New Anion Binders Based on Aromatic Linear and Cyclic Aromatic Oligoamides

在化学系大分子、超分子和纳米化学项目的支持下，布法罗纽约州立大学的龚兵教授将研究具有环状骨架的设计分子，即大环，以及它们如何与阴离子相互作用。这项研究旨在进一步了解大环设计如何进行微调，以建立阴离子特异性，并建立新的方法来结合特定的阴离子，特别是那些对能源和环境很重要的阴离子。该团队还将研究这些大环化合物如何通过不同的屏障（如细胞膜或非极性有机溶液）移动阴离子，这可能在许多不同的领域都很有用。该项目将分子设计与实验研究相结合，并为本科生和研究生提供研究培训机会，包括来自代表性不足群体的学生。研究结果将在科学界广泛宣传，并纳入本科生和研究生教学。本文所针对的大环化合物具有受约束的芳族低聚酰胺骨架，其强制多个酰胺NH和苯基CH基团的会聚放置。这些NH和CH基团定义了一个正电性结合腔，该结合腔是高度预组织的，用于结合阴离子。由于它们的氢键结合能力和对阴离子的偏好差异，大环化合物有望表现出对不同性质的阴离子的多功能结合能力。大环化合物将有助于跨细胞膜或本体非极性有机溶剂运输阴离子。阴离子转运的效率和选择性将使用已建立的荧光测定法进行评估，包括基于囊泡（脂质体）的荧光测定法或使用U形管的荧光测定法。该研究团队将（1）优化和扩大阴离子结合大环化合物的合成，（2）进行系统的阴离子结合研究，以量化大环化合物与不同阴离子在各种溶剂中的结合亲和力，以及（3）检查跨脂质双层或非极性有机溶剂的阴离子转运，以确定转运同源系列阴离子的效率和选择性，该奖项反映了NSF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 Bing Gong of the State University of New York at Buffalo will be studying designer molecules with cyclic scaffolds known as macrocycles and how they interact with anions. This research aims to further understanding of how macrocycle design can be finely tuned to build in anion specificity and to establish new ways to bind particular anions, especially for those that are important for energy and the environment. The team will also be looking at how these macrocycles can move anions through different barriers such as cell membranes or non-polar organic solutions, which could be useful in many different fields. This project will integrate molecular design with experimental studies and provide research training opportunities for undergraduate and graduate students, including students from underrepresented groups. The research results will be publicized broadly in the scientific community and incorporated into undergraduate and graduate teaching.The macrocycles being targeted herein have a constrained aromatic oligoamide backbone that enforces the convergent placement of multiple amide NH and phenyl CH groups. These NH and CH groups define an electropositive binding cavity that is highly pre-organized for binding anions. Because of their hydrogen-bonding capabilities and differences in preference for anions, the macrocycles are expected to exhibit versatile binding capabilities for anions with varying properties. The macrocycles will assist in transporting anions across cell membranes or bulk non-polar organic solvents. The efficiency and selectivity of anion transport will be assessed using established fluorescence assays including those based on vesicles (liposomes) or those using U-shaped tubes. This research team will (1) optimize and scale up the synthesis of the anion-binding macrocycles, (2) conduct systematic anion binding studies to quantify the binding affinities of the macrocycles with different anions in various solvents, and (3) examine anion transport across lipid bilayers or non-polar organic solvents to determine the efficiencies and selectivity of transporting homologous series anions, such as halides and oxoanions.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.