologias da vacância, o que possibilitou identificar as topologias mais estáveis. Acreditamos que esses resultados serão importantes para trabalhos experimentais envolvendo interfaces e superfícies sólidas. / Colloidal suspensions of charged polystyrene microspheres provide an excellent experimental system to study many problems in condensed matter physics. Under appropriate conditions the particles in these suspensions organize themselves in a long-range-ordered crystal, the so-called colloidal crystal. In this thesis we report Molecular Dynamics simulations on point defects, vacancies and interstitials, in a 2D colloidal crystal. We have calculated the formation energy and interaction of these point defects, as well as the energy barriers between the various topological configurations that the defects may adopt while in thermal equilibrium. It is shown that the interstitials are more likely to be formed than the vacancies, and the interaction between defects (vacancy-vacancy and interstitial-interstitial) is attractive. Taken together, these results indicate that point defects may affect the melting process of a 2D colloidal crystal. With regard to the dynamics of the defects, emphasis was placed on the vacancies. The enthalpy for migration of a vacancy was calculated on the basis of exchanges between topologies. We concluded that the vacancy does not diffuse according to a single mechanism, but rather through a mixture of two processes: one is a modified Arrhenius mechanism and the other is represented by a power-law dependence on the temperature. We also calculated the relative enthalpies and entropies associated with the formation of the different topologies of vacancies, which allowed identification of the most stable topologies. We believe these results may have important bearing on experimental works involving interfaces and solid surfaces.

O presente trabalho tem como objetivo o estudo das invalidades dos atos processuais no processo civil. Para isso, é destacado que as formas processuais são importantes, por conceder previsibilidade e organização ao procedimento, porém é certo que elas não representam um fim em si mesmo, já que o processo tem como escopo principal a entrega da prestação jurisdicional de forma célere, justa e eficaz. Nesse sentido, o trabalho identifica os atos processuais dentro do contexto geral dos atos jurídicos, todavia iluminados pelas regras de sobredireito processual: o princípio da instrumentalidade, o princípio do prejuízo, o princípio do interesse e a regra da presunção de validade dos atos. Assim, após a análise das sistematizações mais importantes feitas pela doutrina acerca das invalidades no processo civil, o trabalho destaca os passos cognitivos de um juízo de invalidação, testados em algumas das invalidades cominadas. Por fim, são apresentados alguns vícios da sentença e as suas peculiaridades. / The dissertation explores the invalidity of procedural acts in Brazilian civil procedure. In that sense, while underscoring that procedural form is important, providing predictability and organization to the proceedings, it does not represent an end in and of itself, since the main goal of civil justice is to give a definitive resolution to the dispute in a manner thatnnis timely, just and efficient. Down this path, the dissertation qualifies procedural acts within the general framework of legal acts, but subject to meta-rules of civil procedure: the principle of its instrumental role, the harmless error test (pas de nullité sans grief), the identification of the protected interest and the presumption in favor of validity. After analyzing the most important doctrinal constructions on the topic, the dissertation proposes a framework to organize the cognitive steps of judgments on invalidity of procedural acts, tested and applied in connection with nullity cases. Lastly, the dissertation classifies defects relating to judgments and their peculiarities.

Disruptions in folate metabolism are known to increase the risk for neural tube defects (NTD) and this is preventable by folic acid supplementation. However, the relationship between folate metabolism and cardiac development remains unclear. The interaction between other folate pathway nutrients, choline and riboflavin, and folate metabolism was studied in a murine model of methylenetetrahydrofolate reductase (MTHFR) deficiency. Maternal choline deficiency, riboflavin deficiency and MTHFR deficiency adversely affected embryonic or heart development. The promoters of MTHFR were also examined for interactions with GATA-4, TBX5, MEF2A and NKX-2.5, known transcription factors of cardiac development. Upstream promoter activity was increased in the presence of GATA-4 and this interaction was further enhanced upon the addition of MEF2A. TBX5 appeared to decrease upstream promoter activity. GATA-4 modestly increased downstream promoter activity. These results highlight the importance of adequate nutrient intake during pregnancy and provide a link between folate metabolism and cardiac development.

