Short- and Long-Range Structural Complexity from Ortho-arylene Foldamers

邻亚芳基折叠体的短程和长程结构复杂性

• 批准号: 2304670
• 负责人: Christopher Hartley
• 金额: $ 48万
• 依托单位: Miami University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2304670&HistoricalAwards=false
• 关键词: Short; Long; Range; Structural; Complexity

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor C. Scott Hartley of Miami University will investigate methods by which the folding of non-biological molecules can be controlled. Biochemical systems make use of molecules that are both large and structurally complex. This combination is necessary for the remarkable sophistication, and thus function, of biochemical systems. Constructing comparable non-biological molecules is currently beyond the capabilities of synthetic chemistry. Nature’s strategy for generating structural complexity is by folding a long chain molecule into a specific shape. This research project aims to increase our understanding of the factors that govern the folding of long chain molecules. The ability to control molecular folding into complex 3D structures is important for advanced applications in molecular recognition and catalysis. The work will involve graduate students and undergraduates, who will be trained in synthetic and physical organic chemistry. Additional broader impacts include the development of a new teaching laboratory activity on attractive interactions relevant to molecular folding and work with a program from a consortium of Ohio universities supporting students from underrepresented backgrounds.This project aims to study the folding of a class of non-biological molecules called “foldamers” and to develop two strategies for controlling their folding into 3D structures. More specifically, this project will focus on studying ortho-arylene foldamers. ortho-Phenylenes are a simple class of aromatic foldamers that exhibit two very useful properties: their folded structures can be determined in solution with great precision using nuclear magnetic resonance (NMR) spectroscopy and computational chemistry, and their folding propensities are weak enough to be easily perturbed. These properties make them well suited to progressing from secondary to tertiary structure, a current challenge for foldamers research. In the first strategy, the folding of chains that mix attractive and repulsive interactions within a single molecule will be studied. By programming folding through the incorporation of pyrazine-2,3-diyl units into the sequence, complex structures will be obtained that are to be used to construct the coil segments necessary for tertiary structure. In the second strategy, cage structures incorporating multiple o-phenylene units will be investigated as simple examples of tertiary structure. Emphasis will be placed on understanding how the folding of the o-phenylenes responds to cage geometry and the inclusion of guest molecules. This research has the potential to provide access to and understanding of fundamentally new molecular folder systems to build complex non-biological structures with great potential for binding small molecule analytes and the potential for providing a new molecular scaffold for catalysis.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.

在化学系中的大分子，超分子和纳米化学计划的支持下，迈阿密大学的C. Scott Hartley教授将调查可以控制非生物分子的折叠的方法。生化系统利用既大又结构复杂的分子。这种组合对于生化系统的显着复杂而功能是必要的。目前，构建可比的非生物分子超出了合成化学的能力。大自然产生结构复杂性的策略是将长链分子折叠成特定形状。该研究项目旨在提高我们对控制长链分子折叠的因素的理解。控制分子折叠成复合3D结构的能力对于分子识别和催化中的高级应用很重要。这项工作将涉及研究生和本科生，他们将接受合成和物理有机化学的培训。其他广播公司的影响包括开发与分子折叠相关的有吸引力互动的新教学实验室活动，并与俄亥俄州大学联盟的计划合作，支持来自代表性不足的背景的学生。本项目旨在研究一类称为“ Foldamers”的非生物分子的折叠。控制其折叠成3D结构的策略。更具体地说，该项目将专注于研究正芳烃折叠剂。正苯基烯是一类简单的芳族折叠剂，存在两个非常有用的特性：可以使用核磁共振（NMR）光谱和计算化学性能在溶液中确定它们的折叠结构，并且它们的折叠特性足够弱，足以易于扰动。这些特性使它们非常适合从次级结构到第三级结构，这是当前对折叠剂研究的挑战。在第一个策略中，将研究在单个分子中混合有吸引力和排斥相互作用的链条的折叠。通过编程通过吡嗪-2,3-二二烯基的基础结构折叠成序列，将获得复杂的结构，该结构将用于构造第三纪结构所需的线圈段。第二个策略，将笼子结构纳入多个O-苯基单元，以作为第三级结构的简单例子进行研究。将重点放在理解O-苯基苯甲酸的折叠对笼几何形状和来宾分子的包含方面的反应。这项研究有可能提供并理解从根本上新的分子文件夹系统，以建立具有巨大潜力具有小分子分析物的复杂非生物结构，并提供了提供新的催化分子支架的潜力。该奖项反映了NSF的法规任务，并通过使用基础的知识效果评估来评估，这是NSF的法规任务。

项目成果

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