CRC: Long-Range Electron Transfer in Hybrid Inorganic-Peptide Nucleic Acid Nanoscale Assemblies

大卫H.沃尔德克（匹兹堡大学）、卡塔利纳阿奇姆（卡内基梅隆大学）、大卫N. Beratan（杜克大学），Eric U. Borguet（坦普尔大学）和Marcela马德里（匹兹堡超级计算中心）共同支持研究肽核酸（PNA）为基础的结构中的电子转移过程。该团队将研究在明确定义的位置含有顺磁性过渡金属离子的PNA的性质。该团队将使用实验性的（即，光谱学、显微术和电化学）和理论（即，分子动力学模拟和量子化学）方法来研究这些纳米级组装体的电子传输性质作为总长度、金属离子的性质和PNA支架中金属中心之间的距离的函数。金属离子的其他性质，如配位和还原电位，也会影响电子转移，这些控制手段将被系统地探索。 电子转移是一种基本的化学过程，对自然过程（如光合作用中的能量转换）和合成系统（如晶体管）至关重要。这项工作可能对发展分子尺度的电子学和生物电子学，以及建立对这种未来发展具有根本重要性的概念产生影响。该项目通过化学合作研究计划（CRC）资助，为本科生，研究生和博士后学生提供了获得超分子化学，生物物理学和计算建模知识和技能的绝佳机会。研究小组还提供外展计划，以吸引当地学生对科学的兴趣。

David H. Waldeck (University of Pittsburgh), Catalina Achim (Carnegie Mellon University), David N. Beratan (Duke University), Eric U. Borguet (Temple University) and Marcela Madrid (Pittsburgh Supercomputing Center) are jointly supported to study the electron transfer processes in peptide nucleic acid (PNA)-based structures. The team will study the properties of PNAs that contain paramagnetic transition metal ions in well-defined locations. The team will use experimental (i.e., spectroscopy, microscopy and electrochemistry) and theoretical (i.e., molecular dynamics simulations and quantum chemistry) methods to study the electron transport properties of these nanoscale assemblies as a function of the overall length, the nature of the metal ion, and the distance between metal centers in the PNA scaffold. Other properties of the metal ion, such as coordination and reduction potential, can also affect the electron transfer and these means of control will be explored systematically. Electron transfer is a fundamental chemical process critical to natural processes, such as energy conversion in photosynthesis, and synthetic systems, such as transistors. This work has possible implications for developing molecular-scale electronics and bioelectronics, as well as for establishing the concepts that are of fundamental importance for future advances of this kind. This project is funded through the Collaborative Research in Chemistry Program (CRC) and provides outstanding opportunities for undergraduate, graduate and postdoctoral students to acquire knowledge and skills in supramolecular chemistry, biophysics and computational modeling. The team of researchers also offers outreach programs to interest local students in science.