Barrel-Like Molecular Architecture from Folded Oligomers

本研究的重点是制备新型的分子结构作为催化支架的候选者。靶向低聚物(苯乙炔)S的基本设计包括将极性侧基连接到齐聚物的非极性碳氢化合物主链上。然后，从低聚物折叠回自身的构象中实现二级螺旋结构，使得芳环沿着螺旋轴面对面堆积。这种开发新催化剂的方法得益于通过序列修改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内在手性。建议的催化剂具有比蛋白质更坚固的前景，并有可能催化广泛的有机反应。α-手性酸的去消旋化就是一个例子。通过这个续展奖项，有机化学和高分子化学项目正在支持伊利诺伊大学化学系的杰弗里·S·摩尔博士的研究。摩尔教授将专注于低聚(苯乙炔)S的分子设计、合成和研究，这种低聚(苯乙炔)可以折叠成螺旋构象，从而产生管状空腔。这些疏水溶剂驱动的螺旋结构产生的形状让人想起酶中最常见的活性部位结构域，即α/β桶基序。因此，这项研究的长期目标是使用这种桶状脚手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.