MOLECULAR ENCAPSULATION AND ELECTRON TRANSFER

分子封装和电子转移

• 批准号: 0848637
• 负责人: Angel Kaifer
• 金额: $ 68万
• 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: 2009
• 资助国家: 美国
• 起止时间: 2009-05-15 至 2014-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0848637&HistoricalAwards=false
• 关键词: MOLECULAR; ENCAPSULATION; ELECTRON; TRANSFER

The Organic and Macromolecular Chemistry Program in the Chemistry Division at the National Science Foundation supports Professor Angel E. Kaifer at the University of Miami, who will study the relationship and interplay between molecular structures and electron transfer reactions. This proposal is aimed at elucidating fundamental questions related to electron transfer (ET) reactions and how the ET rates are affected by a host in supramolecular systems. This is a major continuing effort of previous work to better understand electron transfer reactions that occur within noncovalent encapsulated redox centers. By using a redox active guest and a suitable host, the resulting inclusion complex is a structure in which the redox center is partially or completely encapsulated by the host cavity. It may be viewed as analogous to biological host-guest macromolecular systems. These experiments will seek to understand quantitative and qualitative changes in reactivity of encapsulated molecules, such as reorganization energy rates and related thermodynamic parameters. Specific objectives are to i) investigate ferrocene and its derivatives in various cucurbit[n]uril (CBn) and cavitand hosts via noncovalent binding interactions, ii) investigate mediated electron transfer between fully encapsulated ferrocence centers and electrode surfaces, iii) continue binding property studies of CBn hosts within a range of inclusion complexes, and iv) begin new research on the use of nitroxide spin labels to probe the interior space of molecular capsules to better understand the complex factors controlling self-assembly. Since CBn hosts surpass cyclodextrins, a similar class of cyclical-shaped oligosaccharides, in binding affinity and selectivity, these studies will generate meaningful information to better understand supramolecular assembly and molecular recognition of a valuable class of molecules. Cucurbiturils are efficient host molecules in molecular recognition and may find applications as supramolecular catalysts, drug delivery vehicles, play a role in information storage devices, or other materials science applications. Professor Kaifer will continue to actively engage women and underrepresented minorities from high school to post-doctoral levels in his research program. In addition to the excellent research being carried out, Professor Kaifer emphasizes student training beyond the boundaries of the traditional disciplines of chemistry. All group members are required to develop synthetic expertise and must perform their own electrochemical and spectroscopic experiments to characterize the electron transfer reactions, host-guest binding interactions, self-assembly and/or aggregation processes in which their target compounds may engage. The PI?s group has always bestowed a friendly and nurturing atmosphere for the development and training of underrepresented minorities as researchers. Several research components of this application are specifically designed for undergraduate students, since their research work often suffers from schedule limitations that do not affect graduate students and postdoctoral associates. In terms of measurable outcomes in minority training, Professor Kaifer makes the commitment that the research participants in this project will include: (a) a minority/female undergraduate every year, (b) a minority/female high school student every year, and (b) at least a minority/female postdoctoral associate or graduate student during the grant cycle.

美国国家科学基金会化学部的有机和高分子化学项目支持安吉尔·E·史密斯教授。他将研究分子结构和电子转移反应之间的关系和相互作用。这一建议的目的是阐明有关的电子转移（ET）反应的基本问题，以及如何ET率的影响，在超分子系统中的主机。这是一个重大的持续努力，以前的工作，以更好地了解电子转移反应，发生在非共价包封的氧化还原中心。通过使用氧化还原活性客体和合适的主体，所得包合络合物是其中氧化还原中心部分或完全被主体空腔包封的结构。它可以被视为类似于生物主体-客体大分子系统。这些实验将试图了解定量和定性的变化，在封装的分子，如重组能量率和相关的热力学参数的反应。具体目标是i）研究二茂铁及其衍生物在各种葫芦[n]脲（CBN）和空穴主体中通过非共价结合相互作用，ii）研究完全包封的二茂铁中心和电极表面之间的介导的电子转移，iii）继续研究一系列包合络合物内CBN主体的结合性质，以及iv）开始关于使用氮氧自旋标记来探测分子胶囊的内部空间的新研究，以更好地理解控制自组装的复杂因素。由于CBN主机超过环糊精，一个类似的类环状低聚糖，在结合亲和力和选择性，这些研究将产生有意义的信息，以更好地了解超分子组装和分子识别的一类有价值的分子。葫芦脲是分子识别中的有效主体分子，并且可以用作超分子催化剂、药物递送载体、在信息存储装置中发挥作用或其他材料科学应用。教授凯弗将继续积极从事妇女和代表性不足的少数民族从高中到博士后水平在他的研究计划。除了正在进行的优秀研究外，Kaifer教授还强调超越传统化学学科界限的学生培训。所有小组成员都需要发展合成专业知识，必须进行自己的电化学和光谱实验，以表征电子转移反应，主客体结合相互作用，自组装和/或聚集过程中，他们的目标化合物可能参与。私家侦探？该小组一直为发展和培训代表性不足的少数民族研究人员提供友好和培育的氛围。本申请的几个研究部分是专门为本科生设计的，因为他们的研究工作往往受到时间表的限制，不影响研究生和博士后。就少数民族培训的可衡量成果而言，Kaifer教授承诺，该项目的研究参与者将包括：（a）每年一名少数民族/女本科生，（B）每年一名少数民族/女高中生，（B）在赠款周期内至少一名少数民族/女博士后助理或研究生。