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教授试图更好地了解将分子放置在胶囊中的科学。更具体地说，这种“客体分子”的存储将被用来促进它们向新物质的化学转化。预计了解这些转化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。所描述的工作不仅将有助于培训下一代化学家，而且还将被纳入社区外联活动，以促进STEM(科学、技术、工程和数学)教育，并积极影响奥尔良教区和路易斯安那州南部的少数民族人口。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学之间的差距，促进超分子化学的最先进水平；(B)实现合成和探索利用水和疏水效应的新型试剂和催化剂，使反应能够在温和和对环境友好的条件下进行。具体来说，这项工作将涉及(1)一种新的芳环碘化工艺，以产生具有宽底物范围的温和催化过程；(2)研究新型的L(10^-24)胶囊，这种胶囊在低pH值下带负电荷，并将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--即整合到内空间壁上的官能团--从而更好地控制结合的客体。这三个子项目旨在帮助创建新的超分子主客复合体和有机催化的新平台。该奖项反映了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 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.