Agriculture is the backbone of the Haitian economy and provides employment 80% employment to the Haitian population (Lundahl, 1992). Also 85% of people in rural areas generate money from agricultural activities (IFAD, 2008). In the rural areas, men and women participate in agricultural production. However, the women play a vital role in the whole process starting from land preparation to crop sale (Gaspard, 2013). The Haitian women, despite of their function in crop productions (Dor, 2016), face different health issues, which have influence over Haitian agricultural system. Therefore, the research purposed was to investigate the impact of women heath issues on agricultural production Fondwa. A qualitative case study was used to investigate ten women farmers in the community of Fondwa, which is a small farming area in southwest part of Haiti. An interview questionnaire was used for data collection. Findings of the study showed that the women's contribution to farming is vital for promoting agricultural production, and they face different health issues that are linked to the environment and water pollution. Lastly, the women health problems influence agricultural production in the Fondwa area by preventing them from doing their daily agricultural activities, which have a direct impact over family and country's income. / MSLFS

La fonctionnalisation tardive de molécules (Late stage functionalization – LSF) offre l’opportunité d’explorer l’espace chimique plus efficacement, en particulier en considérant les liaisons C-H aromatiques comme des points potentiels de diversification pour générer de nouveaux analogues directement en une seule étape au lieu de faire une synthèse totale dite de novo. La fonctionnalisation directe de composés élaborés peut en particulier se faire en utilisant la technologie superacide comme démontré par les nombreux travaux du professeur Jacquesy. L’un des meilleurs exemples de cette stratégie est certainement la transformation directe de la vinorelbine (Navelbine®) par fluoration en conditions superacides pour conduire à son analogue difluoré (Vinflunine), commercialisé par les laboratoires Pierre Fabre comme agent anticancéreux Javlor®. C’est dans ce contexte que ce travail de thèse a porté sur le développement de nouvelles méthodes de fonctionnalisation directe de composés aromatiques azotés.Il s’agissait effectivement de développer de nouveaux outils de synthèse en conditions superacides afin :1. d’hydroxyler directement des composés aromatiques par voie électrophile;2. d’halogéner des composés aromatiques azotés allant d’anilines simples à des composés élaborés naturels ou de synthèse;3. d’appliquer ces méthodes à la synthèse de molécules marquées par des isotopes stables. / Late-stage functionalization can now be considered as a synthetic tool of choice to create molecular diversity, especially in a medicinal chemistry context. For example, aromatic C-H bonds can be regarded as functional groups and points of potential diversification to generate new analogs of a lead structure without resorting to de novo synthesis.The direct functionalization of elaborated compounds can also be done using superacid chemistry as demonstrated by the previous work of professor Jacquesy. One of the best examples of this strategy is certainly the direct transformation of vinorelbine (Navelbine®) by fluorination in superacid conditions to lead to its difluorinated analogue (Vinflunine), marketed by Pierre Fabre laboratories as an anticancer agent Javlor®.In this context, these studies focused on the development of new methods for the direct functionalization of aromatic nitrogen containing compounds.In particular, this work aimed at developing new synthetic tools in superacid for:1. the direct hydroxylation of aromatic compounds;2. the halogenation of aromatic nitrogen compounds from simple anilines to naturally occurring or synthetic compounds;3. the synthesis of labelled compounds with stable isotopes.

Every year more than 72,000 adolescents and young adults (AYAs) in the United States (US) aged 15-39 years are diagnosed with cancer. AYAs represent a population that falls into a care gap between pediatric and adult medical services. Additionally, AYAs have experienced increased cancer incidence and decreased five-year survival rates compared to other age groups. The spectrum of tumors seen in AYAs differs from children and older adults, with 90% of the tumors stemming from ten cancer types. Melanoma of the skin, characterized by the uncontrolled growth of pigment-producing cells, is the third most common cancer diagnosed among AYAs in the US. Overexposure to ultraviolet (UV) radiation from sunlight or artificial sources is the greatest risk factor for melanoma. AYAs seem to be particularly at risk for developing melanoma due to increased UV exposure early in life. This study’s objectives were to understand the unique characteristics of melanoma in AYAs in Tennessee and identify the predictors of late- stage diagnosis. The sample for this study includes all incident melanoma cancer cases (N=1109) in AYAs from the Tennessee Cancer Registry (TCR) for the years 2004-2008, inclusive. AYA cases were defined as cancer cases that were diagnosed in individuals ages 15-39 years, inclusive. Melanoma cases were defined according to the International Classification of Diseases- Oncology (ICD-O-3) site codes C440-C449. Melanoma cases that had a specified stage at diagnosis were included for final analysis (N= 315). Stage of diagnosis was determined through the SEER Summary Stage 2000 variable and coded into in situ, localized, and combined regional & distant stage. Univariate and multivariate analyses were performed for the following predictor variables: insurance status (private insurance vs. other), age group (5- year groups), and sex (male vs. female). The majority of the sample was white (96.5%), female (63.8%), had private insurance (85%) and was diagnosed with localized stage melanoma (69.4%). Individuals with government insurance were eight times more likely to be diagnosed with late stage melanoma compared to individuals with private insurance (OR 8.4, CI 3.0-23.3, p < 0.01). AYAs in the 15-19 year old age group were six times more likely to be diagnosed with late stage melanoma compared to 35-39 year olds (OR 6.3, CI 1.7-22.9, p=0.01). Females were 57% less likely to be diagnosed with late stage melanoma compared to males (OR 0.53, CI 0.30-0.93, p < 0.05). These findings indicate that individuals with government insurance may not receive adequate melanoma screening and preventative care compared to individuals with private insurance. While females were less likely to be diagnosed with late stage melanoma, females have a much greater risk of being diagnosed with melanoma at any stage. Finally, the increased risk of late stage diagnosis in the 15-19 year old age group may be associated with greater UV exposure from indoor and outdoor tanning. These data suggest the need for targeted cancer awareness and control activities specific to AYAs. Future studies are needed to explore the variations in late stage diagnosis of melanoma in AYAs in Tennessee.

