CAREER: Computational Studies of Aromaticity-Modulated Interactions in Supramolecular Chemistry

职业：超分子化学中芳香性调节相互作用的计算研究

• 批准号: 1751370
• 负责人: Judy I-Chia Wu
• 金额: $ 58.43万
• 依托单位: University of Houston
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-03-01 至 2023-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1751370&HistoricalAwards=false
• 关键词: CAREER; Computational; Studies; Aromaticity; Modulated

Hydrogen bonds are weak chemical interactions that, like the "glue" used to stick items together, can hold many molecules together to create elaborate chemical structures or to perform sophisticated functions. These interactions underlie many biological processes (e.g., DNA replication and enzyme catalysis) which, when artfully mimicked in man-made materials, can have important applications for biomedical, environmental, and renewable energy fields. However, factors that influence the strengths of hydrogen bonds (i.e., how "sticky" they are) in these complex systems remain largely convoluted, making "copying nature" in man-made materials difficult. In this project, Prof. Judy Wu and her students at the University of Houston are applying computational tools to study how hydrogen bonds work in concert in large complex organic molecules. Her research aims to establish new and useful ways of controlling hydrogen bonds, and to demonstrate their broader impacts for the discovery of advanced materials (e.g., gels, plastics, and electronics with novel properties). Integrated to this project are plans to develop a "Numbers to Insights" student workshop and web application to help facilitate the exchange of scientific ideas and findings across computational and experimental chemistry research groups. The proposed project aims to show that the marriage of two fundamental chemical concepts, aromaticity and hydrogen bonding, gives rise to surprising reciprocal effects with important consequences for supramolecular chemistry. Despite the recognition of hydrogen bonding and aromaticity as largely separate concepts in organic chemistry, research from the Wu group is showing that aromaticity can be used to control the strengths of intermolecular hydrogen bonding interactions through a phenomena called aromaticity-modulated hydrogen bonding (AMHB). Computational quantum chemical tools are applied to test the AMHB relationship at the 1) ground and 2) excited states of hydrogen-bonded molecular recognition units, 3) to investigate how AMHB influences the self-assembly modes of hydrogen-bonded molecular building blocks, and 4) to elucidate the role of AMHB in some examples of enzyme catalysis. At the core of this CAREER project is the vision to bridge discoveries of novel chemical relationships to their probable impacts in supramolecular chemistry.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.

氢键是一种弱的化学相互作用，就像用来粘东西的“胶水”一样，可以把许多分子粘在一起，形成复杂的化学结构或执行复杂的功能。这些相互作用是许多生物过程的基础（例如，DNA复制和酶催化），当巧妙地在人造材料中模拟时，可以在生物医学，环境和可再生能源领域具有重要应用。然而，在这些复杂的系统中，影响氢键强度的因素（即它们的“粘性”）在很大程度上仍然令人费解，这使得在人造材料中“复制自然”变得困难。在这个项目中，休斯顿大学的Judy Wu教授和她的学生正在应用计算工具来研究氢键如何在大型复杂有机分子中协同工作。她的研究旨在建立新的和有用的方法来控制氢键，并证明它们对发现先进材料（例如，凝胶，塑料和具有新特性的电子产品）的更广泛的影响。与该项目相结合的计划是开发一个“从数字到洞察”的学生研讨会和网络应用程序，以帮助促进计算和实验化学研究小组之间的科学思想和发现的交流。提议的项目旨在表明两个基本化学概念的结合，芳香性和氢键，产生了令人惊讶的相互作用，对超分子化学有重要影响。尽管在有机化学中，氢键和芳香性在很大程度上是两个独立的概念，但Wu小组的研究表明，芳香性可以通过一种称为芳香调节氢键（AMHB）的现象来控制分子间氢键相互作用的强度。应用计算量子化学工具测试了1)基态和2)氢键分子识别单元激发态下的AMHB关系，3)研究了AMHB如何影响氢键分子构建单元的自组装模式，4)阐明了AMHB在一些酶催化例子中的作用。这个CAREER项目的核心是将新化学关系的发现与它们在超分子化学中的可能影响联系起来。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。

项目成果

How does excited-state antiaromaticity affect the acidity strengths of photoacids?

激发态反芳香性如何影响光酸的酸性强度？

• DOI: 10.1039/d0cc02952a
• 发表时间: 2020
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Wen, Zhili;Karas, Lucas José;Wu, Chia-Hua;Wu, Judy I-Chia
• 通讯作者: Wu, Judy I-Chia

Self-assembling purine and pteridine quartets: how do π-conjugation patterns affect resonance-assisted hydrogen bonding?

自组装嘌呤和蝶啶四重体：α-共轭模式如何影响共振辅助氢键？

• DOI: 10.1039/c9ob02412c
• 发表时间: 2020
• 期刊: Organic & Biomolecular Chemistry
• 影响因子: 3.2
• 作者: Paudel, Hari Ram;Das, Ranjita;Wu, Chia-Hua;Wu, Judy I.
• 通讯作者: Wu, Judy I.

Hydrogen bond design principles

• DOI: 10.1002/wcms.1477
• 发表时间: 2020-05-16
• 期刊: WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
• 影响因子: 11.4
• 作者: Karas, Lucas J.;Wu, Chia-Hua;Wu, Judy I-Chia
• 通讯作者: Wu, Judy I-Chia

Baird’s rules at the tipping point

• DOI: 10.1038/s41557-022-00988-z
• 发表时间: 2022-07
• 期刊: Nature Chemistry
• 影响因子: 21.8
• 作者: L. Karas;J. Wu

Aromaticity gain increases the inherent association strengths of multipoint hydrogen-bonded arrays

芳香度增益增加了多点氢键阵列的固有缔合强度

• DOI: 10.1039/c8cc00422f
• 发表时间: 2018
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Wu, Chia-Hua;Zhang, Yu;van Rickley, Krista;Wu, Judy I.
• 通讯作者: Wu, Judy I.