Ghosh Totan, Fridman Natalia, Kosa Monica, Maayan Galia
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 3200008, Israel.
Angew Chem Int Ed Engl. 2018 Jun 25;57(26):7703-7708. doi: 10.1002/anie.201800583. Epub 2018 May 28.
Metal-ligand coordination is a key interaction in the self-assembly of both biopolymers and synthetic oligomers. Although the binding of metal ions to synthetic proteins and peptides is known to yield high-order structures, the self-assembly of peptidomimetic molecules upon metal binding is still challenging. Herein we explore the self-assembly of three peptoid trimers bearing a bipyridine ligand at their C-terminus, a benzyl group at their N-terminus, and a polar group (N-ethyl-R) in the middle position (R=OH, OCH , or NH ) upon Cu coordination. X-ray diffraction analysis revealed unique, highly symmetric, dinuclear cyclic structure or aqua-bridged dinuclear double-stranded peptoid helicates, formed by the self-assembly of two peptoid molecules with two Cu ions. Only the macrocycle with the highest number of intermolecular hydrogen bonds is stable in solution, while the other two disassemble to their corresponding monometallic complexes.
金属-配体配位是生物聚合物和合成低聚物自组装过程中的关键相互作用。尽管已知金属离子与合成蛋白质和肽的结合会产生高阶结构，但拟肽分子在金属结合时的自组装仍然具有挑战性。在此，我们探索了三种在其C端带有联吡啶配体、N端带有苄基且中间位置带有极性基团（N-乙基-R）（R = OH、OCH₃ 或 NH₂）的类肽三聚体在与铜配位时的自组装情况。X射线衍射分析揭示了由两个类肽分子与两个铜离子自组装形成的独特、高度对称的双核环状结构或水桥联双核双链类肽螺旋体。只有具有最多分子间氢键的大环在溶液中稳定，而其他两种则分解为相应的单金属配合物。
