11 resultados para STRUCTURE-PROPERTY RELATIONS

em Digital Commons at Florida International University


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The Florida Everglades is a highly diverse socionatural landscape that historically spanned much of the south Florida peninsula. Today, the Florida Everglades is an iconic but highly contested conservation landscape. It is the site of one of the world's largest publicly funded ecological restoration programs, estimated to cost over $8 billion (U.S. GAO 2007), and it is home to over two million acres of federally protected lands, including the Big Cypress National Preserve and Everglades National Park. However, local people's values, practices and histories overlap and often conflict with the global and eco-centric values linked to Everglades environmental conservation efforts, sparking environmental conflict. My dissertation research examined the cultural politics of nature associated with two Everglades conservation and ecological restoration projects: 1) the creation and stewardship of the Big Cypress National Preserve, and 2) the Tamiami Trail project at the northern boundary of Everglades National Park. Using multiple research methods including ethnographic fieldwork, archival research, participant observation, surveys and semi-structured interviews, I documented how these two projects have shaped environmental claims-making strategies to Everglades nature on the part of environmental NGOs, the National Park Service and local white outdoorsmen. In particular, I examined the emergence of an oppositional white identity called the Gladesmen Culture. My findings include the following: 1) just as different forms of nature are historically produced, contingent and power-laden, so too are different claims to Everglades nature; 2) identity politics are an integral dimension of Everglades environmental conflicts; and 3) the Big Cypress region's history and contemporary conflicts are shaped by the broader political economy of development in south Florida. My dissertation concluded that identity politics, class and property relations have played a key, although not always obvious, role in shaping Everglades history and environmental claims-making, and that they continue to influence contemporary Everglades environmental conflicts.

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The Florida Everglades is a highly diverse socionatural landscape that historically spanned much of the south Florida peninsula. Today, the Florida Everglades is an iconic but highly contested conservation landscape. It is the site of one of the world’s largest publicly funded ecological restoration programs, estimated to cost over $8 billion (U.S. GAO 2007), and it is home to over two million acres of federally protected lands, including the Big Cypress National Preserve and Everglades National Park. However, local people’s values, practices and histories overlap and often conflict with the global and eco-centric values linked to Everglades environmental conservation efforts, sparking environmental conflict. My dissertation research examined the cultural politics of nature associated with two Everglades conservation and ecological restoration projects: 1) the creation and stewardship of the Big Cypress National Preserve, and 2) the Tamiami Trail project at the northern boundary of Everglades National Park. Using multiple research methods including ethnographic fieldwork, archival research, participant observation, surveys and semi-structured interviews, I documented how these two projects have shaped environmental claims-making strategies to Everglades nature on the part of environmental NGOs, the National Park Service and local white outdoorsmen. In particular, I examined the emergence of an oppositional white identity called the Gladesmen Culture. My findings include the following: 1) just as different forms of nature are historically produced, contingent and power-laden, so too are different claims to Everglades nature; 2) identity politics are an integral dimension of Everglades environmental conflicts; and 3) the Big Cypress region’s history and contemporary conflicts are shaped by the broader political economy of development in south Florida. My dissertation concluded that identity politics, class and property relations have played a key, although not always obvious, role in shaping Everglades history and environmental claims-making, and that they continue to influence contemporary Everglades environmental conflicts.

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Binary skutterudite CoSb3 nanoparticles were synthesized by solvothermal method. The nanostructuring of CoSb3 material was achieved by the inclusion of various kinds of additives. X-ray diffraction examination indicated the formation of the cubic phase of CoSb3. Structural analysis by transmission electron microscopy analysis further confirmed the formation of crystalline CoSb3 nanoparticles with high purity. With the assistance of additives, CoSb3nanoparticles with size as small as 10 nm were obtained. The effect of the nanostructure of CoSb3on the UV–visible absorption and luminescence was studied. The nanosized CoSb3 skutterudite may find application in developing thermoelectric devices with better efficiency. K

