Exploitation of Primitive Molecular Recognition Effects in Electron Transfer Reactions

电子转移反应中原始分子识别效应的开发

• 批准号: 9303682
• 负责人: Joseph Hupp
• 金额: $ 21.87万
• 依托单位: Northwestern University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-06-15 至 1997-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9303682&HistoricalAwards=false
• 关键词: Exploitation; Primitive; Molecular; Recognition; Effects

Professor Hupp of Northwestern University will investigate the effects of molecular recognition on electron transfer rates with support from the Inorganic, Bioinorganic, and Organometallic Program. He plans to probe two fundamental aspects of electron transfer reactions, one being the molecular aspects of the solvation barrier, the other being the influence of the intervening medium on the donor/acceptor electronic coupling strength. He will conduct four classes of experiments to assess these issues. 1) Crown ethers in solution will bind to D/A complexes, and this binding will simulate the molecular aspects of solvation. 2) Donors and acceptors will be trapped inside hemicarcerands, and the influence on bimolecular electron transfer will likewise simulate the molecular aspects of solvation. 3) D/A complexes where the bridging ligand is a crown ether or related moiety will be examined vis-a-vis their binding of cations; this will give information on the effects on coupling strength. 4) D/A complexes will be examined as a function of the conformation of the bridging ligand;this will give information about gated electron transfer and it will help in the interpretation of the studies in part 3. The general outcome of these studies will be an enhanced understanding of how electron transfer over long distances is affected by the intervening and surrounding media. %%% One of the major types of chemical reaction is electron transfer from one atom to another. This can even occur over long distances, when the two atoms are separated because they reside in bulky molecules, or because they reside in remote sites within the same molecule. Under such circumstances the rates of electron transfer are quite sensitive to the intervening medium and also to the surrounding solvent. Experiments to gain a general understanding of these effects will be undertaken by examining electron transfer in molecules that have been designed specifically for this purpose. In particular, aspects of "molecular recognition" will be investigated. Molecular recognition means that the specific structural features of one molecule will cause it to bind to another molecule in a highly controlled way; this binding will then lead to effects on the rates that can be directly attributed to known aspects of the bound molecule.

西北大学的Hupp教授将研究 分子识别对电子转移速率的影响 在无机、生物无机和 组织者方案。 他计划探索两个基本的 电子转移反应的各个方面，其中之一是分子 溶剂化障碍的方面，另一个是影响 供体/受体电子上的介入介质 耦合强度 他将进行四节课的实验 来评估这些问题。 1)溶液中的冠醚会结合 D/A复合物，这种结合将模拟分子 溶剂化的方面。 2)捐赠者和接受者会被困住 以及对双分子生物学的影响 电子转移同样会模拟分子方面 溶剂化。 3)D/A络合物，其中桥连配体是 冠醚或相关部分将被检查，维斯它们的 阳离子的结合;这将提供有关影响的信息 耦合强度。 4)D/A复合物将作为一种 桥连配体的构象的功能;这将 提供有关门控电子转移的信息，这将有助于 第三部分研究的解释。 总 这些研究的结果将是加强对以下方面的了解： 电子在长距离上的转移是如何受到 介入和包围媒体。 %%% 化学反应的主要类型之一是电子 从一个原子转移到另一个原子。 这甚至可以发生在 当两个原子分开时， 存在于庞大的分子中，或者因为它们存在于遥远的 在同一分子中。 在这种情况下， 电子转移的速率对 中间介质以及周围的溶剂。 实验以获得对这些效应的一般理解 将通过研究分子中的电子转移来进行 专门为此而设计。 在 特别地，“分子识别”的方面将被 研究了 分子识别意味着特定的 一个分子的结构特征会导致它与 另一种分子以高度受控的方式结合;这种结合将 然后导致对利率的影响， 归因于结合分子的已知方面。