ortho-Phenylenes in Complex Foldamer Architectures

复杂Foldamer架构中的邻亚苯基

• 批准号: 1608213
• 负责人: Christopher Hartley
• 金额: $ 43.06万
• 依托单位: Miami University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1608213&HistoricalAwards=false
• 关键词: ortho; Phenylenes; Complex; Foldamer; Architectures

The Macromolecular, Supramolecular, and Nanochemistry Program of the Chemistry Division supports the work of Prof. C. Scott Hartley in the Department of Chemistry & Biochemistry at Miami University. In nature, the structural complexity of large molecules (e.g., proteins), and ultimately their function, is generated by the folding of smaller molecular pieces (oligomers and polymers). This fact has inspired many efforts to study non-biological "foldamers" smaller molecular pieces that fold in well-defined ways. Research in the Hartley group focuses on the ortho-phenylenes, a simple class of foldamers formed from directly connected aromatic rings. In this project, the Harley group develops methods to control the folding of o-phenylenes and incorporates the rings into more complex structures. The project involves graduate students, undergraduates, and high-school teachers working to understand fundamental concepts of molecular folding, self-assembly, and molecular recognition, using the techniques of organic synthesis, computational chemistry, and various characterization methods.The ortho-phenylenes combine several features that make them attractive as "next-generation" foldamers. They are straightforward to synthesize. Their folding behavior is easily modeled using simple, inexpensive methods. Their exact, solution-phase folding state can be characterized by NMR spectroscopy. This project has three specific aims that take advantage of these features. First, the twist-sense of o-phenylene folding is controlled using chiral end groups. While this sort of control over oligomer folding has been demonstrated in other systems, it is critical for more advanced uses of o-phenylenes. If successful, may be used to test o-phenylenes for spin-selective electron transport. Second, o-phenylene subunits are linked together into macrocycles. This simple system represents a first step toward incorporating o-phenylene secondary structures (i.e., helices) into higher-order structures, and provides a framework to test the conformational interaction between bridged foldamer subunits. Finally, o-phenylenes are functionalized with macrocycles to create binding sites along their sides. The architectures represents a first step toward o-phenylene-based molecular recognition.

化学部的大分子，超分子和纳米化学计划支持C. Scott Hartley教授在迈阿密大学化学与生物化学系的工作。在自然界中，大分子（例如蛋白质）及其功能的结构复杂性是通过较小分子碎片（低聚物和聚合物）的折叠而产生的。这一事实激发了许多研究以明确定义的方式折叠的非生物“折叠”较小分子零件的努力。 Hartley组的研究重点是邻苯甲烯，这是一类由直接连接的芳族环形成的简单折叠剂。在这个项目中，Harley组开发了控制O-苯基苯甲酸折叠的方法，并将环将环纳入更复杂的结构中。该项目涉及研究生，本科生和高中老师，他们使用有机合成，计算化学和各种表征方法的技术来理解分子折叠，自组装和分子识别的基本概念。等苯基苯甲酸杆菌结合了几种功能，使它们具有吸引力，使它们像“下一层”一样有吸引力。 它们直接合成。 他们的折叠行为很容易使用简单，廉价的方法建模。 它们的确切，溶液相折叠状态可以通过NMR光谱法来表征。该项目具有利用这些功能的三个特定目标。首先，使用手性末端组控制O-苯基折叠的扭曲宽度。尽管在其他系统中已经证明了对低聚物折叠的这种控制，但对于更先进的O-苯基烯词至关重要。 如果成功，则可以用于测试O-苯基烯烯的自旋选择性电子传输。其次，将O-苯基亚基链接到大环。这个简单的系统代表了将O-苯基二级结构（即螺旋）纳入高阶结构的第一步，并提供了一个框架来测试桥接的折叠式折叠子亚基之间的构象相互作用。最后，O-苯基烯烯与大环的功能化，以沿其侧面形成结合位点。这些体系结构代表了迈向基于O-苯基的分子识别的第一步。