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This dissertation analyzes the obstacles against further cooperation in international economic relations. The first essay explains the gradual nature of trade liberalization. I show that existence of asymmetric information between governments provides a sufficient reason for gradualism to exist. Governments prefer starting small to reduce the cost of partner’s betrayal when there is sufficient degree of information asymmetry regarding the partner’s type. Learning about partner’s incentive structure enhances expectations, encouraging governments to increase their current level of cooperation. Specifically, the uninformed government’s subjective belief for the trading partner being good is improved as the partner acts cooperatively. This updated belief, in turn, lowers the subjective probability of future betrayal, enabling further progress in cooperation. The second essay analyzes the relationship between two countries facing two policy dilemmas in an environment with two way goods and capital flows. When issues are independent and countries are symmetric, signing separate agreements for tariffs (Free Trade Agreements-FTA) and for taxes (Tax Treaties-TT) provides the identical level of enforcement as signing a linked agreement. However, linkage can still improve the joint welfare by transferring the slack enforcement power in a case of asymmetric issues or countries. I report non-results in two cases where the policy issues are interconnected due to technological spillover effect of FDI. Moreover, I show that linking the agreements actually reduces enforcement when agreements are linked under a limited punishment rule and policy variables are strategic substitutes. The third essay investigates the welfare/enforcement consequences of linking trade and environmental agreements. In the standard literature, linking the agreements generate non-trivial results only when there is structural relation between the issues. I focus on institutional design of the linkage and show that even if environmental aspects of international trade are negligible linking the agreements might still have some interesting welfare implications under current GATT Rules. Specifically, when traded goods are substitutes in consumption, linking the environmental agreement with trade agreement under the Withdrawal of Equivalent Concession Rule (Article XXVIII) will reduce the enforcement. However, enforcement in environmental issue increases when the same rule is implemented in the absence of linkage.

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The current research considers the capacity of a local organic food system for producer and consumer empowerment and sustainable development outcomes in western Guatemala. Many have argued that the forging of local agricultural networks linking farmers, consumers, and supporting institutions is an effective tool for challenging the negative economic, environmental, and sociopolitical impacts associated with industrial models of global food production. But does this work in the context of agrarian development in the developing world? Despite the fact that there is extensive literature concerning local food system formation in the global north, there remains a paucity of research covering how the principles of local food systems are being integrated into agricultural development projects in developing countries. My work critically examines claims to agricultural sustainability and actor empowerment in a local organic food system built around non-traditional agricultural crops in western Guatemala. Employing a mixed methods research design involving twenty months of participant observation, in-depth interviewing, surveying, and a self-administered questionnaire, the project evaluates the sustainability of this NGO-led development initiative and local food movement along several dimensions. Focusing on the unique economic and social networks of actors and institutions at each stage of the commodity chain, this research shows how the growth of an alternative food system continues to be shaped by context specific processes, politics, and structures of conventional food systems. Further, it shows how the specifics of context also produce new relationships of cooperation and power in the development process. Results indicate that structures surrounding agrarian development in the Guatemalan context give rise to a hybrid form of development that at the same time contests and reinforces conventional models of food production and consumption. Therefore, participation entails a host of compromises and tradeoffs that result in mixed successes and setbacks, as actors attempt to refashion conventional commodity chains through local food system formation.^

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A two-year longitudinal study was conducted to investigate late adolescents in transition. An initial investigation with senior high school students assessed students prior to leaving home for college and after college entrance. Of the original 131 participants recontacted two years after their graduation, 78 returned surveys. The study (a) explored changes in social network structure and function, (b) determined whether late adolescent-parent-peer relations change over time, and (c) identified prospectively the impact of social support, adolescent-parent-peer relations, and attachment security on well-being and feelings about the transition after high school. Students attending college locally reported an increase in total network support at Time 2. Regardless of location, more support from friends was received after the transition from high school, whereas family support did not vary across time. Parent relations were closer after the transition and were predictive of various well-being measures and feelings about the transition from high school. ^

