Functional Metal-Ligand Assemblies: Molecular Recognition and Biomimetic Catalysis

功能性金属配体组装：分子识别和仿生催化

• 批准号: 2002619
• 负责人: Richard Hooley
• 金额: $ 48万
• 依托单位: University of California-Riverside
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2002619&HistoricalAwards=false
• 关键词: Functional; Metal; Ligand; Assemblies; Molecular

Professor Richard J. Hooley of the University of California-Riverside is supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) and the Chemical Catalysis (CAT) Programs of the Division of Chemistry to develop self-assembly approaches to creating new chemical structures that act in a manner similar to enzymes and to explore the potential applications of these structures in catalysis. Large biomolecules such as enzymes (a type of protein) control many cellular processes, and chemists strive to mimic their behavior with artificial analogs, but these mimics cannot approach the complexity of natural enzymes. One approach to create large, complex molecules in a rapid manner is self-assembly, whereby individual pieces are reversibly arranged to make superstructures. This project aims to develop self-assembly approaches to create new chemical structures that act in a manner similar to enzymes and to explore the potential applications of these structures in catalysis. This project provides interdisciplinary research training to a diverse group of graduate and undergraduates students in areas that bridge chemistry, biology and materials science. In the course of conducting this project, research results are incorporated in the chemistry curriculum and new courses are developed with a focus on promoting diversity and increasing retention of students in STEM fields.Self-assembled cage complexes have a wide array of applications, but their use as biomimetic catalysts is constrained by the lack of activating groups in their “active site” cavities. This project seeks to remedy this by creating synthetic receptors via metal-ligand based self-assembly that display reactive functional groups to their cavity interiors. This project focuses on three specific areas: 1) creation and host:guest properties of new self-assembled cage complexes with internally oriented acidic, basic and/or ambiphilic groups; 2) application of these cages as enzyme-mimicking catalysts, focusing on novel reactivity patterns that are not accessible with small molecule catalysts such as unusual stereochemistry in oxocarbenium ion cyclizations, and sequential tandem catalysis; 3) creation of robust covalent cage catalysts via post-assembly reaction of the reversible cages and the study of their function in protease-mimicking reactivity. An important objective in this area is to ensure that the cage catalysts are stable to a variety of reaction conditions, and can be applied in multiple different environments, including aqueous solution.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.

加州大学河滨分校的Richard J. Hooley教授得到了化学系的大分子，超分子和纳米化学（MSN）和化学催化（CAT）计划的支持，以开发自组装方法来创建以类似于酶的方式起作用的新化学结构，并探索这些结构在催化中的潜在应用。大的生物分子如酶（一种蛋白质）控制着许多细胞过程，化学家们努力用人工类似物来模仿它们的行为，但这些模拟物无法接近天然酶的复杂性。快速制造大型复杂分子的一种方法是自组装，即将单个片段可逆地排列以形成超结构。该项目旨在开发自组装方法，以创建以类似于酶的方式起作用的新化学结构，并探索这些结构在催化中的潜在应用。该项目提供跨学科的研究培训，以研究生和本科生在桥梁化学，生物学和材料科学领域的不同群体。 在实施该项目的过程中，将研究成果纳入化学课程，并开发了新课程，重点是促进STEM领域的多样性和提高学生的保留率。自组装笼状复合物具有广泛的应用，但其作为仿生催化剂的应用受到其“活性位点”空腔中缺乏活化基团的限制。该项目旨在通过基于金属配体的自组装来创建合成受体，从而将反应性官能团展示到其腔体内部。该项目主要集中在三个方面：1）新型自组装笼状化合物的构建和主客体性质，这些笼状化合物具有内部定向的酸性、碱性和/或两亲性基团; 2）这些笼状化合物作为模拟酶催化剂的应用，重点关注小分子催化剂无法实现的新型反应模式，如氧碳正离子环化中的不寻常立体化学，以及顺序串联催化; 3）通过可逆笼的后组装反应产生稳定的共价笼催化剂，并研究它们在蛋白酶模拟反应中的功能。该领域的一个重要目标是确保笼型催化剂在各种反应条件下保持稳定，并可应用于多种不同的环境，包括水溶液。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。

项目成果

Modifying the internal substituents of self-assembled cages controls their molecular recognition and optical properties

修饰自组装笼的内部取代基可控制其分子识别和光学性质

• DOI: 10.1039/d2dt01451c
• 发表时间: 2022
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Woods, Connor Z.;Wu, Hoi-Ting;Ngai, Courtney;da Camara, Bryce;Julian, Ryan R.;Hooley, Richard J.
• 通讯作者: Hooley, Richard J.

Selective Anion Sensing in High Salt Water via a Remote Indicator Displacement Assay

通过远程指示剂位移测定选择性检测高盐水中的阴离子

• DOI: 10.1039/d3cc01974h
• 发表时间: 2023
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Hickey, Briana L;Raz, Alexie Andrea;Chen, Junyi;Moreno, Jose L.;Hartman, Joshua D;Zhong, Wenwan;Hooley, Richard James
• 通讯作者: Hooley, Richard James

Gated, Selective Anion Exchange in Functionalized Self‐Assembled Cage Complexes

功能化自组装笼状复合物中的门控选择性阴离子交换

• DOI: 10.1002/chem.202203588
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: da Camara, Bryce;Ziv, Noa Bar;Carta, Veronica;Mota Orozco, Gabriela A.;Wu, Hoi‐Ting;Julian, Ryan R.;Hooley, Richard J.
• 通讯作者: Hooley, Richard J.