Structure and Dynamics of Radical Intermediates in Biological Electron Transfer Reactions

在这个由化学系实验物理化学项目资助的奖项中，Judy E.加州大学圣地亚哥分校的Kim和她的研究生和本科生同事将研究在远程电子转移和催化反应中发挥重要作用的氨基酸自由基。特别的重点将放在芳香族残基色氨酸。这项研究的一个独特的方面是组装一套强大的光谱技术，包括皮秒时间分辨和紫外共振拉曼，瞬态吸收和电子顺磁共振，探测自由基中间体的结构和动力学。我们将探讨几个主题，例如蛋白质微环境和pH对自由基稳定性的作用，以及与自由基形成相关的动力学。这些研究的结果不仅将增强我们对生物自由基的理解，而且可能影响蛋白质模拟物和其他关键催化反应合成系统的设计。除了为学生提供参与跨学科研究的机会外，目前的提案还大力促进教学，培训和学习。本科和研究生教育将通过在这些项目中整合不同的学生得到支持。与社区和K-12学生的参与将促进化学和生物化学的UCSD部门和当地社区之间的密切关系的发展。总的来说，目前的研究和教育活动准备通过以下方式造福社会：（1）影响化学，生物学和物理学领域的电子转移反应的关键发现，以及（2）本科生和研究生以及社区成员的教育增强。

In this award, funded by the Experimental Physical Chemistry Program of the Chemistry Division, Prof. Judy E. Kim of the University of California, San Diego, and her graduate and undergraduate student colleagues will study amino acid radicals that play important roles in long-range electron transfer and catalytic reactions. Special focus will be placed on the aromatic residue tryptophan. A unique aspect of this research is the assembly of a suite of powerful spectroscopic techniques, including picosecond time-resolved and UV resonance Raman, transient absorption, and electron paramagnetic resonance, to probe the structures and kinetics of radical intermediates. Several topics will be explored, such as the role of the protein microenvironment and pH on radical stability as well as kinetics associated with radical formation.Results from these studies will not only enhance our understanding of biological radicals, but may impact the design of protein mimics and other synthetic systems for critical catalytic reactions. In addition to providing students with the opportunity to participate in interdisciplinary research, the current proposal strongly promotes teaching, training and learning. Undergraduate and graduate education will be bolstered through the integration of a diverse set of students in these projects. Involvement with the community and K-12 students will foster the development of a close relationship between the UCSD Department of Chemistry and Biochemistry and the local community. In general, the current research and education activities are poised to benefit society through (1) critical discoveries in electron transfer reactions that impact fields in chemistry, biology, and physics, and (2) educational enhancements for undergraduate and graduate students as well as community members.