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  • Qin, Jun (University of Vermont. Dept. of Chemistry, 2003-05
      Chiral a-branched amines are important components found within many diverse classes of biologically active natural products, designed pharmaceuticals and chiral building blocks. The study in the synthesis of chiral a-branched amines continues to be the focus of the methodology advancements due to their biological importance. In this dissertation, design and synthesis of novel chiral N-acylhydrazones and their applications in chiral a-branched amine and natural product synthesis are presented. Chiral N-acylhydrazones derived from N-aminooxazolidinone underwent intermolecular radical additions mediated by Bu3SnH. Simple secondary and tertiary radicals afforded N-acylhydrazine addition product in excellent stereocontrol in all cases in the presence of ZnCl2. Reduction of ketone acylhydrazones by Bu3SnH provided product hydrazines in high yield and moderate stereoselectivity. It was also found that Mn2(CO)10-mediated stereoselective intermolecular radical addition of different alkyl halides, including primary and difunctional alkyl iodides to different chiral hydrazones upon irradiation. Mn2(CO)10-mediated radical addition reactions tolerated additional functionality in either reactant, enabling hybrid radical-ionic annulation. Application of this methodology to natural product synthesis was demonstrated by an effective asymmetric synthesis of coniine and a synthetic approach to quinine.
  • Herrera, Ingrid (University of Vermont. Dept. of Psychology, 2004-04
      Historically, society's concept of violence and victimization has focused on assaults occurring between acquaintances and strangers. Yet, it is well known today that a woman's greatest risk of assault is not from strangers, but from intimates. Furthermore, domestic violence is a highly significant social problem that affects more than 4.4 million women in this country every year. Given the importance of domestic violence in society, the most troubling and predominant failing in the literature is the fact that much of the research takes into account only physical violence, ignoring the multidimensionality of the domestic abuse experience for many women. In reality, domestic violence towards women generally involves additional forms of harm, including psychological and sexual abuse by their partners. One fact that has been well established in the domestic violence literature is that women who have been abused by their partners are at significantly increased risk for psychological, health, and trauma-related problems. However, there is considerable variability among these women in the effects that they experience. It is important to investigate factors that may account for a woman's ability to cope, as well strategies that have been helpful in mediating the negative effects of trauma, which could be useful clinically in treating women who are in relationships characterized by domestic violence. This dissertation, a study of women currently or recently in battering relationships, explored these issues. The participants consisted of 58 women who were currently in or had recently left (within the past six months) a relationship characterized by domestic abuse, and who were not currently in treatment or in living in shelters. They were recruited through newspaper advertisements and community fliers. The results of the study showed that domestic abuse has multiple components - physical, sexual, and psychological - and that sexual and psychological abuse were related to negative physical and psychological health outcomes for women who were currently in or had recently left their relationship. Physical abuse was not found to be related to psychological or physical health outcomes for either group. Although the total amount of abuse a woman experienced was not found to be important in the psychological adjustment and physical health of these women, women who stayed in the relationship had more physical and psychological symptoms, such as depression, anxiety, post-traumatic stress disorder and physical health problems, than those who had left. Three types of coping strategies (cognitive restructuring, social support, and disengaged coping) were significantly related to physical and mental health outcomes, particularly for women who were still in the relationship, with cognitive restructuring and social support predicting more positive outcomes, and disengaged coping predicting more negative ones.
  • Henkin, Joshua Adam (University of Vermont. Dept. of Biology, 2004-03
      Proteomics, the wide scale characterization of protein products from a genome, is a new field of study that describes the qualitative and quantitative differences between two states of a cell, tissue or organism. One of the major challenges in the field of proteomics is to identify proteins and examine their binding interactions. The overall goal of this dissertation was to characterize the Drosophila indirect flight muscle (IFM) proteomes in wild-type and mutant strains through one and two dimensional gel electrophoresis, mass spectrometry and muscle mechanics. Drosophila IFM is an excellent model for this type of research because specific proteins from the IFM can be altered by a mutation while preserving the viability of the fly. The effect of these mutations can be studied in vivo and characterized to identify putative protein-protein interactions (PPI). Chapter I reviews traditional and modern methods used to identify PPI with an emphasis on techniques that permit the identification of PPI via high throughput technology. The concept of mutational proteomics is introduced as an approach for utilizing Drosophila IFM as a model for examining functional PPI by comparing proteomes of different IFM mutants to monitor how a mutation affects the expression of other proteins in the proteome. Proteome analysis was accomplished by gel separation followed by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry for protein identification. Chapter 2 describes a simple method enhancement that reduces the number of non sample masses submitted to database search engines used to identify proteins. This technique improved the significance of 6 out of 10 control sample identifications as well as 7 out of 16 Drosophila IFM putative protein identifications. The method described in Chapter 2 was used extensively in Chapter 3, which details a proteome wide analysis of IFM myofibrillar proteins from wild-type and two mutant Drosophila strains, actin null (Act88FKM88) and myosin null (Mhc7). In the wild-type myofibrillar proteome, 22 of the 28 detected proteins were identified and compared to proteins expressed in mutant proteomes to determine the effect of those specific mutations on the proteome. This data was used to test the currently accepted theory that mutations in thick filaments do not affect thin filament assembly and vice versa. The results indicated that the mutations might exert a wider range of changes in the proteome than previously expected. Results from this study also revealed many putative PPI in need of further analysis and confirmation via direct binding assays. Chapter 4 examines the functional implications of a specific PPI detected between myosin and flightin. Sinusoidal analysis was performed on skinned IFM fibers from wild-type and mutant Drosophila strains. This revealed that flies lacking flightin had significantly reduced passive stiffness, dynamic stiffness and power output, thus, demonstrating the significance of the flightin-myosin interaction in the IFM.