The natural product celastrol (1) possesses a wide array of promising biological activities related to diseases characterized by protein misfolding including those associated with neuronal degradation, inflammation, and cancer. Relevant to cancer, celastrol functions as a non-ATP-competitive inhibitor of heat shock protein-90, providing a potential lead for the development of new inhibitors with improved pharmacology. A laboratory preparation of the small molecule was undertaken to provide access to the unnatural enantiomer of celastrol. The lack of understanding of the chemistry and biology of the growing class of celastroids is attributed to the incompatibility of biologically inspired polyene cyclization strategies to assemble friedelin triterpenoids. As a result of these problems residing at the interface of chemistry and biology, a purely synthesis-based strategy for polyene cyclizations to rapidly construct the pentacyclic core of the friedelin and celastroid natural products has been developed. This efficient strategy is gram scalable culminating in the first total synthesis of wilforic acid (127) and an advanced intermediate capable of delivering celastrol (1) as well as numerous celastroid natural products. Phenols possess broad utility serving as key materials in all facets of chemical industries, especially the pharmaceutical industry. The ideal synthesis of a phenolic compound entails the direct oxidation of an aryl C-H bond remains to be a difficult synthetic challenge. Following our initial report describing the hydroxylation of arenes using phthaloyl peroxide, new peroxide derivatives were investigated to probe their reactivity in an effort to hydroxylate aromatics which were previously unreactive. Electronically poor to moderately rich arenes were successfully hydroxylated with a broad functional group tolerance using 4,5-dichlorophthaloyl peroxide. This protocol has been applied toward the rapid synthesis of phenolic analogs and metabolites of current pharmaceuticals as well as biocides. Mechanistic studies using kinetic isotope effect, competition, and benzylic oxidation experiments indicate that a novel diradical reverse-rebound mechanism is the likely pathway. Further examination of the transition-state using linear free energy relationships with sigma vs. sigma+ values established a linear trend with a low negative rho value (- 3.92) corresponding best using sigma values supporting a diradical reverse-rebound addition. / text

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Base flow recession curve during a dry period is a distinct hydrologic signature of a watershed. The base flow recession analysis for both streamflow and spring flow has been extensively studied in the literature. Studies have shown that the recession behaviors during the early stage and the late stage are different in many watersheds. However, research on the transition from early stage to late stage is limited and the hydrologic control on the transition is not completely understood. In this dissertation, a novel cumulative regression analysis method is developed to identify the transition flow objectively for individual recession events in the well-studied Panola Mountain Research Watershed in Georgia, USA. The streamflow at the watershed outlet is identified when the streamflow at the perennial stream head approaches zero, i.e., flowing streams contract to perennial streams. The identified transition flows are then compared with observed flows when the flowing stream contracts to the perennial stream head. As evidenced by a correlation coefficient of 0.90, these two characteristics of streamflow are found to be highly correlated, suggesting a fundamental linkage between the transition of base flow recession from early to late stages and the drying up of ephemeral streams. At the early stage, the contraction of ephemeral streams mostly controls the recession behavior. At the late stage, perennial streams dominate the flowing streams and groundwater hydraulics governs the recession behavior. The ephemeral stream densities vary from arid regions to humid regions. Therefore, the characteristics of transition flow across the climate gradients are also tested in 40 watersheds. It is found that climate, which is represented by climate aridity index, is the dominant controlling factor on transition flows from early to late recession stages. Transition flows and long-term average base flows are highly correlated with a correlation coefficient of 0.82. Long-term average base flow and the transition flow of recession are base flow characteristics at two temporal scales, i.e., the long-term scale and the event scale during a recession period. This is a signature of the co-evolution of climate, vegetation, soil, and topography at the watershed scale. The characteristics of early and late recession are applied for quantifying human impacts on streamflow in agricultural watersheds with extensive groundwater pumping for irrigation. A recession model is developed to incorporate the impacts of human activities (such as groundwater pumping) and climate variability (such as evapotranspiration) on base flow recession. Groundwater pumping is estimated based on the change of observed base flow recession in watersheds in the High Plains Aquifer. The estimated groundwater pumping rate is found consistent compared with the observed data of groundwater uses for irrigation. Besides streamflow recession analysis, this dissertation also presents a novel spring recession model for Silver Springs in Florida by incorporating groundwater head, spring pool altitude, and net recharge into the existing Torricelli model. The results show that the effective springshed area has continuously declined since 1988. The net recharge has declined since the 1970s with a significant drop in 2002. Subsequent to 2002, the net recharge increased modestly but not to the levels prior to the 1990s. The decreases in effective springshed area and net recharge caused by changes in hydroclimatic conditions including rainfall and temperature, along with groundwater withdrawals, contribute to the declined spring flow.

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