The research objectives for this project were to explicitly define the anchor bolt corrosion problem in the state of Georgia and recommend action to the Georgia Department of Transportation. The bearing assembly of concern is the plate bearing assembly, in which carbon steel and/or bronze plates are anchored by either carbon steel or stainless steel anchor bolts. Inspection report data revealed that anchor bolt corrosion was ubiquitous for all environments in Georgia; the problem was reported for 27% of the steel girder bridges throughout the state. Based on a synthesis of the field investigations, bolt failure analyses, laboratory experimental testing, and review of GDOT inspection report surveys, the corrosion of carbon steel anchor bolts is caused universally by concentration cell corrosion. Other corrosion mechanisms of concern are galvanic and crevice corrosion, which are both enhanced by the current bearing design. Corrosion protection provided through zinc galvanization cannot sufficiently protect the carbon steel bolt for its entire service life. Corrosion potential and cyclic polarization data confirmed that ASTM Type 304, Type 316, Type 2101, and Type 2205 were protected from concentration cell and localized corrosion in the simulated bearing environment. Therefore, it is recommended that the stainless steel anchor bolts of these types be use in future designs and that the bolts should be electrically separated from all dissimilar metals using a Nylon or Teflon washer to prevent preferential corrosion of carbon steel. It is further recommended that the bronze lube plate should be eliminated entirely and that the bearing type should be a reinforced elastomeric bearing. Maintenance of existing sliding plate bearings should include regular cleaning by brushing away debris from the bearing surfaces, and bridges with carbon steel anchor bolts should be retrofitted to provide additional lateral restraint according to current maintenance procedures.

Suspensões coloidais de microesferas de poliestireno carregadas proporcionam um sistema experimental excelente para estudar muitos problemas em física da matéria condensada. Sob condições apropriadas as partículas nessas suspensões podem se auto-organizar em um cristal com ordem de longo alcance, o chamado cristal coloidal. Neste trabalho apresentamos resultados de simulações por Dinâmica Molecular relacionados a defeitos pontuais, vacâncias e interstícios, em um cristal coloidal 2D. Calculamos a energia de formação e a interação destes defeitos pontuais, mostrando que um interstício é mais provável de ser criado do que uma vacância e que a interação entre os defeitos (vacância-vacância e interstício-interstício) é atrativa. Em conjunto esses resultados apontaram que os defeitos pontuais podem afetar o mecanismo de fusão do cristal coloidal 2D. Com relação à dinâmica dos defeitos, o foco foi sobre as vacâncias. Calculamos as entalpias de migração deste defeito de uma forma original, baseada na troca de topologias. Concluímos que a vacância não difunde de acordo com um único mecanismo, mas sim um misto de dois comportamentos, são eles: relação de Arrhenius corrigida e relação de potência com a temperatura. Calculamos também as entalpias e entropias relativas de formação das topologias da vacância, o que possibilitou identificar as topologias mais estáveis. Acreditamos que esses resultados serão importantes para trabalhos experimentais envolvendo interfaces e superfícies sólidas. / Colloidal suspensions of charged polystyrene microspheres provide an excellent experimental system to study many problems in condensed matter physics. Under appropriate conditions the particles in these suspensions organize themselves in a long-range-ordered crystal, the so-called colloidal crystal. In this thesis we report Molecular Dynamics simulations on point defects, vacancies and interstitials, in a 2D colloidal crystal. We have calculated the formation energy and interaction of these point defects, as well as the energy barriers between the various topological configurations that the defects may adopt while in thermal equilibrium. It is shown that the interstitials are more likely to be formed than the vacancies, and the interaction between defects (vacancy-vacancy and interstitial-interstitial) is attractive. Taken together, these results indicate that point defects may affect the melting process of a 2D colloidal crystal. With regard to the dynamics of the defects, emphasis was placed on the vacancies. The enthalpy for migration of a vacancy was calculated on the basis of exchanges between topologies. We concluded that the vacancy does not diffuse according to a single mechanism, but rather through a mixture of two processes: one is a modified Arrhenius mechanism and the other is represented by a power-law dependence on the temperature. We also calculated the relative enthalpies and entropies associated with the formation of the different topologies of vacancies, which allowed identification of the most stable topologies. We believe these results may have important bearing on experimental works involving interfaces and solid surfaces.

