I. Development of the In Situ Reductive Ozonolysis of Alkenes with Tertiary Amine N-Oxides. II. Progress toward the Asymmetric Synthesis of Peroxyplakoric Acid A3.

Ozone, first discovered in the mid 1800’s, is a triatomic allotrope of oxygen that is a powerful oxidant. For over a century, research has been conducted into the synthetic application and mechanism of reactions of ozone with organic compounds. One of the major areas of interest has been the ozonolysis of alkenes. The production of carbonyl compounds is the most common synthetic application of ozonolysis. The generally accepted mechanism developed by Rudolf Criegee for this reaction involves the 1,3-electrocyclic addition of ozone to the π bond of the alkene to form a 1,2,3-trioxolane or primary ozonide. The primary ozonide is unstable at temperatures above -100 °C and undergoes cycloreversion to produce the carbonyl oxide and carbonyl intermediates. These intermediates then recombine in another 1,3-electrocyclic addition step to form the 1,2,4-trioxolane or final ozonide. While the final ozonide is often isolable, most synthetic applications of ozonolysis require a subsequent reductive or oxidative step to form the desired carbonyl compound. During investigations into the nucleophilic trapping of the reactive carbonyl oxide, it was discovered that when amines were used as additives, an increased amount of reaction time was required in order to consume all of the starting material. Surprisingly, significant amounts of aldehydes and a suppression of ozonide formation also occurred which led to the discovery that amine N-oxides formed by the ozonation of the amine additives in the reaction were intercepting the carbonyl oxide. From the observed production of aldehydes, our proposed mechanism for the in situ reductive ozonolysis reaction with amine N-oxides involves the nucleophilic trapping of the carbonyl oxide intermediate to produce a zwitterionic adduct that fragments into 1O2, amine and the carbonyl thereby avoiding the formation of peroxidic intermediates. With the successful total syntheses of peroxyacarnoates A and D by Dr. Chunping Xu, the asymmetric total synthesis of peroxyplakorate A3 was investigated. The peroxyplakoric acids are cyclic peroxide natural products isolated from the Plakortis species of marine sponge that have been found to exhibit activity against malaria, cancer and fungi. Even though the peroxyplakorates differ from the peroxyacarnoates in the polyunsaturated tail and the head group, the lessons learned from the syntheses of the peroxyacarnoates have proven to be valuable in the asymmetric synthesis of peroxyplakorate A3. The challenges for the asymmetric synthesis of peroxyplakorate A3 include the stereospecific formation of the 3-methoxy-1,2-dioxane core with a propionate head group and the introduction of oxidation sensitive dienyl tail in the presence of a reduction sensitive 1,2-dioxane core. It was found that the stereochemistry of two of the chiral centers could be controlled by an anti-aldol reaction of a chiral propionate followed by the stereospecific intramolecular cyclization of a hydroperoxyacetal. The regioselective ozonolysis of a 1,2-disubstituted alkene in the presence of a terminal alkyne forms the required hydroperoxyacetal as a mixture of diastereomers. Finally, the dienyl tail is introduced by a hydrometallation/iodination of the alkyne to produce a vinyl iodide followed by a palladium catalyzed coupling reaction. While the coupling reaction was unsuccessful in these attempts, it is still believed that the intramolecular cyclization to introduce the 1,2-dioxane core could prove to be a general solution to many other cyclic peroxides natural products.

Medical Students' Attitudes Toward The Medical College Admission Test

The following study analyzed the attitudes held by pre-clinical medical students about the Medical College Admission Test or MCAT. One hundred and eighty first-year and second-year medical students at a public Midwestern medical university participated in this study. Participants completed the “Medical Students Attitudes toward the Medical College Admission Test” survey during their morning lectures near the end of their spring semester. A composite scale score of the Likert items of the survey was computed and the proportion of students with attitudes ranging from strongly agree to strongly disagree was calculated. For six of the twelve Likert items the largest proportion of participants disagreed with the statements about the MCAT and its use in the admission process and its applicability to their current medical education. Other questions included how participants prepared for the MCAT and if they completed each of the subsections were addressed as well. Future research could determine if attitudes between students accepted into medical school and those not accepted are drastically different. Advisor: Kurt F. Geisinger

