Barrel-Like Molecular Architecture from Folded Oligomers

本研究的重点是制备新的分子结构作为催化脚手架的候选物。目标低聚物（苯乙炔）s的基本设计包括将极性侧基团连接到低聚物的非极性烃主链上。二级螺旋结构然后从低聚物自身折叠的构象中实现，使得芳香环沿螺旋轴面对面堆叠。这种开发新催化剂的方法受益于通过序列修饰获得的巨大分子多样性，这些自发组织的管状室的完整三维定义以及螺旋的固有手性。所提出的催化剂有希望比蛋白质更强大，并有潜力催化广泛的有机反应。手性酸的去消酰基化就是一个例子。有了这个更新奖，有机和大分子化学项目支持了伊利诺伊大学化学系杰弗里·s·摩尔博士的研究。摩尔教授将把他的工作重点放在分子设计、合成和研究寡聚（苯乙烯-乙炔）上，寡聚（苯乙烯-乙炔）折叠成螺旋构象，从而形成管状腔。这些疏溶剂驱动的螺旋结构产生的形状让人联想到酶中最常见的活性位点域，即α / β -桶基元。因此，研究的长期目标是使用这种桶状支架作为催化剂发现的架构。

The focus of this research is the preparation of novel molecular architectures as candidates for catalytic scaffolding. The basic design of the targeted oligo(phenylene ethynylene)s involves attaching polar side groups to the oligomer's non-polar hydrocarbon backbone. Secondary helical structure is then realized from a conformation in which the oligomer folds back upon itself such that the aromatic rings stack face-to-face along the helix axis. This approach to the development of new catalysts benefits from the enormous molecular diversity available through sequence modification, the full three-dimensional definition of these spontaneously organized tubular compartments and the intrinsic chirality of the helix. The proposed catalysts hold the promise of being more robust that proteins and have the potential to catalyze a wide range of organic reactions. The deracemization of alpha-chiral acids is an example. With this renewal award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Jeffrey S. Moore of the Department of Chemistry at the University of Illinois. Professor Moore will focus his work on the molecular design, synthesis and study of oligo(phenylene ethynylene)s that fold into helical conformations, thereby creating tubular cavities. These solvophobically driven helical structures produce a shape that is reminiscent of the most common active site domain observed in enzymes, the alpha/beta-barrel motif. Thus, a long term goal of the research is to use this barrel-like scaffolding as an architecture for catalyst discovery.