Stimulus Responsive Oligopyrrole Macrocycles

在化学系大分子、超分子和纳米化学项目的支持下，德克萨斯大学奥斯汀分校的Jonathan L. Sessler教授及其同事将致力于开发新的超分子系统，其开关功能在电子结构、离子识别和自组装方面的变化是明显的。追求特定于项目的目标将加强同事培训，并提供精通技术的员工队伍。自2020年以来，德克萨斯大学奥斯汀分校成为了一个为西班牙裔服务的机构，这为Sessler团队提供了一个机会，让他们以教育者和研究员的身份接触到服务不足的群体的成员；他将致力于为不同阶层的学生提供教育机会，包括协助当地的外展活动，以及从学术角度教授超分子化学和知识产权方面的短期课程。具有固有手性的超分子体系，特别是由低聚吡啶大环组成的超分子体系，是一个尚未开发的前沿领域。本项目将研究手性对非平衡方式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特性，除其他外，使用手性磺酸和氨基酸作为假定的底物。将致力于探索手性，包括“外”和“内”结合，对刺激诱导的环扩张和收缩的影响。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低吡咯笼和从杯状[3]吡咯体系衍生的新的手性受体。最后，基于受体的集成将被创建，以发展超分子系统中化学通信的概念，其中小分子信使被用来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系统中分子识别和化学通讯的基本理解具有广泛、长期的科学影响。该奖项反映了美国国家科学基金会的法定使命，并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，被认为值得支持。

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.