Dynamics of Spin Polarized Free Radicals in Polymeric and Photobiological Systems

本研究项目涉及自由基对动力学的基础研究及其在光生物学和聚合物化学中的应用。福布斯教授将开发一种方法来观察和分析单一氨基酸、短肽和蛋白质中的自旋极化现象。利用一种新的染料增感反应，他将表征几种氨基酸自由基阳离子和中性自由基，并研究它们的构象和化学动力学。在聚合物领域，一个主要问题将是确定大分子长程运动对时间分辨电子顺磁共振(TREPR)谱中局部测量的动态效应的影响程度。北卡罗来纳州超级计算中心将对有趣的胶束进行新的分子动力学模拟，并将合成新的光化学活性表面活性剂，以了解是否可以对随后的自由基扩散的起点进行控制。将利用增感剂和可见光对啤酒进行光化学降解方面的进一步工作。这项工作有可能影响整个饮料行业每年数百万美元的收入。有了这个奖项，国际科学和工程办公室的有机和高分子化学项目以及中欧和东欧项目继续支持北卡罗来纳大学教堂山分校的马尔科姆·D·E·福布斯教授的研究。福布斯教授的工作走在了光化学研究的前沿。他正在开发复杂的磁共振方法以及计算机建模，以获得关于几个重要化学系统的有价值的信息。

This research project deals with fundamental studies in radical pair dynamics with applications in photobiology and polymer chemistry. Professor Forbes will develop methodology for the observation and analysis of spin polarization phenomena in single amino acids, short peptides and proteins. Using a new dye sensitization reaction, he will characterize several amino acid radical cations and neutral radicals and investigate their conformational and chemical dynamics. In the polymer area, a major issue will be to determine the degree of influence of long range macromolecular motion on the locally measured dynamic effects in the time-resolved electron paramagnetic resonance (TREPR) spectra. New molecular dynamic simulations of interesting micelles will be carried at the North Carolina Supercomputing Center and new photochemically active surfactants will be synthesized to learn if control can be exerted over the starting point for diffusion of the ensuing free radicals. Further work will be done on the photochemical degradation of beer using sensitizers and visible light. This work has the potential to impact the entire multi-million dollar per year beverage industry.With this Award, the Organic and Macromolecular Chemistry Program and the Central and Eastern Europe Program in the Office of International Science and Engineering continues support for the research of Professor Malcolm D. E. Forbes of the University of North Carolina at Chapel Hill. Professor Forbes work is at the forefront of photochemical research. He is developing sophisticated magnetic resonance methods along with computer modeling to obtain valuable information on several important chemical systems.