Electrostatic Regulation of Cavity-Mediated Catalysis

空腔介导催化的静电调节

• 批准号: 1800354
• 负责人: Zhenqiang Wang
• 金额: $ 42万
• 依托单位: University of South Dakota Main Campus
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800354&HistoricalAwards=false
• 关键词: Electrostatic; Regulation; Cavity; Mediated; Catalysis

Catalysis is a process in which a small amount of a substance (a catalyst) accelerates the rate of desirable chemical reactions. Catalysis plays a vital role in many industrial applications. Manufacturing valuable products such as pharmaceuticals, plastics, agrochemicals, and clean fuels often requires properly designed catalysts. Traditional catalysts are highly effective in promoting a wide range of chemical reactions. However, it remains a daunting task to make catalysts that emulate the remarkable performance of enzymes, which are Nature's catalysts. The challenge arises largely from the difficulty of constructing molecules that resemble the complexity of enzymes. In this project, Dr. Zhenqiang Wang of the University of South Dakota is applying several biology-inspired principles to synthesize new classes of molecules that mimic enzymes. This research is integrated with educational outreach programs targeting Native American students to promote STEM (science, technology, engineering, and mathematics) education. These programs are engaging local tribal college students through tribal student-faculty research teams hosted in Dr. Wang's laboratory and through chemistry workshops at regional tribal colleges. The outreach also includes onsite hosting of students from local primarily undergraduate institutions (PUIs) and "at-home" support for student-faculty research teams at their home institutions.In this project funded by the Chemical Catalysis program of the Chemistry Division, the team led by Dr. Wang at the University of South Dakota is utilizing a unique class of synthetic receptors, known as metal-organic supercontainers (MOSCs), to investigate new concepts of catalysis. The MOSC-based supramolecular catalysts are structurally unique in that they are constructed from container-molecule precursors (i.e., sulfonylcalixarenes) and feature multiple nano-cavities that serve as substrate binding sites. The MOSC catalysts also feature functionally versatile metal-bound H2O species, which may promote hydrogen-bond, Bronsted-acid, Bronsted-base, and cascade catalysis. Two key strategies, namely, multifunctional nano-cavities and electrostatic regulation, are used to promote the catalytic efficacy, enhance reaction selectivity, and regulate supramolecular reactivity. The unique structural characteristics of the MOSCs, including their compositional versatility, structural modularity, and multi-pore architecture, distinguish them from other synthetic receptor molecules and provide unprecedented opportunities for functionalizing catalytic active sites and engineering supramolecular reactivity. The strategy to modulate supramolecular catalysis using ionic species as electrostatic regulators, which are catalytically inert on their own, is conceptually distinct from conventional methods that rely on encapsulating catalytically active species. The concept of electrostatic regulation is not yet fully recognized by chemists, but has the potential to not only significantly expand the scope of accessible reactions, but fundamentally transform how supramolecular catalysis can be designed.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.

催化是一个过程，其中少量的物质（催化剂）加速所需的化学反应的速率。催化剂在许多工业应用中起着至关重要的作用。制造有价值的产品，如药品，塑料，农用化学品和清洁燃料，通常需要适当设计的催化剂。传统的催化剂在促进广泛的化学反应方面非常有效。然而，制造催化剂来模仿酶的卓越性能仍然是一项艰巨的任务，酶是自然界的催化剂。挑战主要来自于构建类似于酶的复杂性的分子的困难。在这个项目中，南达科他州大学的王振强博士应用了几个受生物学启发的原理来合成新型的模拟酶的分子。这项研究与针对美国原住民学生的教育推广计划相结合，以促进STEM（科学，技术，工程和数学）教育。这些项目通过在王博士实验室举办的部落师生研究团队以及地区部落学院的化学研讨会吸引当地部落大学生的参与。在这个由化学系化学催化项目资助的项目中，南达科他州的王博士领导的团队正在利用一类独特的合成受体，称为金属有机超级容器（MOSC），来研究催化的新概念基于MOSC的超分子催化剂在结构上是独特的，因为它们由容器分子前体（即，磺酰基杯芳烃），并以用作底物结合位点的多个纳米空腔为特征。MOSC催化剂还具有功能多样的金属结合的H2O物质，其可以促进氢键、布朗斯台德酸、布朗斯台德碱和级联催化。两个关键的策略，即多功能纳米腔和静电调控，被用来提高催化效率，提高反应选择性，并调节超分子反应性。MOSC的独特结构特征，包括其组成的多功能性、结构模块性和多孔结构，将它们与其他合成受体分子区分开来，并为官能化催化活性位点和工程化超分子反应性提供了前所未有的机会。使用离子物质作为静电调节剂来调节超分子催化的策略在概念上不同于依赖于包封催化活性物质的常规方法，所述离子物质本身是催化惰性的。静电调节的概念尚未得到化学家的充分认可，但它不仅有可能显着扩大可及反应的范围，而且有可能从根本上改变超分子催化的设计方式。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

Precise Assembly and Supramolecular Catalysis of Tetragonal- and Trigonal-Elongated Octahedral Coordination Containers

四方和三方拉长八面体配位容器的精密组装和超分子催化

• DOI: 10.31635/ccschem.021.202100987
• 发表时间: 2022
• 期刊: CCS Chemistry
• 影响因子: 11.2
• 作者: Sheng, Tian-Pu;He, Can;Wang, Zhenqiang;Zheng, Guo-Zong;Dai, Feng-Rong;Chen, Zhong-Ning
• 通讯作者: Chen, Zhong-Ning