Foldamer Heterosequences: A Modular Approach to Customizable Molecular Containers

本研究的重点是开发的方法，用于在一个模块化的方式来定制的空间内的分子隔室来自构象有序的低聚物的杂序列的使用。 将开发统计计算机辅助设计（SCAD）算法，以帮助合理设计这些隔间内的体积要求和凹面，以补充特定的客人，中间或过渡状态的兴趣。 将开发用于制备低聚亚苯基亚乙炔基（PE）杂序列的改进方法，并将探索新的构建单元，以使由折叠PE杂序列产生的隔室的大小、形状和内部官能化多样化。 将制备通过SCAD鉴定的优化序列，并测量对N，N '-二苯基哌嗪的结合亲和力，并与预测对该配体具有低亲和力的一组异构体对照序列进行比较。 在这些发展的基础上，提出了催化反应筛分的概念，作为一种手段，以实现基于尺寸的选择性活化反应底物。有了这个奖项，有机和高分子化学计划是支持博士的研究。伊利诺伊大学香槟分校化学系的摩尔和杰弗里G。宾夕法尼亚大学化学系的Saven说。 这项合作的努力将集中在方法的发展，为建设寡聚序列，将折叠成纳米级容器。 这种方法，在理论和实验的指导下，将允许在分子隔室内产生定制的空间，这反过来又会带来特定的分子识别，最终目的是控制化学反应性。 该项目具有理论和实验整合活动的更广泛的影响，从而为本科生，研究生和博士后学生的多学科培训提供了一个很好的环境。

The focus of this research is the development of methodology for the use of heterosequences in a modular way to customize the space inside molecular compartments derived from conformationally ordered oligomers. Statistical computer aided design (SCAD) algorithms will be developed to help rationally design both the volume requirements and concave surfaces inside these compartments complementary to a particular guest, intermediate or transition state of interest. Improved methods for the preparation of oligomeric phenylene ethynylene (PE) heterosequences will be developed and new building blocks will be explored in order to diversify the size, shape and internal functionalization of compartments created by folded PE heterosequences. Optimized sequences identified by SCAD will be prepared and binding affinity to N,N'-diphenylpiperazines will be measured and compared to a set of isomeric control sequences predicted to have low affinity for this ligand. Building on these developments, the concept of catalytic reactive sieving is proposed as a means to achieve size-based selective activation of reactive substrates. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Jeffrey S. Moore of the Department of Chemistry at the University of Illinois at Urbana-Champaign and Dr. Jeffrey G. Saven of the Department of Chemistry at the University of Pennsylvania. This collaborative effort will focus on the development of methodology for the construction oligomeric sequences that will fold into nanoscale containers. This approach, guided by theory and experiment, will allow the production of a customized space inside a molecular compartment and this, in turn will bring about specific molecular recognition for the eventual purpose of controlling chemical reactivity. The project has the broader impact of integrating activities in both theory and experimentation thus providing an excellent setting for the multidisciplinary training of undergraduate, graduate and postdoctoral students.