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Hydrophobicity as measured by Log P is an important molecular property related to toxicity and carcinogenicity. With increasing public health concerns for the effects of Disinfection By-Products (DBPs), there are considerable benefits in developing Quantitative Structure and Activity Relationship (QSAR) models capable of accurately predicting Log P. In this research, Log P values of 173 DBP compounds in 6 functional classes were used to develop QSAR models, by applying 3 molecular descriptors, namely, Energy of the Lowest Unoccupied Molecular Orbital (ELUMO), Number of Chlorine (NCl) and Number of Carbon (NC) by Multiple Linear Regression (MLR) analysis. The QSAR models developed were validated based on the Organization for Economic Co-operation and Development (OECD) principles. The model Applicability Domain (AD) and mechanistic interpretation were explored. Considering the very complex nature of DBPs, the established QSAR models performed very well with respect to goodness-of-fit, robustness and predictability. The predicted values of Log P of DBPs by the QSAR models were found to be significant with a correlation coefficient R2 from 81% to 98%. The Leverage Approach by Williams Plot was applied to detect and remove outliers, consequently increasing R 2 by approximately 2% to 13% for different DBP classes. The developed QSAR models were statistically validated for their predictive power by the Leave-One-Out (LOO) and Leave-Many-Out (LMO) cross validation methods. Finally, Monte Carlo simulation was used to assess the variations and inherent uncertainties in the QSAR models of Log P and determine the most influential parameters in connection with Log P prediction. The developed QSAR models in this dissertation will have a broad applicability domain because the research data set covered six out of eight common DBP classes, including halogenated alkane, halogenated alkene, halogenated aromatic, halogenated aldehyde, halogenated ketone, and halogenated carboxylic acid, which have been brought to the attention of regulatory agencies in recent years. Furthermore, the QSAR models are suitable to be used for prediction of similar DBP compounds within the same applicability domain. The selection and integration of various methodologies developed in this research may also benefit future research in similar fields.

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Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: (1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (E LUMO) via QSAR modelling and analysis; (2) to validate the models by using internal and external cross-validation techniques; (3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl ) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: (1) Linear or Multi-linear Regression (MLR); (2) Partial Least Squares (PLS); and (3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: (1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; (2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; (3) E LUMO are shown to correlate highly with the NCl for several classes of DBPs; and (4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

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In 2005 we initiated a project designed to better understand tree island structure and function in the Everglades and the wetlands bordering it. Focus was on the raised portions at the upstream end of the islands, where tropical hardwood species adapted to well-drained conditions usually are the most prominent component of the vegetation. The study design is hierarchical, with four levels; in general, a large number of sites is to be surveyed once for a limited set of parameters, and increasingly small sets of islands are to be sampled more intensively, more frequently, and for more aspects of ecosystem function. During the first year of the 3-year study, we completed surveys of 41 Level 1 (i.e., the least intensive level) islands, and established permanent plots in two and three islands of Levels 2 and 4 intensity, respectively. Tree species richness and structural complexity was highest in Shark Slough “hammocks”, while islands in Northeast Shark Slough and Water Conservation Area 3B, which receive heavy human use, were simpler, more park-like communities. Initial monitoring of soil moisture in Level 4 hammocks indicated considerable local variation, presumably associated with antecedent rainfall and current water levels in the adjacent marsh. Tree islands throughout the study area were impacted significantly by Hurricanes Katrina and Wilma in 2005, but appear to be recovering rapidly. As the project continues to include more islands and repeated measurements, we expect to develop a better grasp of tree island dynamics across the Everglades ecosystem, especially with respect to moisture relations and water levels in the adjacent marsh. The detailed progress report which follows is also available online at http://www.fiu.edu/~serp1/projects/treeislands/tree_islands_2005_annual_report.pd

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The aim of this work was to develop a new methodology, which can be used to design new refrigerants that are better than the currently used refrigerants. The methodology draws some parallels with the general approach of computer aided molecular design. However, the mathematical way of representing the molecular structure of an organic compound and the use of meta models during the optimization process make it different. In essence, this approach aimed to generate molecules that conform to various property requirements that are known and specified a priori. A modified way of mathematically representing the molecular structure of an organic compound having up to four carbon atoms, along with atoms of other elements such as hydrogen, oxygen, fluorine, chlorine and bromine, was developed. The normal boiling temperature, enthalpy of vaporization, vapor pressure, tropospheric lifetime and biodegradability of 295 different organic compounds, were collected from open literature and data bases or estimated. Surrogate models linking the previously mentioned quantities with the molecular structure were developed. Constraints ensuring the generation of structurally feasible molecules were formulated and used in commercially available optimization algorithms to generate molecular structures of promising new refrigerants. This study was intended to serve as a proof-of-concept of designing refrigerants using the newly developed methodology.

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Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: 1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (ELUMO) via QSAR modelling and analysis; 2) to validate the models by using internal and external cross-validation techniques; 3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: 1) Linear or Multi-linear Regression (MLR); 2) Partial Least Squares (PLS); and 3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: 1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; 2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; 3) ELUMO are shown to correlate highly with the NCl for several classes of DBPs; and 4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.