Novel Cyclodextrin-Based and Electroactive Rotaxanes

新型环糊精基电活性轮烷

• 批准号: 9304262
• 负责人: Angel Kaifer
• 金额: $ 27.8万
• 依托单位: University of Miami
• 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: 1993-06-01 至 1996-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9304262&HistoricalAwards=false
• 关键词: Novel; Cyclodextrin; Based; Electroactive; Rotaxanes

The chemistry of rotaxanes will be pursued. Rotaxanes are supramolecules in which a bead is threaded by a linear subunit. Bead dissociation is sterically prevented by two bulky groups (stoppers) attached to both ends of the linear subunit. A substantial portion of this work will be done with rotaxanes in which cyclodextrins are used as the beads. This project will investigate the nature of the fundamental interactions leading to self-assembly of cyclodextrin-based ı3!rotaxanes and ı4!rotaxanes, structures with either two or three cyclodextrin beads, respectively. In a second aspect of the work, rotaxanes will be synthesized where the cyclodextrin bead completely encapsulates a redox-active group. These systems will allow an evaluation of the importance of solvent reorganization in electron transfer reactions. The third aspect of the work will investigate the possibility of electrochemically controlling the position of an electron acceptor bead encapsulated on a thread with two different donor stations. %%% This grant from the Organic Dynamics Program supports the work of Professor Angel K. Kaifer at the University of Miami. Large molecular systems will be prepared that are composed of a bead molecule which encapsulates a linear string molecule. Bulky groups will be placed at the ends of the string to prevent dissociation of the bead. The assembly process to form these large molecular systems will be studied. A particular portion of the string will be oxidized to generate a positive charge and the effect of the bead on this process will be evaluated in the context of solvation. Control of the movement of the bead along the string by oxidizing or reducing different stations on the string, and thereby changing charge at these stations, will be studied.

将研究轮烷的化学性质。轮烷是超分子，其中珠子由线性亚基串接。 连接到线性亚基两端的两个大基团（终止子）在空间上防止珠子解离。这项工作的很大一部分将使用轮烷来完成，其中环糊精用作珠子。该项目将研究导致基于环糊精的 3!轮烷和 4!轮烷（分别具有两个或三个环糊精珠的结构）自组装的基本相互作用的性质。在该工作的第二个方面，将合成轮烷，其中环糊精珠完全封装氧化还原活性基团。这些系统将允许评估电子转移反应中溶剂重组的重要性。这项工作的第三个方面将研究以电化学方式控制封装在具有两个不同供体站的线上的电子受体珠的位置的可能性。 %%% 有机动力学计划的这笔赠款支持迈阿密大学 Angel K. Kaifer 教授的工作。将制备由封装线性串分子的珠分子组成的大分子系统。庞大的基团将被放置在绳子的末端，以防止珠子解离。将研究形成这些大分子系统的组装过程。线的特定部分将被氧化以产生正电荷，并且珠子对此过程的影响将在溶剂化的背景下进行评估。 将研究通过氧化或还原串上的不同位置来控制珠子沿串的运动，从而改变这些位置处的电荷。