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

氢键是一种弱化学相互作用，就像用于将物品粘合在一起的“胶”一样，可以将许多分子结合在一起，以创建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(如DNA复制和酶催化)的基础，当这些过程被巧妙地模拟在人造材料中时，可以在生物医学、环境和可再生能源领域有重要的应用。然而，影响这些复杂系统中氢键强度(即它们有多“粘性”)的因素在很大程度上仍然错综复杂，使得在人造材料中“复制自然”变得困难。在这个项目中，休斯顿大学的朱迪·吴教授和她的学生正在应用计算工具来研究氢键如何在大的复杂有机分子中协同工作。她的研究旨在建立控制氢键的新的有用方法，并展示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)的更广泛影响。与该项目相结合的是计划开发一个“从数字到洞察”的学生讲习班和网络应用程序，以帮助促进计算化学和实验化学研究小组之间的科学思想和发现的交流。这项拟议的项目旨在表明，芳香性和氢键这两个基本化学概念的结合，会产生令人惊讶的相互作用，并对超分子化学产生重要影响。尽管在有机化学中氢键和芳香性在很大程度上是独立的概念，但吴小组的研究表明，芳香性可以通过一种称为芳香性调制氢键(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氢键分子识别单元的基态和激发态的AMHB关系，研究了AMHB如何影响氢键分子构筑块的自组装模式，以及4)阐明了AMHB在一些酶催化实例中的作用。这个职业项目的核心是将新的化学关系的发现与它们在超分子化学中可能产生的影响联系起来。这一奖项反映了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。

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.