Dynamic metallo-supramolecular oligomers stabilized by Cucurbit[8]uril connectors: self-assembly applied to combinatorial chemistry

Cucurbit[8]uril 连接器稳定的动态金属超分子低聚物：自组装应用于组合化学

• 批准号: 1507321
• 负责人: Eric Masson
• 金额: $ 43.5万
• 依托单位: Ohio University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-06-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1507321&HistoricalAwards=false
• 关键词: Dynamic; metallo; supramolecular; oligomers; stabilized

With the support of the Macromolecular, Supramolecular and Nanochemistry (MSN) program of the NSF Division of Chemistry, Prof. Masson investigates the recognition properties of water soluble metal-ligand complexes towards CB[n] and develops dynamic combinatorial approaches to preparing dynamic oligomers and polymers. Synthetic polymers are found in most objects used in everyday life. Polymers that spontaneously adjust their composition depending on their environment in water are of particular interest to Professor Eric Masson at Ohio University. His research group studies the formation and properties of a novel type of dynamic polymers in which the interchangeable building blocks are tied to one another with a pumpkin-shaped, hollow molecular ring called cucurbit[8]uril (CB[8]). The project has potential applications in biochemistry, as the dynamic polymers can interact with medically or biologically relevant materials such as proteins and cells, and in analytical chemistry, as the polymers can be used as sensors in quality control and drug detection applications. This project is multidisciplinary, and provides training to undergraduate and graduate students with a broad range of interests and talents, from organic synthesis, to biochemistry and statistical analysis. In addition, students are involved in the upgrade of an organic synthesis board game created by Professor Masson for computer tablets. The building blocks of the dynamic oligomers targeted herein are metal-terpyridine complexes linked to CB[8]-binding units. The terpyridine ligands bear phenyl or naphthyl groups at the 4'-position to promote binding in the CB[8] ring. The terpyridine ligands are also functionalized with bio-inspired side chains (based mostly on amino acid residues) at the 4- and 4"-positions for interactions with the outer wall of CB[8] and for target recognition. The metal-ligand complexes are connected non-covalently via binding to the CB[8] rings. The outer wall of CB[8] participates de facto in the target recognition process once the metal-ligand/CB[8] oligomers are formed. This project involves (1) the preparation of a library of metal-ligand complexes (such as iron(II)-, ruthenium(II)- and iridium(III)-terpyridine) with a variety of pendent groups; (2) the assessment of their recognition properties towards CB[n]s and the interactions between the pendent groups with the outer convex surface of CB[n]s; and (3) the preparation and characterization of the metal-ligand/CB[8] dynamic oligomers in the absence and presence of biologically relevant targets.

在NSF化学部的大分子，超分子和纳米化学（MSN）计划的支持下，Masson教授研究了水溶性金属配体络合物对CB[n]的识别特性，并开发了制备动态低聚物和聚合物的动态组合方法。合成聚合物存在于日常生活中使用的大多数物体中。俄亥俄州大学的埃里克·马森教授特别感兴趣的是，根据水中环境自发调整其组成的聚合物。他的研究小组研究了一种新型动态聚合物的形成和性质，其中可互换的构建块通过一种称为葫芦[8]脲（CB[8]）的南瓜形状的中空分子环相互连接。该项目在生物化学中具有潜在的应用，因为动态聚合物可以与医学或生物相关材料（如蛋白质和细胞）相互作用，并且在分析化学中，聚合物可以用作质量控制和药物检测应用中的传感器。该项目是多学科的，为本科生和研究生提供培训，从有机合成到生物化学和统计分析，具有广泛的兴趣和才能。此外，学生们还参与了Masson教授为平板电脑创建的有机合成棋盘游戏的升级。本文靶向的动态低聚物的结构单元是与CB[8]-结合单元连接的金属-三联吡啶络合物。 三联吡啶配体在4 '-位带有苯基或萘基以促进CB[8]环中的结合。 三联吡啶配体还在4-和4”-位置用生物启发侧链（主要基于氨基酸残基）官能化，用于与CB的外壁相互作用[8]和用于靶识别。 金属-配体络合物通过与CB[8]环结合而非共价连接。 一旦金属配体/CB[8]寡聚物形成，CB[8]的外壁事实上参与靶识别过程。 本计画包括（1）金属配位体配合物库的制备（2）评价了它们对CB[n]s的识别性能以及侧基与CB[n]s外凸表面的相互作用;以及（3）在不存在和存在生物学相关靶标的情况下金属配体/CB[8]动态寡聚物的制备和表征。