Organic fluorine in solid-state [2+2] photocycloadditions

Abstract

Supramolecular chemistry is the branch of chemistry concerned with the interplay between individual molecular assemblies and intermolecular bonds, i.e. "chemistry beyond the molecule." Nature utilizes highly directional forces to influence and achieve the formation of complex structures and architectures (proteins, enzymes, etc.). Mimicking nature, chemists can capitalize on such forces to successfully engineer functional artificial materials. To further understanding, the MacGillivray research group utilizes principles of supramolecular chemistry to construct targeted organic and metal-organic solid materials, for the purpose of conducting chemical transformations. Solid-state synthesis (i.e. conducting chemical transformations in a solid, as opposed to a liquid or gas) has emerged as a means to achieve the formation of molecular targets that are often inaccessible via solution phase synthesis. We have developed a template strategy that can facilitate carboncarbon bond formation ([2+2] photodimerization) in a solvent-free environmenteliminating the need for petroleum-based solvents. Although the template-directed strategy has helped circumvent certain problems associated with conducting reactions in solids, the solid state is still not routinely used for synthesis, owing, in part, to a lack of expansion to multifunctional olefins and molecular targets. My research focuses on incorporating fluorine into solid-state [2+2] photodimerizations. viii TABLE OF CONTENTS LIST OF TABLES.

F8 haplotype and inhibitor risk: results from the Hemophilia Inhibitor Genetics Study (HIGS) Combined Cohort

“…Typing was completed for all but 7.1% of the markers. An EM algorithm [11,12] was used to infer haplotypes for individuals with missing information. Individuals with missing genotypes were assigned the haplotype that demonstrated the highest posterior probability.…”