Supramolecular Design of Novel Reagents and Organo-Catalysts for Aqueous Solution

在化学系大分子、超分子和纳米化学项目的支持下，杜兰大学的Bruce C. Gibb教授试图更好地理解将分子放入胶囊的科学。更具体地说，这种“客体分子”的储存将用于促进它们向新物质的化学转化。预计了解这些转变将导致新的高效和环境友好的合成方法，从而有助于化工企业的进步。所描述的工作不仅有助于培养下一代化学家，而且还将整合到社区外展活动中，以促进STEM（科学、技术、工程和数学）教育，并对奥尔良教区和路易斯安那州南部的少数民族人口产生积极影响。这项工作有两个相互关联的目标：(a)通过帮助弥合该领域与合成方法之间的差距，为超分子化学的最新发展做出贡献；(b)实现利用水和疏水效应的新试剂和催化剂的合成和探索，使反应在温和和无害环境的条件下发生。具体来说，这项工作将涉及(1)一种新的芳香环碘化工艺，以创建一个广泛底物范围的温和催化过程；(2)研究新的yoctoliter （10^ - 24 L）胶囊，这种胶囊在低pH下带负电荷，可以促进或催化涉及阳离子中间体和过渡态的反应；(3)合成具有内官能团的新型超分子胶囊，这些官能团集成到内空间的壁上，可以更好地控制结合客体。这三个子项目旨在帮助创建新的超分子主客体复合物和有机催化的新平台。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 Bruce C. Gibb of Tulane University seeks to gain a better understanding of the science of placing molecules within capsules. More specifically, this storage of “guest molecules” will be used to facilitate their chemical transformation into new matter. It is anticipated that understanding these transformations will lead to new efficient and environmentally friendly synthetic methods, and so contribute to the advancement of the chemical enterprise. The described work will not only help train the next generation of chemists, but will also be integrated into community outreach activities to promote STEM (science, technology, engineering and mathematics) education and positively impact the minority population of Orleans Parish and Southern Louisiana.There are two interrelated aims to the work: (a) to contribute to the state-of-the-art of supramolecular chemistry by helping bridge the gap between the field and synthetic methodology, and (b) to achieve the synthesis and exploration of new reagents and catalysts that utilize water and the hydrophobic effect to enable reactions that occur under mild and environmentally benign conditions. Specifically, the work will involve (1) a novel iodination process for aromatic rings to create a mild catalytic process of broad substrate scope; (2) studies into new yoctoliter (10^–24 L) capsules that are negatively charged at low pH and will promote or catalyze reactions involving cationic intermediates and transition states, and (3) the synthesis of new supramolecular capsules possessing endo-functionality — functional groups that are integrated into the walls of the inner-space — that will lead to better control of the bound guest. These three sub-programs aim to help create new supramolecular host-guest complexes and new platforms for organocatalysis.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.