SIDE EFFECTS OF PERSISTENT TOXICANTS

As you can see from the general tenor of the printed program for this seminar, I am in the unenviable position of trying to discourage you from certain types of chemical control; but my assigned topic "Side Effects of Persistent Toxicants," implies that mission. However, my remarks may be somewhat anticlimax at this time, because it is now generally conceded that we need to reevaluate certain chemicals in control work and to restrict or severely curtail use of those that per¬sist for long periods in the environment. So let me detail my reasons for a somewhat negative attitude toward the use of the persistent hydrocarbons from my experience with the effects of these materials on birds. But first a few words of caution about control work in general, which so often disrupts natural processes and leads to new and unforseen difficulties. As an example, I think of the irruption of mice in the Klamath valley in northern California and southern Oregon in the late '50's. Intensive predator control, particularly of coyotes, but also of hawks and owls, was followed by a severe outbreak of mice in the spring of 1958. To combat the plague of mice, poisoned bait (1080 and zinc phosphide) was widely distributed in an area used by 500,000 waterfowl each spring. More than 3,000 geese were poisoned, so driv¬ing parties were organized to keep the geese off the treated fields. Here it seems conceivable that the whole chain of costly events--cost of the original and probably unnecessary predator control, economic loss to crops from the mouse outbreak, another poisoning campaign to combat the mice, loss of valuable waterfowl resources, and man-hours involved in flushing geese from the fields--might have been averted by a policy of not interfering with the original predator-prey relationship. This points to a dilemma we always face. (We create deplorable situations by clumsy interference with natural processes, then seek artificial cures to correct our mistakes.) For example, we spend millions of dollars in seeking cures for cancer, but do little or nothing about restricting the use of known or suspected carcinogens such as nicotine and DDT.

Improving the Effectiveness of Independent Practice with Corrective Feedback

In this action research study of my 8th grade Algebra class, I investigated the effects of teacher-to-student written corrective feedback on student performance and attitude toward mathematics. The corrective feedback was given on solutions for selected independent practice problems assigned as homework. Each problem being assessed was given a score based on a 3- point rubric and additional comments were written. I discovered that providing teacher-to-student written corrective feedback for independent practice problems was beneficial for both students and teachers. The feedback positively affected the attitudes of students and teacher toward independent practice work resulting in an improved quality of solutions produced by students. I plan to extend my research to explore ways to provide corrective feedback to students in all of my mathematics classes.

Can homework become more meaningful with the inclusion of oral presentations?

In this action research study of my 7th grade math class, I investigated the inclusion of homework presentations to see if they would improve students’ attitude toward mathematics, participation, and understanding. I discovered that although the implementations of presentations into our homework routine did not drastically influence grades, or even improve attitudes (according to test grades and student surveys), a multitude of other changes surfaced. These changes consisted of an increase in discussion, a team effort among students in my class, and an overall “learning community” effect. I plan to continue to pursue presentations as a major part of my homework routine, and also incorporate presentations into review sessions.

The Role of Manipulatives in the Eighth Grade Mathematics Classroom

In this action research study of my classroom of eighth grade mathematics, I investigated the use of manipulatives and its impact on student attitude and understanding. I discovered that overall, students enjoy using manipulatives, not necessarily for the benefit of learning, but because it actively engages them in each lesson. I also found that students did perform better on exams when students were asked to solve problems using manipulatives in place of formal written representations of situations. In the course of this investigation, I also uncovered that student attitude toward mathematics improved when greater manipulative use was infused into the lessons. Students felt more confident that they understood the material, which translated into a better attitude regarding math class. As a result of this research, I plan to find ways to implement manipulatives in my teaching on a more regular basis. I intend to create lessons with manipulatives that will engage both hands and minds for the learners.

