Stimulus Responsive Oligopyrrole Macrocycles

在化学系大分子、超分子和纳米化学计划的支持下，德克萨斯大学奥斯汀分校的乔纳森·L·塞斯勒教授和他的同事们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显而易见的。追求特定项目的目标将加强同事培训，并提供一支精通技术的劳动力队伍。得克萨斯大学奥斯汀分校自2020年以来一直是一个为拉美裔服务的机构，这使塞斯勒小组有机会接触到服务不足群体的成员，成为一名教育工作者和研究人员；他将投入相当大的努力，提供跨越几个不同阶层的教育机会，包括从学术角度帮助当地的外联活动和教授关于超分子化学和知识产权的短期课程。具有固有手性的超分子体系，特别是由低聚吡咯大环组成的超分子体系是一个未被探索的前沿。本项目将研究手性对手性堆积体系非平衡驱动自组装的影响。建议的基于吡咯的手性大环将测试其阴离子识别性能，特别是使用手性磺酸和氨基酸作为假定底物。将致力于探索对手性的影响，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聚吡咯笼子和来自杯[3]吡咯体系的新的手性受体。最后，将创建基于受体的系综，以发展超分子系统中的化学通信概念，在超分子系统中，小分子信使被用于将化学信息从一个离散的识别位置转移到另一个位置。这些研究的结果对超分子系统中分子识别和化学通信的基本理解具有巨大的潜在的广泛的、长期的科学影响。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势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.