O presente trabalho tem como objetivo o estudo das invalidades dos atos processuais no processo civil. Para isso, é destacado que as formas processuais são importantes, por conceder previsibilidade e organização ao procedimento, porém é certo que elas não representam um fim em si mesmo, já que o processo tem como escopo principal a entrega da prestação jurisdicional de forma célere, justa e eficaz. Nesse sentido, o trabalho identifica os atos processuais dentro do contexto geral dos atos jurídicos, todavia iluminados pelas regras de sobredireito processual: o princípio da instrumentalidade, o princípio do prejuízo, o princípio do interesse e a regra da presunção de validade dos atos. Assim, após a análise das sistematizações mais importantes feitas pela doutrina acerca das invalidades no processo civil, o trabalho destaca os passos cognitivos de um juízo de invalidação, testados em algumas das invalidades cominadas. Por fim, são apresentados alguns vícios da sentença e as suas peculiaridades. / The dissertation explores the invalidity of procedural acts in Brazilian civil procedure. In that sense, while underscoring that procedural form is important, providing predictability and organization to the proceedings, it does not represent an end in and of itself, since the main goal of civil justice is to give a definitive resolution to the dispute in a manner thatnnis timely, just and efficient. Down this path, the dissertation qualifies procedural acts within the general framework of legal acts, but subject to meta-rules of civil procedure: the principle of its instrumental role, the harmless error test (pas de nullité sans grief), the identification of the protected interest and the presumption in favor of validity. After analyzing the most important doctrinal constructions on the topic, the dissertation proposes a framework to organize the cognitive steps of judgments on invalidity of procedural acts, tested and applied in connection with nullity cases. Lastly, the dissertation classifies defects relating to judgments and their peculiarities.

One of the first embryonic structures generated during early human development is the neural tube. The embryonic process of neurulation, including neural tube closure, is necessary for proper brain and spinal cord development, whereas improper closure leads to neural tube defects including anencephaly, spina bifida, and craniorachischisis. The mechanism by which these defects occur is unknown, but some evidence suggest that redox disruption may play a role. Cellular redox state is important in regulating key processes during neural tube closure, including differentiation, proliferation, gene expression, and apoptosis. This study aims to determine whether redox potential shifts and these key processes are affected similarly or differentially after treatment with three neural tube defect-inducing developmental toxicants: ceramide (C2), valproic acid (VPA), and fumonisin (FB1). Using the P19 cell model of neurogenesis, in both undifferentiated and terminally differentiated cells, we analyzed glutathione (GSH) redox (Eh) potential to evaluate the effect of each toxicant over time. We show that in C2 and VPA treated cultures an oxidizing shift occurs, but interestingly, FB1 treatment results in a reducing shift in embryonic GSH Eh as compared to untreated cultures. Using the chick embryo model, comparable redox shifts were observed as were seen in P19 cells, supporting similarity between the models. To better understand how differential shifts in the redox state can result in similar defects, we then examined potential variances in neuronal differentiation and cellular proliferation, survival, metabolism, adhesion, and gene expression under each treatment. We report changes to cellular and embryonic endpoints that support dysmorphogenesis, likely the result of oxidizing or reducing stress that altered redox state. These results support the need for broad comparative analyses such as this to determine whether toxicants that cause the same types of defects, whether NTDs or others, act through similar or different mechanisms. This can better inform preventative measures used to reduce the risk and occurrence of birth defects.

The purpose of this quantitative study was to examine data describing nitrate concentration and cases of congenital cardiac defects. Residents with private wells and other stakeholders need data to make informed environmental decisions about the adverse health implications of nitrate contamination of private well water. Researchers have examined the exposure of nitrate in contaminated groundwater, but they have not examined nitrate levels in unregulated water systems. This gap in the literature highlighted the need to provide nitrate data for future research and private well users. Guided by the social ecological model, a quantitative, cross-sectional, nonexperimental design was used to survey 231 adult participants about community perceptions of stakeholders' collaboration about groundwater and the sustainability of private water wells. Multiple linear regression was used to test the hypotheses. Survey results showed that gender, age group, and distance from animal waste sites or farmland were associated with barriers to community collaboration to achieve groundwater sustainability. Use of private wells for irrigation and distance from animal waste sites or farmland were associated with community members' perceptions of community collaboration to achieve groundwater sustainability. Community perceptions and barriers to stakeholders' collaboration were not affected by any demographic factors. The data will facilitate the design and implementation of effective public health outreach services for private well users. The implications for positive social change include increased understanding of stakeholders' perceptions of private well nitrate contamination and reduction of the risk factors for birth defects.