Macromolecular, Supramolecular, and Biological Free Radical Chemistry

在化学系有机动力学项目的支持下，北卡罗来纳大学教堂山分校化学系的马尔科姆·福布斯教授将研究大分子、超分子和生物光化学的几个新领域。特别是，福布斯教授试图了解随机和嵌段共聚物如何在溶液中降解，并探索新型主链聚合物自由基的动力学。还将合成和探索这些动力学的新的线性和循环模型，这些模型表现为随着温度的变化而变化的线宽。自由基的扩散将在新的超分子结构中进行探索，如多聚体、表面活性剂稳定的纳米晶体和基于二氧化碳的反胶束。基于微反模型的自旋相关自由基对理论的发展，以及对自由基结构的计算研究，将有助于推动新的实验和合成。最后，机制光生物学的两个项目将开始，(1)光系统II中质子耦合电子转移反应的模型系统的研究，以及(2)在人眼晶状体中发现的被称为犬尿氨酸的紫外线保护剂化合物的降解。北卡罗来纳大学教堂山分校的福布斯教授的研究将提供对自由基反应和光化学的基本理解，这对于解决能量存储(光系统II)以及生物自由基形成和破坏的影响等问题至关重要。这项拟议的研究结束了从这些事件的基础科学到解决重要的长期问题的循环。该研究培训研究人员小分子和聚合物合成、结构分析、光化学和激光光谱、磁共振(包括微波工程)、分子和大分子动力学、表面化学和计算化学。在美国，很少有实验室将所有这些活动都放在一个综合研究计划下进行，所有级别的学生都在定量物理有机化学的许多方面都有扎实的基础。福布斯教授继续在他良好的国际合作记录的基础上，与来自四个不同国家的研究人员在六个不同领域开展积极的项目。国内和国际的广泛合作使他的实验室成为与激进分子相关的基础研究的国际中心。

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Malcolm Forbes of the Chemistry Department at the University of North Carolina- Chapel Hill will investigate several new areas in macromolecular, supramolecular, and biological photochemistry. In particular, Professor Forbes seeks to understand how random and block copolymers degrade in solution, and to probe the dynamics of novel main chain polymeric free radicals. New linear and cyclic models for these dynamics, which manifest themselves as alternating line widths as a function of temperature, will also be synthesized and explored. Diffusion of free radicals will be probed inside new supramolecular structures such as polysomes, surfactant-stabilized nanocrystals, and CO2-based reverse micelles. Advances in the theory of mobile spin correlated radical pairs via the micro-reactor model, as well as computational studies on radical structures, will help drive new experiments and syntheses. Finally, two projects in mechanistic photobiology will begin, (1) investigation of model systems for proton-coupled electron transfer reactions in Photosystem II, and (2) the degradation of UV protectant compounds called kynurenines found in the human eye lens. Research by Professor Forbes at the University of North Carolina- Chapel Hill will provide a fundamental understanding of free radical reactions and photochemistry that is essential to addressing problems such as energy storage ( photosystem II) and the effects of biological radical formation and damage. The proposed research closes the loop from the basic science of these events to solving long term questions of great importance. The research trains researchers in small molecule and polymer synthesis, structural analysis, photochemistry and laser spectroscopy, magnetic resonance (including microwave engineering), molecular and macromolecular dynamics, surface chemistry, and computational chemistry. There are few laboratories in the U.S. where all of these activities take place under one umbrella research program and students at all levels are well prepared with a solid foundation in many aspects of quantitative physical organic chemistry. Professor Forbes continues to build on his strong track record for international collaboration, with active projects in six different areas with researchers from four different countries. Extensive collaborations both nationally and internationally make his laboratory an international center for basic radical-related research.