Mechanisms of Electrode Reactions

该项目属于分析和表面化学的一般领域，以及电化学反应动力学的子领域。将研究几种截然不同的修饰电极体系的电化学性质，包括聚合物和粘土薄膜修饰电极、有序分子组装和脱氧核糖核酸(DNA)体系。电化学方法将被用来研究小分子的结构、电荷和极性如何影响它们与DNA的相互作用，并尝试选择性地切割DNA链。基于能够在极低温度下工作的新型惰性溶剂(例如液体二氧化硫)的电解液将被用来产生以前没有制备过的超氧剂。为了了解结构变化和分子内相互作用对氧化还原电位的影响，还将研究在电子转移上表现出较大构象变化的有机金属物种和包含多个电活性基团的有机金属物种的反应的动力学和能量学。本研究项目涉及作为分析工具的电化学方法的持续发展及其在化学问题中的应用。电化学分析方法对更普遍使用的光谱方法起到补充作用，并提供对电子转移过程的动力学和电化学反应的氧化还原电位的特殊洞察。

This project is in the general area of analytical and surface chemistry and in the subfield of electrochemical reaction dynamics. The electrochemical properties of several widely different modified electrode systems will be investigated, including electrodes modified with polymer and clay films, organized molecular assemblies, and deoxyribonucleic acid (DNA) systems. Electrochemical methods will be used to investigate how the structure, charge and polarity of small molecules affect their interactions with DNA and to attempt selective cleavage of the DNA strand. Electrolytes based on novel inert solvents capable of operation at very low temperatures, e.g., liquid sulfur dioxide, will be used to generate superoxidizing agents that have not previously been prepared. The kinetics and energetics of reactions of organometallic species that exhibit large conformational changes on electron transfer and those that contain multiple electroactive groups will also be studied in order to gain information about the effects of structural changes and intramolecular interactions on oxidation-reduction potential. This research project is concerned with the continued development of electrochemical methods as analytical tools and their application to chemical problems. Electrochemical methods of analysis play a complementary role to the spectroscopic methods more generally used and provide special insight into the kinetics of electron transfer processes and the oxidation-reduction potentials of electrochemical reactions.