Electrostatic Regulation of Cavity-Mediated Catalysis

催化作用是一种少量物质（催化剂）加速理想化学反应速率的过程。催化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。传统催化剂在促进多种化学反应方面非常有效。然而，要制造出能够模仿酶的卓越性能的催化剂仍然是一项艰巨的任务，酶是大自然的催化剂。挑战主要来自于构建与酶的复杂性相似的分子的困难。在这个项目中，南达科他大学的王振强博士正在应用几种受生物学启发的原理来合成模拟酶的新型分子。这项研究与针对美国原住民学生的教育推广项目相结合，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的实验室主持的部落师生研究小组和在地区部落学院举办的化学研讨会，吸引了当地部落大学的学生。外展活动还包括接待当地主要本科院校（PUIs）的学生，以及为学生所在院校的师生研究团队提供“在家”支持。在这个由化学学部化学催化项目资助的项目中，南达科他州大学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（MOSCs），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，因为它们是由容器分子前体（即磺酰基杯芳烃）构成的，并且具有多个纳米空腔作为底物结合位点。MOSC催化剂还具有功能多样的金属结合H2O，可以促进氢键、bronsted酸、bronsted碱和级联催化。利用多功能纳米空腔和静电调节两种关键策略来提高催化效能、增强反应选择性和调节超分子反应活性。MOSCs独特的结构特征，包括其组成的多功能性、结构模块化和多孔结构，使其区别于其他合成受体分子，并为催化活性位点功能化和工程超分子反应性提供了前所未有的机会。使用离子作为静电调节剂来调节超分子催化的策略，其本身具有催化惰性，在概念上与依赖于封装催化活性物质的传统方法不同。静电调节的概念尚未得到化学家的充分认可，但它不仅有可能显著扩大可达反应的范围，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。

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.