Stimulus Responsive Oligopyrrole Macrocycles

在化学系的大分子、超分子和纳米化学项目的支持下，乔纳森·L。德克萨斯大学奥斯汀分校的Sessler及其同事将致力于开发新的超分子系统，其开关功能表现在电子结构，离子识别和自组装的变化方面。追求项目的具体目标将加强同事的培训，并提供一个技术娴熟的劳动力。得克萨斯大学奥斯汀分校自2020年以来一直是西班牙裔服务机构，这为Sessler集团提供了作为教育家和研究人员接触服务不足群体成员的机会;他将致力于为不同阶层提供教育机会，其中包括帮助当地的外展活动，并从一个学术机构教授关于超分子化学和知识产权的短期课程。perspective.超分子体系，特别是那些由低聚吡咯大环组成的体系，具有固有的手性，代表了一个未开发的前沿。本计画将探讨非平衡态下，手性对驱动手性堆叠系统自组装的影响。提出的吡咯基手性大环将测试其阴离子识别性能，阿利亚是使用手性磺酸和氨基酸作为推定的底物。努力将致力于探索手性的影响，包括“外”和“内”绑定，刺激诱导的环膨胀和收缩。为了补充这些研究，将制备具有3D和带状形态的非共轭手性寡吡咯笼和来自杯[3]吡咯系统的新手性受体。最后，将创建基于受体的集合，以发展超分子系统中的化学通讯概念，其中小分子信使用于将化学信息从一个离散的识别位点转移到另一个。 这些研究结果对超分子体系中分子识别和化学通讯的基本理解具有广泛的、长期的科学影响潜力。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。

With the support of the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Professor Jonathan L. Sessler of the University of Texas at Austin and coworkers will undertake to develop new supramolecular systems whose switching functions are manifest in terms of changes in electronic structure, ion recognition, and self-assembly. Pursuing the project-specific aims will enhance coworker training and provide a technically savvy workforce. The University of Texas at Austin ia a Hispanic-Serving Institution since 2020, and this affords the Sessler group the opportunity to reach out to members of underserved groups as an educator and researcher; he will devote considerable effort to providing educational opportunities across several different strata, which include helping with local outreach activities and teaching short courses on supramolecular chemistry and intellectual property from an academic perspective. Supramolecular systems, particularly those comprised of oligopyrrolic macrocycles, possessing inherent chirality represent an unexplored frontier. This project will investigate the influence of chirality on driving self-assembly of a chiral stacked system in an off-equilibrium fashion. The proposed pyrrole-based chiral macrocycles will be tested for their anion recognition properties using, inter alia, chiral sulfonic acids and amino acids as putative substrates. Efforts will be devoted to exploring the effect on chirality, including "outside" and "inside" binding, on stimulus-induced ring expansion and contraction. To complement these studies, non-conjugated chiral oligopyrrole cages bearing 3D- and belt-like morphologies and new chiral receptors derived from the calix[3]pyrrole systems will be prepared. Finally, receptor-based ensembles will be created to develop the concept of chemical communication in supramolecular systems wherein small molecule messengers are used to transfer chemical information from one discrete recognition site to another. There is significant potential for broad, long term scientific impact of the results of these studies upon the fundamental understanding of molecular recognition and chemical communication in supramolecular systems.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.