Metal-Linked Artificial Peptide Duplexes as Self-Assembled, Multifunctional Wires

作为自组装多功能导线的金属连接人工肽双链体

• 批准号: 0718373
• 负责人: Mary Williams
• 金额: $ 40.5万
• 依托单位: Pennsylvania State Univ University Park
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-07-01 至 2011-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0718373&HistoricalAwards=false
• 关键词: Metal; Linked; Artificial; Peptide; Duplexes

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Professor Mary Elizabeth Williams at the Pennsylvania State University to use metal coordination to self-assemble artificial peptide duplexes that operate as functional redox systems for studying multiple electron transfers. Structures with directly connected redox sites would allow multi-electron transfers between weakly coupled metal complexes predominantly by electron hopping, a regime that is largely unexplored in molecular assemblies. Functional architectures with di- and trimetallic model compounds will be built and studied as to how electrons move through them. Goals are to: 1) use metal coordination to self-assemble homometallic macromolecules; 2) extend this approach to make modular and heterofunctional structures; and, 3) measure electron transfers in di- and trimetallic functional redox systems. Initial work will be done with homometallic systems and move forward with simple heterofunctional structures. Facile modifications using available monomers and rational design (i.e. hairpin and self-aligning strands) will be used in constructing these assemblies. NMR and solution x-ray scattering will be applied to obtain structural analyses of the solution-phase homometallic and heterometallic species. Electrochemical methods and time resolved fluorescence spectroscopy will be used to test and understand the mechanisms and rates of electron transport in the multi-electron transfers of these self-assembled structures. Student and postdoctoral researchers will be broadly trained in molecular design and synthesis, use of a wide range of experimental methodologies, and electron and energy transfer theory. The complexity of this project requires that researchers working on these problems make connections to groups and experts within the department and across campus, and with researchers at Argonne National Labs. Students will be recruited through the Research Experience for Undergraduates and the Penn State Summer Research Opportunities Programs. Senior graduate students and postdoctoral researchers will serve as mentors and oversee the projects of younger group members, thereby gaining teaching and supervisory experience as part of their professional training.

无机，生物无机和有机化学计划的这一奖项支持宾夕法尼亚州立大学的玛丽伊丽莎白威廉姆斯教授使用金属配位自组装人工肽双链体，作为功能性氧化还原系统用于研究多电子转移。具有直接连接的氧化还原位点的结构将允许主要通过电子跳跃的弱耦合金属络合物之间的多电子转移，这是在分子组装中基本上未探索的一种方式。将建立和研究具有二金属和三金属模型化合物的功能结构，以了解电子如何通过它们。目标是：1）使用金属配位来自组装同质大分子; 2）将这种方法扩展到制造模块化和异质功能结构;以及3）测量二金属和三金属功能氧化还原系统中的电子转移。 最初的工作将与homophysical系统和简单的异功能结构向前推进。使用可用单体和合理设计（即发夹和自对准链）的简易修饰将用于构建这些组装体。NMR和溶液X-射线散射将被应用于获得溶液相的homometrium和heteromaticalspecies的结构分析。电化学方法和时间分辨荧光光谱将被用来测试和理解这些自组装结构的多电子转移中的电子传输机制和速率。学生和博士后研究人员将在分子设计和合成，使用广泛的实验方法，以及电子和能量转移理论方面进行广泛的培训。这个项目的复杂性要求研究这些问题的研究人员与系内和校园内的小组和专家以及阿贡国家实验室的研究人员建立联系。学生将通过本科生研究经验和宾夕法尼亚州立大学夏季研究机会计划招募。 高年级研究生和博士后研究人员将担任导师，监督年轻成员的项目，从而获得教学和监督经验，作为他们专业培训的一部分。