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

有机和大分子化学项目支持北卡罗来纳大学教堂山分校的Malcolm D. E. Forbes教授，他的目标是了解自由溶液和受限介质中新型自由基的结构、反应性和分子动力学。利用时间分辨光谱方法和先前开发的理论模型，Forbes教授将探测自由基在胶束、反胶束和囊泡中的扩散。通过时间分辨EPR光谱在这些受限介质中创建和检测自旋相关自由基对，并使用“微反应器”模型模拟它们的光谱，他们将能够提取各种超分子体系的扩散系数和交换耦合参数。这种关于自由基的数据很难用其他方法在这种精度水平上得到。福布斯教授还将从生物学相关的底物中创造和检测新的自由基，如蛋氨酸自由基阳离子，这是阿尔茨海默病和其他神经系统疾病的分子基础。有机和大分子化学项目支持Malcolm D. E. Forbes教授，他的工作将为许多生物学上重要的自由基提供高分辨率的磁共振数据，同时，研究它们在小分子系统中的反应性。这项工作很重要，因为有数百种生化反应途径涉及自由基，但它们通常在低浓度或冷冻条件下产生，难以原位表征。从事这项工作的研究生和博士后将接触到许多具有挑战性的科学领域，例如基对的自旋物理学。福布斯教授的实验室和项目是培养年轻科学家的绝佳场所。研究结果将对光化学、生物化学、磁共振和仿生化学等领域的研究人员产生重要影响。

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.