Dynamic control and self-assembly of ortho-phenylene foldamers

化学系的大分子、超分子和纳米化学项目获得这一奖项，资助迈阿密大学的C.Scott Hartley博士开发复制并最终补充自然产生的大分子非凡能力的分子。很长一段时间以来，合成化学家一直在努力制备与蛋白质和核酸相当的大小和复杂程度的分子。人体在任何地方都需要20秒到几分钟的时间来制造蛋白质。相比之下，如果有可能的话，将数百种氨基酸准备和组装成相同蛋白质的长链需要化学家几天到几个月的时间。此外，基于生化构建块设计新的结构复杂的系统是极其具有挑战性的。该项目通过利用更小和更容易制备的分子的组装来避免繁琐的合成路线。这一奖项的结果有望提供有关结构复杂分子之间的性质、动力学和相互作用的基本答案，这对开发具有类似生物大分子能力的人工系统具有重要意义。虽然目标化合物在化学上不一定等同于生物大分子，但它们在折叠和识别等相关过程中的行为相似。这项工作的更广泛的影响包括为有机化学入门课程开发实验室模块，本科生参与研究，以及参与俄亥俄州大学联盟，旨在支持STEM领域中代表性不足的少数族裔学生。这项工作集中于邻苯二烯折叠体的动态控制和自组装的研究。在开发这些折叠酶的过程中，生物大分子的能力，如分子识别、催化和反应行为(分子“机械”)，可能会被复制，通过简单和非繁琐的分子设计提供进入复杂过程的途径。为了实现这一目标，人们开展了一些研究，包括含氟邻苯类化合物的开发，具有可切换扭曲和远程构象通讯的动力学系统的控制，以及扭曲大环组装的结构-性质效应。氟核磁共振光谱的使用特别有趣，因为这项技术简单，但提供了一种有效的方法来阐明这些邻苯二烯体系的折叠行为。从概念上讲，这项工作有望在更广泛的领域、构象动力学和复杂结构合成的背景下提供基本的答案。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。

With this award, the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry is funding Dr. C. Scott Hartley from Miami University to develop molecules that replicate and ultimately complement the remarkable capabilities of naturally occurring macromolecules. For a very long time, synthetic chemists have struggled to prepare molecules of comparable size and complexity to proteins and nucleic acids. It takes the human body anywhere between 20 seconds to a couple of minutes to make a protein. In contrast, preparing and assembling hundreds of amino acids into a long chain of the same protein would take a chemist days to months, if it is even possible at all. Further, designing new structurally-complex systems based on biochemical building blocks is extremely challenging. This project avoids tedious synthetic paths by taking advantage of the assembly of smaller and more-easily prepared molecules. The results from this award are expected to provide fundamental answers about the nature, dynamics and interactions between structurally complex molecules, which are of relevance to developing artificial systems with similar capabilities to large biological molecules. While the target compounds are not necessarily chemically equivalent to biomacromolecules, their behavior in relevant processes such as folding and recognition is similar. The broader impacts of this work include the development of laboratory modules for introductory organic chemistry courses, undergraduate involvement in research, and participation in a consortium of Ohio universities aimed at supporting underrepresented minority students in the STEM fields.This work is focused on the investigation of the dynamic control and self-assembly of ortho-phenylene foldamers. In developing these foldamers, the capabilities of biomacromolecules, such as molecular recognition, catalysis, and responsive behavior (molecular "machinery"), can potentially be replicated, providing access to complex processes through simple and non-tedious molecular design. Several studies are carried out in order to achieve this goal, involving the development of fluorinated o-phenylenes, controlling dynamic systems with switchable twist and long-range conformational communication, and structure-property effects for the assembly of twisted macrocycles. The use of fluorine nuclear magnetic resonance spectroscopy is particularly interesting because this technique is simple and yet offers an impactful method for elucidating the folding behavior of these ortho-phenylene systems. Conceptually, this work is expected to provide fundamental answers in the context of the foldamer field, conformational dynamics, and the synthesis of complex structures.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.