Dynamic control and self-assembly of ortho-phenylene foldamers

邻亚苯基折叠体的动态控制与自组装

• 批准号: 1904236
• 负责人: Christopher Hartley
• 金额: $ 47万
• 依托单位: Miami University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904236&HistoricalAwards=false
• 关键词: Dynamic; control; self; assembly; ortho

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.

化学系的大分子、超分子和纳米化学项目将资助迈阿密大学的C. Scott Hartley博士开发能够复制并最终补充天然大分子的卓越能力的分子。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大小和复杂程度的分子。人体需要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，将数百个氨基酸组装成一条长链的同一种蛋白质将需要化学家花费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具挑战性的。该项目通过利用更小、更容易制备的分子的组装，避免了繁琐的合成路径。该奖项的结果有望为结构复杂分子之间的性质、动力学和相互作用提供基本答案，这与开发具有与大型生物分子相似能力的人工系统相关。虽然目标化合物不一定在化学上等同于生物大分子，但它们在折叠和识别等相关过程中的行为是相似的。这项工作的广泛影响包括开发有机化学入门课程的实验室模块，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民族学生。本文主要研究了邻苯折叠膜的动态控制和自组装。在开发这些文件夹的过程中，生物大分子的能力，如分子识别、催化和响应行为（分子“机器”），可以被潜在地复制，通过简单和不繁琐的分子设计提供了复杂过程的途径。为了实现这一目标，开展了几项研究，包括氟化邻苯乙烯的开发，具有可切换扭转和远程构象通信的控制动态系统，以及扭曲大环组装的结构-性能效应。氟核磁共振波谱的使用特别有趣，因为这种技术很简单，但却为阐明这些邻苯体系的折叠行为提供了一种有效的方法。从概念上讲，这项工作有望在折叠场，构象动力学和复杂结构综合的背景下提供基本的答案。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

Aromatic foldamers as molecular springs in network polymers

芳香族折叠分子作为网络聚合物中的分子弹簧

• DOI: 10.1039/d2cc01223e
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Miller, K. Andrew;Dodo, Obed J.;Devkota, Govinda Prasad;Kirinda, Viraj C.;Bradford, Kate G.;Sparks, Jessica L.;Hartley, C. Scott;Konkolewicz, Dominik
• 通讯作者: Konkolewicz, Dominik

PET‐RAFT Polymerization of Star Polymers with Folded ortho ‐Phenylene Cores

具有折叠邻位-亚苯基核的星形聚合物的 PET-RAFT 聚合

• DOI: 10.1002/marc.202300094
• 发表时间: 2023
• 期刊: Macromolecular Rapid Communications
• 影响因子: 4.6
• 作者: Bradford, Kate G. E.;Kirinda, Viraj C.;Gordon, Emma A.;Hartley, C. Scott;Konkolewicz, Dominik
• 通讯作者: Konkolewicz, Dominik

Fluorine Labeling of ortho -Phenylenes to Facilitate Conformational Analysis

邻亚苯基的氟标记促进构象分析

• DOI: 10.1021/acs.joc.1c01770
• 发表时间: 2021
• 期刊: The Journal of Organic Chemistry
• 作者: Kirinda, Viraj C.;Vemuri, Gopi Nath;Kress, Nicholas G.;Flynn, Kaitlyn M.;Kumarage, Nuwanthika Dilrukshi;Schrage, Briana R.;Tierney, David L.;Ziegler, Christopher J.;Hartley, C. Scott
• 通讯作者: Hartley, C. Scott

Observing the Transient Assembly and Disassembly of Carboxylic Anhydrides in the Organic Chemistry Laboratory

• DOI: 10.1021/acs.jchemed.3c00731
• 发表时间: 2023-12
• 期刊: Journal of Chemical Education
• 影响因子: 3
• 作者: Sumalatha Peddi;Jacob R. Franklin;C. S. Hartley