Method Development for the Stereoselective Synthesis of Heterocycles.

Efforts made to improve the scope of palladium-catalyzed carboetherification and carboamination reactions are illustrated herein, and strategies for overcoming various limitations to the method are discussed. As described in this thesis, the synthesis of bis-, fused- and poly-substituted tetrahydrofurans, 1,3-oxazolidines, benzopyrans and benzoxepines was achieved through the palladium-catalyzing coupling of γ-hydroxy alkenes, O-vinyl-1, 2-amino-alcohols, homoallylphenols and 2-(pent-4-en-1-yl)phenols with aryl and alkenyl halides. The synthesis of the aforementioned heterocycles represents a significant advancement in the methodology toward the synthesis of natural products, especially the annonaceous acetogenins. In Chapter 2, a novel strategy for the synthesis of bis- and fused-tetrahydrofurans is described. Sequential Pd-catalyzed carboetherification reactions were performed to yield bis- and fused-THFs, which enabled access into biologically active compounds such as the annonaceous acetogenins. As described in Chapter 3, the diastereoselectivity of Pd-catalyzed carboetherification reactions of substrates bearing internal alkenes was improved by employing S-Phos, an electron-rich, bulky monodentate biaryl ligand, which promoted reductive elimination and suppressed β-hydride elimination. As a result, poly-substituted tetrahydrofurans were produced in excellent diastereoselectivity, and biologically active compounds possessing this motif, such as Simplakidine A, a cytotoxic marine natural product, may be synthesized using the proposed methodology. In Chapter 4, the synthesis of 1,3-oxazolidines using a catalyst system based on S-Phos is described. The use of S-Phos promoted reductive elimination, which was disfavored due to the presence of electron withdrawing substituents on the substrate. Through the work described in this thesis, 1,3-oxazolidines, an important structural motif in organic synthesis, can be obtained using Pd-catalyzed carboamination reactions. A catalyst system composed of Pd2(dba)3/S-Phos also proved to be useful for the production of benzopyrans, which are common in antioxidants and were previously inaccessible through our methodology. As outlined in Chapter 5, the scope of the methodology was expanded to include homoallylphenols, highlighting the ability of the catalyst to overcome entropic effects and the low nucleophilicity of phenols. Heterocycles containing 6-membered rings were produced in a convergent manner, allowing access into motifs common in biologically active materials. In Chapter 6, the methodology was extended towards benzoxepines, enabling the synthesis of biologically relevant materials.Ph.D.ChemistryUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/91561/1/amanfran_1.pd

School Leadership and Equity : an examination of policy response in Scotland

In this paper we adopt a critical perspective on the implementation of policy on school leadership and equity in Scotland, viewing policy as both an attempt to solve problems and an attempt to persuade social actors to subscribe to particular beliefs that delineate action. We begin by offering a definition of “policy response”, and then examine how policy “conversations” establish consensus around such things as school leadership and equity. We examine Scottish policy on school leadership and equity and consider what practices this policy does, and does not permit. In so doing, our examination of the implementation of policy on school leadership and equity in Scotland acknowledges that such policy is in part extemporized, and in part the attempt to make inevitable a “de-stated” account of governance. We conclude by contextualising our forthcoming empirical study of the Leadership Standards for Social Justice in Scotlan

Soil P Status and Nitrogen Fixation on Organic Dairy Farms in Ontario and Nova Scotia

Legumes are a key source of nitrogen (N) in organic production systems. However, there is evidence that reduced inputs may be leading to deficient soil phosphorus (P) on some organic dairy farms (Roberts et. al. 2008). This may affect crop performance and N fixation in forage legumes. This study aims to gauge the relationship between soil P dynamics in organic dairy systems and legume biological nitrogen fixation (BNF). The study has two main sub-projects: 1. A field survey of soil-test P and legume forage productivity and N fixation on dairy farms in Ontario and Nova Scotia, Canada. 2. Growth chamber and greenhouse studies examining: a) The role of P nutrition in legume growth and N fixation, and b) The P-supplying power of composts, struvite, and a rock P source. Field data was commenced in the 2008 season, and was completed in 2009. Growth chamber and greenhouse studies were conducted in 2009. Analyses of 2009 samples are not complete at the report date

Measurement of Perceived School Climate for Active Travel in Children.

Objectives : To describe the development of an original scale that measures perceived school climate for active travel in fourth- and fifth-grade girls and boys. Methods : The data were analyzed using confirmatory factor analysis (CFA) to provide evidence of factorial validity, factorial invariance, and construct validity. Results : The CFA supported the fit of a 3-factor (encouragement, praise, and importance) correlated model for the school climate for active travel measure. This hierarchical model was invariant between sex and across a 7-month time period, and initial evidence for construct validity was provided. Conclusions : School climate for active travel is a measurable construct, and preliminary evidence suggests relationships with more support for active travel from friends and family

A comparative review of palliative care development in six countries represented by the Middle East Cancer Consortium (MECC)

