Macromolecular, Supramolecular, and Biological Free Radical Chemistry

在化学学部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Malcolm Forbes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，并探索新的主链聚合物自由基的动力学。这些动力学的新的线性和循环模型，表现为交替的线宽作为温度的函数，也将被合成和探索。自由基的扩散将在新的超分子结构中进行探索，如聚体、表面活性剂稳定的纳米晶体和基于二氧化碳的反胶束。通过微反应器模型的移动自旋相关自由基对理论的进展，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，将开始机械光生物学的两个项目，(1)研究光系统II中质子耦合电子转移反应的模型系统，(2)在人眼晶状体中发现的称为犬尿氨酸的紫外线防护化合物的降解。北卡罗莱纳大学教堂山分校的Forbes教授的研究将提供对自由基反应和光化学的基本理解，这对于解决诸如能量储存（光系统II）和生物自由基形成和损伤的影响等问题至关重要。拟议的研究完成了从这些事件的基础科学到解决非常重要的长期问题的循环。该研究培养了小分子和聚合物合成、结构分析、光化学和激光光谱学、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方面的研究人员。在美国，很少有实验室将所有这些活动都放在一个研究项目下进行，并且各级学生在定量物理有机化学的许多方面都有坚实的基础。福布斯教授继续建立他在国际合作方面的良好记录，与来自四个不同国家的研究人员在六个不同领域开展了积极的项目。国内外的广泛合作使他的实验室成为基础自由基相关研究的国际中心。

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.