Photogenerated o-Azaxylylenes: Mechanistic Studies and Synthetic Applications

This research sets out to build upon excited state o-azaxylylene cycloaddition. The mechanism behind the excitation and cycloaddition process of photogenerated o-azaxylylenes was determined experimentally. Time-correlated single-photon counting, steady-state spectroscopy, triplet quenching experiments, and quantum yield studies provided evidence suggesting that excited state intramolecular proton transfer is followed by intersystem crossing and stepwise addition to the tethered unsaturated pendant. In keeping with the principles of diversity oriented synthesis, a modular approach was taken to gain access to a diverse array of N,O,S-Polyheterocycles which were modified postphotochemically via Suzuki coupling to yield fused biaryls. Cycloaddition products, outfitted with halogens in the aromatic ring of the o-azaxylylene, proved to be reactive with a variety of boronic acids resulting in a rapid growth in structural complexity. A novel procedure was developed that utilized multiple o-azaxylylene cores in a photochemical cascade transformation yielding complex scaffolds of unprecedented topology. The photoprecursors were produced in a one-pot two-step sequence from commercially available starting materials, and upon irradiation yield structures containing up to five fused hetrocyclic rings, and showed complete diastereoselectivity.

Assessment of Natural and Manmade Materials in US Artificial Reef Programs

Natural coral reefs are in a state of serious decline worldwide. The pressures of over fishing, recreational activities, environmental pollutants, and global warming have stressed these marine ecosystems to the breaking point. One of the oldest methods of augmenting natural reef systems is the implementation of artificial reefs. These projects are not as simple as dumping waste or scrap materials in offshore areas. Proper material selection is vital to produce a healthy artificial marine habitat that is completed on schedule and on budget. This Capstone Project will evaluate the most commonly used materials and provide a comparison of their strengths and weaknesses. This comparison provides a valuable tool for project managers as they begin the reef planning process.

Developing an Interdependent Relationship between Preservation and Recreation: Managing Mountain Bicycling in National Parks

Increasing demand from mountain bikers for greater access to riding in National Park Service (NPS) units is driving the need for park managers to seriously look at the impacts from and feasibility of permitting this recreational use. Currently, NPS units that permit mountain bicycling do not have formal mountain bicycling management plans. An analysis of recreational policies and existing research was conducted to identify criteria for effective mountain bicycling management strategies. Criteria were developed for trail selection, establishment, use, closures and rehabilitation. Criteria were also developed for user education, participatory planning and monitoring. This study shows that the NPS needs formal mountain bicycling management plans that focus on the preservation of natural and cultural resources and consider the appropriateness of proposed recreational uses.