State of the Arctic October 2006

This State of the Arctic Report presents a review of recent data by an international group of scientists who developed a consensus on the information content and reliability. The report highlights data primarily from 2000 to 2005 with a first look at winter 2006, providing an update to some of the records of physical processes discussed in the Arctic Climate Impact Assessment (ACIA, 2004, 2005). Of particular note: • Atmospheric climate patterns are shifting (Fig. 1). The late winter/spring pattern for 2000–2005 had new hot spots in northeast Canada and the East Siberian Sea relative to 1980–1999. Late winter 2006, however, shows a return to earlier climate patterns, with warm temperatures in the extended region near Svalbard. • Ocean salinity and temperature profiles at the North Pole and in the Beaufort Sea, which changed abruptly in the 1990s, show that conditions since 2000 have relaxed toward the pre-1990 climatology, although 2001–2004 has seen an increase in northward ocean heat transport through Bering Strait (Fig. 2), which is thought to impact sea ice loss. • Sea ice extent continues to decrease. The sea ice extent in September 2005 was the minimum observed in summer during the satellite era (beginning in 1979), marking an unprecedented series of extreme ice extent minima beginning in 2002 (Fig. 3). The sea ice extent in March 2006 was also the minimum observed in winter during the satellite era. • Tundra vegetation greenness increased, primarily due to an increase in the abundance of shrubs. Boreal forest vegetation greenness decreased, possibly due to drought conditions (Fig. 4). • There is increasing interest in the stability of the Greenland ice sheet. The velocity of outlet glaciers increased in 2005 relative to 2000 and 1995, but uncertainty remains with regard to the total mass balance. • Permafrost temperatures continue to increase. However, data on changes in the active layer thickness (the relatively thin layer of ground between the surface and permafrost that undergoes seasonal freezing and thawing) are less conclusive. While some of the sites show a barely noticeable increasing trend in the thickness of the active layer, most of them do not. • Globally, 2005 was the warmest year in the instrumental record (beginning in 1880), with the Arctic providing a large contribution toward this increase. Many of the trends documented in the ACIA are continuing, but some are not. Taken collectively, the observations presented in this report indicate that during 2000–2005 the Arctic system showed signs of continued warming. However, there are a few indications that certain elements may be recovering and returning to recent climatological norms (for example, the central Arctic Ocean and some wind patterns). These mixed tendencies further illustrate the sensitivity and complexity of the Arctic physical system. They underline the importance of maintaining and expanding efforts to observe and better understand this important component of the climate system to provide accurate predictions of its future state.

Talent Management in Higher Education: Developing Emerging Leaders Within the Administration at Private Colleges and Universities

This research focused on identifying a series of successful practices relating to administrative talent management within the higher education setting. The field study included a thorough examination of seven small to mid-size private colleges and universities that have incorporated employee development strategies. These strategies were aimed at growing future leaders from within the organization in order to achieve continuity and support institutional priorities. Specifically, several focus areas were investigated including presidential vision, leadership commitment, talent management’s place among institutional priorities, program characteristics, and program evaluation. Among the commonalities that were gathered included support at the senior officer level who serve as advocates, mentors, and program facilitators, a strong connection between talent management and the institutions’ strategic plans, and a holistic approach to developing talent at all levels of the organizations. In addition, both coaching and opportunities for growth in the work environment were evident within several of the institutions. Also, academic leadership development was considered to be a part of the talent management strategy within three of the colleges and universities. The key differentiators included the incorporation of organizational and leadership competencies to provide focus toward the performance development process at two institutions, the implementation of a succession planning model at another institution, and the location of human resource generalists in departments across two of the institutions to identify learning opportunities for both individuals and work teams. Based on both the findings from the field study and the literature review, a comprehensive procedural model is introduced that serves to support human resource departments and higher education professionals, in general, who are looking to either begin or broaden their own talent management approach. However, despite the progress that has been made across several institutions noted throughout the research study, much more must be learned in terms of how the time and resources invested in talent management translates to institutional success. Advisor: James O‘Hanlon

Dispelling the Mascot Myth: The Misuse of Indigenous Peoples as Mascots in American Schools

This workshop details the deculturalization process that takes place when Indigenous Peoples are used as mascots in school-related activities; examines the arguments(s) and defensive tactics used by sports fans and school officials to maintain these hegemonic images; and offers successful strategies for developing policy toward the elimination of Indigenous Peoples as mascots.