Institute for Complex Molecular Systems, Laboratory of Macromolecular and Organic Chemistry, Laboratory of Chemical Biology, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
J Am Chem Soc. 2011 Apr 6;133(13):4742-5. doi: 10.1021/ja2004494. Epub 2011 Mar 15.
Enzymes are a source of inspiration for chemists attempting to create versatile synthetic catalysts. In order to arrive at a polymeric chain carrying catalytic units separated spatially, it is a prerequisite to fold these polymers in water into well-defined compartmentalized architectures thus creating a catalytic core. Herein, we report the synthesis, physical properties, and catalytic activity of a water-soluble segmented terpolymer in which a helical structure in the apolar core is created around a ruthenium-based catalyst. The supramolecular chirality of this catalytic system is the result of the self-assembly of benzene-1,3,5-tricarboxamide side chains, while the catalyst arises from the sequential ruthenium-catalyzed living radical polymerization of the different monomers followed by ligand exchange. The polymers exhibit a two-state folding process and show transfer hydrogenation in water.
酶是化学家试图创造多功能合成催化剂的灵感来源。为了得到空间上分离的带有催化单元的聚合链，必须将这些聚合物在水中折叠成具有明确分隔结构的聚合物，从而形成催化核心。在此，我们报告了一种水溶性分段三聚物的合成、物理性质和催化活性，其中在基于钌的催化剂周围形成了非极性核中的螺旋结构。该催化体系的超分子手性是苯-1,3,5-三羧酸酰胺侧链自组装的结果，而催化剂则来自不同单体的顺序钌催化活性自由基聚合，随后进行配体交换。聚合物表现出两态折叠过程，并在水中显示转移氢化。
