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.

有了这个奖项，化学划分的大分子，超分子和纳米化学计划是为迈阿密大学的C. Scott Hartley博士提供资金，以开发复制并最终补充自然发生的大分子的显着能力的分子。 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似的大小和复杂性的分子。 人体需要20秒到几分钟的时间才能制造蛋白质。 相比之下，即使有可能的话，将数百种氨基酸制备成数百种氨基酸将需要几天到几个月的化学家。此外，设计基于生化构件的新结构复合系统非常具有挑战性。 该项目通过利用组装较小且较详细的分子来避免乏味的合成路径。预计该奖项的结果将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，这些分子与开发与大型生物分子相似能力的人工系统相关。 虽然靶化合物在化学上不一定等同于生物分子，但它们在相关过程（例如折叠和识别）中的行为相似。 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. 在开发这些折叠剂时，可以重复复制生物大分子的能力，例如分子识别，催化和响应式行为（分子“机械”），从而通过简单且非怪异的分子设计提供了对复杂过程的访问。 为了实现这一目标，进行了几项研究，涉及氟化的O-苯基烯，以可切换的扭曲和远距离构象交流来控制动态系统，以及用于组装扭曲的大环的结构质体效应。 氟核磁共振光谱的使用特别有趣，因为该技术很简单，但为阐明这些正苯基系统的折叠行为提供了有影响力的方法。 从概念上讲，这项工作有望在折叠剂领域，构象动态和复杂结构的合成的背景下提供基本答案。该奖项反映了NSF的法定任务，并认为值得通过基金会的知识分子的智力优点和更广泛的影响来通过评估来提供支持。

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

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

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