  • Puryear, Kristen (University of Vermont. Dept. of Botany, 2004-05
      Executive Summary Grassland birds are declining throughout most of their range. As a result, artificial habitats such as the agricultural fields of Vermont's Champlain Valley have been identified as important for grassland bird conservation. In order to address the regional and statewide concerns about grassland bird populations, Audubon Vermont has recognized two Important Bird Areas (IBAs) in the Champlain Valley, Dead Creek and Little Otter Creek. Audubon Vermont has also proposed the development of a Landscape-Level Important Bird Area Complex that would encompass these two IBAs and contribute to regional grassland bird conservation efforts as they are developed by the North American Bird Conservation Initiative and Partners in Flight. In the summer of 2003 I surveyed grassland birds in the two IBAs to assess the effects of agricultural management on breeding success. I also developed a habitat model that identifies the best potential habitat for grassland birds in the Champlain Valley , to help Audubon Vermont develop a strategy towards landscape-level grassland bird conservation. The following considerations for Audubon Vermont summarize my findings. For additional information about each consideration, please refer to the associated chapter, noted below. Grassland Bird Inventory (Chapter 1) Develop and implement a more extensive Upland Sandpiper monitoring program within Dead Creek and Little Otter Creek Important Bird Areas (IBAs) that will assess breeding success on an annual basis. Regularly monitor the same fields using a method that can detect breeding success (such as behavior mapping with a reproductive index [Vickery et al. 1992] or nest searching), which can provide information on breeding success, demographics, and responses to field management. Broadcasting surveys could be used as a supplemental tool for identifying additional survey fields and previously undetected individuals, and to help measure abundance. Monitor fields within the IBAs more than once during the breeding season to increase ,the chance of detecting rare species, assess breeding success, and help detect whether fields are ecological traps or sinks. Share field inventory results with the Vermont Department of Fish and Wildlife to help inform future revisions to their management plans for Dead Creek and Little Otter Creek Wildlife Management Areas (WMAs). Breeding Success and Field Management (Chapter 2) To maximize the potential for young to fledge, encourage a delay of mowing on hayfields until at least July 15, but preferably August 1. The later date will help protect species that fledge late or are attempting a second clutch after a failed nest attempt. On pastures being managed for grassland birds, encourage the reduction of stocking densities and delayed pasturing until July 15. Encourage a delay of mowing the pasture for forage until after July 15 (preferably August 1). Gather data on the day-to-day mowing trends within the two week period from late June to early July and on farmers needs for forage cut at that time. Assess the costs and benefits to the farmer and the grassland birds of delaying mowing for a few additional days during this critical breeding stage. Grassland Bird Survey Methods ( Chapter 3) If the monitoring objective is to calculate density, abundance and species richness values for grassland bird species, then point count surveys are recommended as a time efficient and informative method. This method is capable of detecting relative differences between survey areas. If the monitoring objective is to collect as much information as possible regarding species richness (i.e., detecting less abundant species or individuals that are sitting on nests and would likely be missed by a stationary observer), to detect breeding- related activity or breeding success, or to monitor trends as they change through the breeding season or with field management, then behavior mapping using a reproductive index (Vickery et al. 1992) is recommended as the most useful and potentially informative method. This is a reliable method for recording the progress of birds through the stages of breeding behavior (when compared with ground-truthed nest data), and provides a better approximation of bird abundance (when compared to point counts, which survey a smaller area). Landscape Level Grassland Bird Conservation Area (Chapter 4) The zones that are mapped as the "best" potential habitat should be ground- truthed in order to test the accuracy of the Scored Grassland Bird Habitat Map, and 1) verify that the mapped conditions currently exist (i.e., landcover type or amount of edge), and 2) test the assumptions made in terms of what constitutes the best habitat for grassland birds in the Champlain Valley. Gaps in knowledge of grassland bird distribution should be addressed, especially for species that could serve as focal species (Upland Sandpiper) or are rare and will require extra attention for management and protection (Grasshopper Sparrow and Sedge Wren). To enhance monitoring, land protection, management, and advocacy for grassland birds, a collaborative effort between interested organizations and agencies will be important. Collaborate with The Nature Conservancy of Vermont to create a strategy for grassland bird conservation that does not conflict with future Valley Clayplain Forest restoration. To maximize the potential for maintaining grassland bird species richness, abundance, number of breeding pairs, and potential for protecting species with large area requirements, consider protecting a complex of fields that together provide at least 50 ha but preferably 200 ha of habitat. Adjust the size, location, and management of protected fields according to species, population, or habitat conservation goals as those goals are developed. Consider the costs and benefits of locating grassland bird conservation efforts in heavily agricultural areas, where economic needs for higher productivity and intense field management decrease the chance that birds will breed successfully. Consider locating grassland bird conservation efforts in less agricultural areas that still contain suitable habitat but may be surrounded by land that is managed with less intensity. Less productive or wet fields should also be considered, as they are less likely to be managed as intensively. Within these areas, alternative farming practices (such as delayed mowing) may be more practical and more accepted by landowners and conservation organizations. Combining Grassland Bird and Marsh Bird Conservation (Chapter 5) Address the habitat needs of both grassland and marsh bird species by protecting and managing land where their habitat overlaps, such as upland fields that are adjacent to marshes.
  • Unknown author (2004-10-12

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