Palliative care development and services were reviewed in the region represented by the six members of the Middle East Cancer Consortium: Cyprus, Egypt, Israel, Jordan, the Palestinian Authority, and Turkey. The multimethod review synthesized evidence from ethnographic field visits to inpatient units, home care hospice teams and free-standing hospices, including interviews with hospice and palliative care clinicians, administrators, volunteers, policy makers and academic researchers. Public health data and relevant literature were collated together with internet-accessed information on services and health care systems. A total of 69 services were located; two country members have a history of relatively sustained development of hospice and palliative care, but provision across the Middle East Cancer Consortium region is highly variable at a local level. Considerable barriers to service development were identified in a region already struggling with many military and political conflicts. Key problems are a lack of secure funds and government support, inadequate professional training programs, opioid phobia in professionals and the public, and a lack of awareness and understanding of palliative care needs at public, government, and professional levels. Key areas for further attention were increasing national and international professional training and public education programs, improving opioid legislation and health care policies, negotiating for secure government or health insurance funding provision, raising awareness about the need for pediatric services and for patients with other illnesses, as well as for those with cancer, and working to integrate palliative care into mainstream health service provision and education

Body Image and Body Mass Index: An Investigation of Preadolescent Low-Income, Urban Ethnic Minority Girls

Utilizing a sample of low-income, urban preadolescent African American and Latina girls, this study examined ethnic differences in two aspects of body image (i.e., body dissatisfaction and weight descriptions), and determined if this relation varied as a function of age. This study also examined the relation between the body image variables and self-esteem and BMI and self-esteem, and determined if these relations differed depending on age or ethnicity. Participants were recruited from 3rd through 5th grade at five Chicago Public Schools, and completed measures of body dissatisfaction, weight descriptions, self-esteem, and had their anthropometric measurements taken. Results showed that Latina girls experienced more body dissatisfaction than African American girls, while no differences emerged for weight descriptions. Body dissatisfaction was the only variable that was significantly related to self-esteem, and this relation was strongest for younger, Latina girls. Overall, older girls in the sample demonstrated higher self-esteem and decreased body dissatisfaction. These findings have important implications for developing prevention and intervention programs, and explanations for understanding these results are discussed

A Multi-Method Analysis of Body Mass Index, Physical Activity, and Executive Functions Among Urban Minority Girls

Recent evidence suggests that the summer months represent an especially vulnerable time of year for weight gain, inactivity, and cognitive decline, particularly among adolescent girls. To explore these issues, this study examined the relations between changes in physical activity (PA), body mass index (BMI), and executive functions (EFs) among a sample of sixty-eight, 10-to 14-year-old girls participating in a four-week, community-based summer camp. Objectively measured PA data (i.e., accelerometer), BMI measurements, and EF neuropsychological assessments were conducted prior to the first week of camp and during the last week of camp. Results revealed that girls increased in all measurements of PA, as well as maintained stable zBMI and BMI percentile across the camp. Findings related to the influence of PA on EFs were somewhat mixed, as increases in specific aspects of PA were related to both lower zBMI and improvement in inhibition skills at the end of camp, but poorer performance on the shifting and working memory tasks. Additionally, higher zBMI was associated with improved working memory performance for participants who demonstrated larger increases in PA throughout the camp. Findings suggest that summertime physical activity programs may be one cost-effective avenue through which policy makers and educators might intervene to buffer negative physical and cognitive health outcomes

Ranaviruses in North America: A Brief Review in Wild Herpetofauna

Ranaviruses are globally emerging pathogens of poikilothermic vertebrates. They affect over 40 species of amphibians in the USA and at least nine species in Canada. Additionally, ranaviruses have been found in at least eight species of reptiles in the USA and two species in Canada. Several of the species that are known to be affected are listed by state or federal agencies as they are of conservation concern (e.g., Cryptobranchus alleganiensis alleganiensis and Terrapene carolina carolina). In this brief review, we discuss the diversity and distribution, the species affected, the clinical signs of ranavirus disease (ranavirosis) that one would see in the field, morbidity and mortality events and their likely triggers, and conservation implications from the emergence of ranaviruses in populations of North American herpetofauna. We also would like to stress that ranaviruses are reportable infections in amphibians (according to the OIE, World Health Organization for Animals) and if an infection is suspected, the incident should be reported the proper authorities. Additionally, biosecurity measures should be taken to avoid the spread of ranaviruses between individuals and between field sites

The Biochemical and Pathophysiological Effects of Alcohol Consumption

While the stance of some conservative Christian (and other) groups advocating abstinence from alcohol intake may not be popular, contemporary research into alcohol and its effects on the body may lend weight to such a position. The consumption of alcohol, coupled with its addictive properties, can lead to a wide not only costly in medical terms but also in terms of domestic violence, accidents and antisocial behaviour. Alcohol is metabolised by the liver and this organ may be consequently damaged resulting in serious impairment of normal hepatic structure and function. Nearly all the physiological systems of the body are adversely affected by alcohol to varying degrees and the behavioural effects observed with intoxication are associated with compromised neurotransmitter functions in the brain and altered brain structure in the long term. Adverse consequences of alcohol intake may be evident in other systems including the cardiovascular, gastrointestinal, reproductive and immunological systems. There is an increased risk of atherosclerosis, cancers of the oral cavity, pancreatitis and immune system disturbances associated with prolonged alcohol intake. In pregnant women alcohol metabolism is reduced and as the developing foetus has lowered ability to metabolise blood alcohol compared to an adult there is an elevated risk of serious consequences associated with foetal alcohol syndrome. Despite the nearly overwhelming negative consequences of alcohol intake, the beneficial effects of drinking red wine linked to lowered heart disease despite a high fat diet (the ‘French Paradox’) may be associated with the antioxidants and other polyphenols also found in non-alcoholic red grape juice. Serious consideration of the effects of alcohol on the body should inform decisions on the intake of alcohol