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

超分子和小分子体系中新型自由基的结构、动力学和反应性

• 批准号: 0518300
• 负责人: Malcolm Forbes
• 金额: --
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-09-01 至 2008-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0518300&HistoricalAwards=false
• 关键词: Structure; Dynamics; Reactivity; Novel; Free

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.

有机和高分子化学计划支持教授马尔科姆D。E.福布斯在北卡罗来纳州-查佩尔山的大学，其目标是了解结构，反应性和分子动力学的新自由基在自由溶液和限制介质。使用时间分辨光谱方法和理论模型开发以前，教授福布斯将探测自由基在胶束，反胶束和囊泡的扩散。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系统的扩散系数和交换耦合参数。在这种精确度下，很难通过其他方法获得自由基的此类数据。福布斯教授还将从生物相关底物中创造和检测新的自由基，如蛋氨酸自由基阳离子，这是阿尔茨海默氏病和其他神经系统疾病的分子基础的嫌疑人。E.福布斯的工作将提供高分辨率的磁共振数据，许多生物学上重要的自由基，而在同一时间，调查他们的反应，在小分子系统。这项工作很重要，因为有数百种涉及自由基的生化反应途径，但它们通常在低浓度或冷冻条件下产生，难以原位表征。进行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，例如自由基对的自旋物理学。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。研究结果将引起光化学、生物化学、磁共振和仿生化学领域研究人员的兴趣。