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Structure, Dynamics and Reactivity of Novel Free Radicals in Supramolecular and Small Molecule Systems

$435,606FY2005MPSNSF

University Of North Carolina At Chapel Hill, Chapel Hill NC

Investigators

Abstract

The Organic and Macromolecular Chemistry Program supports Professor Malcolm D. E. Forbes at the University of North Carolina- Chapel Hill whose goal is to understand the structure, reactivity and molecular dynamics of novel free radicals in free solution and in confined media. Using time-resolved spectroscopic methods and a theoretical model developed previously, Professor Forbes will probe the diffusion of free radicals in micelles, reverse micelles, and vesicles. By creating and detecting spin correlated radical pairs in these confined media by time-resolved EPR spectroscopy and simulating their spectra using the "micro-reactor" model, they will be able to extract diffusion coefficients and exchange coupling parameters for a variety of supramolecular systems. Such data for free radicals is difficult to obtain by other methods at this level of precision. Professor Forbes will also create and detect novel free radicals from biologically relevant substrates such as the methionine radical cation, which is a suspect in the molecular basis for Alzheimer's disease and other neurological disorders. The Organic and Macromolecular Chemistry Program supports Professor Malcolm D. E. Forbes whose work will provide high-resolution magnetic resonance data for many biologically important free radicals, while at the same time, investigating their reactivity in small molecule systems. This work is important because there are hundreds of biochemical reaction pathways involving free radicals but they are often produced in such low concentrations or in frozen conditions that they are difficult to characterize in situ. Graduate students and postdocs carrying out this work will be exposed to many challenging areas of science, such as the spin physics of radical pairs. Professor Forbes' lab and projects are excellent training grounds for young scientists. The research results will be of interest to researchers in the fields of photochemistry, biochemistry, magnetic resonance and bio-mimetic chemistry.

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